United States
Environmental Protection
Agency
Office of Research and
Development
Washington DC 20460
EPA/540/A5-89/012
September 1990
&EPA
Ultrox International
Ultraviolet
Radiation/Oxidation
Technology
Applications Analysis Report
SUPERFUND INNOVATIVE
TECHNOLOGY EVALUATION
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EPA/540/A5-89/012
September 1990
Ultrox International Ultraviolet
Radiation/Oxidation Technology
Applications Analysis Report
Risk Reduction Engineering Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
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Notice
The information in this document has been funded by the U.S. Environmental
Protection Agency under the auspices of the Superfund Innovative Technology
Evaluation (SITE) program (Contract No. 68-03-3484). It has been subjected to the
Agency's peer and administrative review and it has been approved for publication.
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 (SARA). The program is a
joint effort between EPA's Office of Research and .Development (ORD) and Office of
Solid Waste and Emergency Response (OSWER). The purpose of the program is to
assist the development of hazardous waste treatment technologies necessary to
implement new cleanup standards which require greater reliance on permanent
remedies. This is accomplished through technology demonstrations which are
designed to provide engineering and cost data on selected technologies.
This project is a field demonstration under the SITE Program and is designed to
analyze Ultrox International's ultraviolet radiation/oxidation technology. The
technology demonstration took place at a former drum recycling facility in San Jose,
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 that describes the field activities and laboratory
results; and (2) this Applications Analysis Report that provides an interpretation of
the data and discusses the potential applicability of the technology.
A limited number of copies of this report will be available at no charge from EPA's
Center for Environmental Research Information, 26 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. You can also call the SITE Clearinghouse
hotline at (800) 424-9346 or (202) 382-3000 in Washington, D.C., to inquire about the
availability of other reports.
E. Timothy Oppelt, Director
Risk Reduction Engineering Laboratory
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Abstract
In support of the U.S. Environmental Protection Agency's (EPA) Superfund
Innovative Technology Evaluation (SITE) Program, this report evaluates the Ultrox
International technology and its applicability as an on-site treatment method for
contaminated groundwater. The ULTROX® technology (a registered trademark of
Ultrox International) simultaneously uses ultraviolet (UV) radiation, ozone, and
hydrogen peroxide to oxidize dissolved organic contaminants (subject of a U.S. patent),
including chlorinated hydrocarbons and aromatic compounds, found in groundwater or
wastewater. This report evaluates both treatment efficiency and economic data from
the SITE demonstration and seven case studies.
Under the SITE Program, the ULTROX® technology demonstration was conducted at
the Lorentz Barrel and Drum (LB&D) site, San Jose, California, in February and
March of 1989. During this demonstration, the Ultrox system achieved volatile
organic compound (VOC) removals greater than 90 percent. The majority of VOCs
were removed through chemical oxidation. However, stripping also contributed
toward removal of a few VOCs, such as 1,1,1- trichloroethane (1,1,1-TCA) and 1,1-
dichloroethane (1,1-DCA). The treated groundwater met the applicable National
Pollutant Discharge Elimination System (NPDES) standards for discharge into a local
waterway. In addition, there were no harmful air emissions to the atmosphere from
the Ultrox system, which is equipped with an off-gas treatment unit.
The results from seven case studies are also summarized in this report. Six of the seven
case studies involved facilities that were primarily contaminated with VOCs and
polychlorinated biphenyls, in the ppm and ppb concentration ranges. The other case
study involved a wood treatment facility contaminated with phenol at 150 to 200 mg/L
and pentachlorophenol at 1 mg/L. In all the case studies, effluent from the Ultrox
system met the applicable discharge standards. Pretreatment was required for
influent that contained high levels of manganese, oil and grease, and suspended solids.
Potential sites for applying this technology to contaminated groundwater include
facilities with sources of petroleum, wood treatment facilities, and facilities with
sources of chlorinated or nonchlorinated solvents. Economic data indicate that the
capital costs for the reactor and ozone generator would range between $70,000 to
approximately $260,000. Operation and maintenance costs can be as low as $0.25 per
1,000 gallons treated, considering only oxidant and electrical costs, or exceed $17 per
1,000 gallons treated, if extensive pretreatment is required.
IV
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Contents
Page
Foreword iii
Abstract iv
Figures vii
Tables vii
Acknowledgments viii
1. Executive Summary 1
Introduction 1
Overview of the SITE Demonstration 1
Results from the SITE Demonstration 1
Results from the Case Studies 2
Waste Applicability 2
Economics 3
2. Introduction 5
Purpose, History, and Goals of the SITE Program 5
Documentation of the SITE Demonstration Results 5
Purpose of the Applications Analysis Report 6
Technology Description 6
3. Technology Applications Analysis , 9
Introduction 9
Technology Evaluation 9
Site Characteristics 13
Materials Handling Required by the Technology 14
Personnel Requirements 15
Potential Community Exposures 16
Regulatory Requirements 16
4. Economic Analysis 21
Introduction 21
Site-Specific Factors Affecting Cost 21
Basis of Economic Analysis 21
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Contents (Continued)
References 25
Appendices 27
A. Key Contacts for the SITE Demonstration 27
The Ultrox Technology 29
The SITE Program 29
The Demonstration Site 29
B. Vendor's Claims for the Technology 31
Introduction 34
Description of the ULTROX® Process 34
ULTROX® Equipment 35
Applications of the ULTROX® System 35
Selected Case Studies * 39
Cost Information 40
Summary 40
C. SITE Demonstration Results 43
Introduction , 46
Site Characteristics 46
Waste Characteristics 47
Review of Technology and Equipment Performance 48
Review of Treatment Results 51
References 53
D. Case Studies 55
Introduction 58
D-l Department of Energy, Kansas City Plant, Missouri 58
D-2 Hewlett Packard Facility, Palo Alto, California 60
D-3 FBI Microwave, Sunnyvale, California 63
D-4 Golf Course, City of South Gate, California 65
D-5 Xerox Facility, Webster, New York 66
D-6 Koppers Industries, Denver, Colorado 68
D-7 General Electric Company, Lanesboro, Massachusetts 69
References 69
VI
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Figures
Number
2-1
3-1
Isometric view of the Ultrox System
Dye tests showing effects of gas flow rates on the mixing
characteristics of a bubble diffuser ozone contact basin .
Page
. 7
12
Tables
2-1 Comparison of Technologies for Treating VOCs in Water ..
4-1 Estimated Costs Associated with Three Ultrox System Units
8
21
VII
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Acknowledgments
This report was prepared under the direction and coordination of Norma Lewis, U.S.
Environmental Protection Agency (EPA) Superfund Innovative Technology
Evaluation (SITE) Project Manager in the Risk Reduction Engineering Laboratory,
Cincinnati, Ohio. Mr. David Fletcher, Ultrox International, contributed greatly to this
report. Many other individuals provided information useful in summarizing the case
studies.
Dr. Gary Welshans, Dr. Kirankumar Topudurti, Barbara Sootkoos, and Sharon
Weinberg of PRC Environmental Management, Inc., prepared this report for EPA's
SITE Program under Contract No. 68-03-3484.
viu
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Section 1
Executive Summary
Introduction
The Ultrox International ultraviolet (UV)
radiation/oxidation technology (ULTROX®, a
registered trademark of Ultrox International) was
evaluated under the U. S. Environmental Protection
Agency's (EPA) Superfund Innovative Technology
Evaluation (SITE) Program. The Ultrox technology
demonstration was conducted at the Lorentz Barrel
and Drum (LB&D) site in San Jose, California,
during February and March of 1989. The Ultrox
treatment process (U.S. Patent No. 4,792,407) uses a
combination of UV radiation, ozone, and hydrogen
peroxide to oxidize organic compounds in water. The
developer claims that the final reaction products are
salts, water, carbon dioxide, and possibly some
organic acids.
The technology demonstration had the following four
objectives: ,
1. Evaluate the technology's ability to treat organic
contaminants in the groundwater at the site
2. Evaluate the effects of major process parameters
on the technology's performance
3. Evaluate the efficiency of the ozone decomposer
(Decompozon) unit in treating ozone in the off-gas
from the Ultrox reactor
4. Develop information useful for evaluating
whether this technology is suitable for other
hazardous waste sites with similar conditions
The purpose of this report is to provide information,
based on the results from the SITE demonstration
and other case studies, necessary for implementing
the Ultrox technology at Superfund and Resource
Conservation and Recovery Act (RCRA) hazardous
waste sites. Section 2 presents an overview of the
SITE Program and a description of the Ultrox
technology. Information relevant to the technology's
application, including pre- and post-treatment
requirements, operation and maintenance
requirements, potential community exposures, and
environmental regulations are presented in Section
3. Section 4 summarizes the costs associated with
implementing the technology. A list of contacts
familiar with the demonstration, the vendor's claims
regarding the technology's performance, a summary
of the SITE demonstration results; and seven case
studies are included in Appendices A through D,
respectively.
Overview of the Site Demonstration
The shallow groundwater at the LB&D site was
selected as the waste stream to be used for evaluating
the Ultrox treatment process. This groundwater was
primarily contaminated with volatile organic
compounds (VOC) such as trichlproethylene (TCE)
and vinyl chloride, at levels of 100 and 40 ug/L,
respectively. Other VOCs present at relatively low
concentrations (in the range of 5 to 15 ug/L) included
1,1-dichloroethane (1,1-DCA), 1,1,1- trichloroethane
(1,1,1-TCA), 1,2-dichloroethane (1,2-DCA), benzene,
chloroform, and tetrachloroethylene. Semivolatiles
and polychlorinated biphenyls (PCB)/pesticides were
not detected.
The total organic carbon (TOG) concentration of the
groundwater was approximately 25 mg/L. However,
the concentration of priority pollutants (VOCs and
semivolatiles) was only 2 percent of the TOG
concentration.
The pH and alkalinity of the groundwater were about
7.2 and 950 mg/L as CaCOs, respectively. These
measurements indicated that the bicarbonate ion
(HCOs"), which acts as an oxidant scavenger, was
present at high levels. Other oxidant scavengers such
as bromide, cyanide, and sulfide were not detected.
The experimental demonstration program evaluated
the performance of the Ultrox technology in
removing VOCs from the groundwater under various
operating conditions. During the demonstration
program, hydraulic retention times, oxidant doses
and ratios, UV radiation intensities, and influent pH
levels were varied for each test. The Ultrox system
was shut down at the end of each test and was not
started up until the next test.
Results from the Site Demonstration
The groundwater treated by the Ultrox system met
the applicable National Pollutant Discharge
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Elimination System (NPDES) standards for
discharge into a local waterway under certain
operating conditions. The Ultrox system achieved
removal efficiencies as high as 90 percent for the total
VOCs present in the groundwater. The removal
efficiencies for TCE were greater than 99 percent.
The maximum removal efficiencies for 1,1-DCA and
1,1,1-TCA under optimal operating conditions were
about 65 and 85 percent, respectively.
One set of operating conditions included a hydraulic
retention time of 40 minutes, ozone dose of 110 mg/L,
hydrogen peroxide dose of 13 mg/L, all 24 UV lamps
(at 65 watts each) operating, and influent pH of 7.2
(unadjusted). These "preferred" parameters were
selected for verification of subsequent runs during
the demonstration based on achieving acceptable
effluent at the lowest operating cost.
Within the treatment system, the removals of 1,1-
DCA and 1,1,1-TCA appear to be due to both
chemical oxidation and stripping. Specifically,
stripping accounted for 12 to 75 percent of the total
removals for 1,1,1-TCA, and for 5 to 44 percent of the
total removals for 1,1-DCA. However, stripping
accounted for less than 10 percent of the total
removals for TCE and vinyl chloride. For other VOCs
such as 1,1-dichloroethylene, 1,2-dichloroethylene,
benzene, acetone, and 1,1,2,2-tetrachloroethane,
stripping was negligible. Volatile organics present in
the gas phase within the reactor at levels of
approximately 0.1 to 0.5 ppm were removed to below
detection levels in the Decompozon unit.
The Decompozon unit destroyed ozone in the Ultrox
reactor off-gas to levels less than 0.1 ppm
(Occupational Safety and Health Act (OSHA)
standards). The ozone destruction efficiencies were
observed to be greater than 99.99 percent.
Based on the gas chromatography (GC) and GC and
mass spectrometry (MS) analyses performed for
VOCs, semivolatile organics, and PCBs/pesticides, no
new compounds were detected in the effluent. In
addition, very low TOG removal occurred. Since
VOCs made up less than 2 percent of the TOC,
complete conversion of VOCs to carbon dioxide and
water could not be verified.
The Ultrox system's average electrical energy
consumption was about 11 kilowatt-hours/hour of
operation.
Results from the Case Studies
Information on the Ultrox technology's performance
at seven facilities was evaluated to provide additional
performance data. These facilities were:
1. The Department of Energy, Kansas City,
Missouri
2. Hewlett Packard, Palo Alto, California
3. FBI Microwave, Sunnyvale, California
4. Golf Course, City of South Gate, California
5. Xerox, Webster, New York
6. General Electric Company, Lanesboro,
Massachusetts
7. Koppers Industries, Denver, Colorado
Groundwater treated by the Ultrox system at
Facilities 1 through 6 was generally contaminated
with several VOCs, including vinyl chloride, TCE,
benzene, toluene, xylene, tetrachloroethylene,
methylene chloride, 1,1-DCA, and 1,1,1-TCA, and
PCBs. The contaminant concentrations in the
influent were in both the ppb and ppm ranges. The
effluent from the Ultrox system was able to meet the
discharge standards in all cases, with treatment
efficiencies ranging from 90 to 99.99 percent in most
of the cases. The removal efficiencies for 1,1-DCA arid
1,1,1-TCA were less than 40 percent.
At Facility 7, wood treatment wastewater
contaminated with phenols, pentachlorophenols
(PCP), and oil and grease was treated by the Ultrox
system. Phenol was present at 150 to 200 mg/L, PCPs
at 1 mg/L, and oil and grease at 3 percent in the
influent. The effluent from the Ultrox unit met the
applicable discharge standards.
Pretreatment was required for cases where the
influent contained high levels of iron, manganese, oil
and grease, or suspended solids. Pretreatment
included precipitation of iron and manganese
followed by filtration, breaking of the oil-water
emulsion, and removal of suspended solids by
filtration.
Operational problems were encountered at Facility 1,
which resulted in frequent shutdowns of the Ultrox
system. Some operational problems included
frequent cleaning of UV lamps and ozone spargers,
and the ultimate replacement of ozone spargers.
These problems were due to the precipitation of iron
and manganese within the reactor. The facility also
reported the following additional operational
problems: (1) air compressor systems do not yield air
that is adequately dry; (2) ozone generator has a
highly variable ozone output; and (3) the unit suffers
from poor transfer of ozone from the gas to liquid
phase.
Waste Applicability
This technology can be applied to groundwater and
industrial wastewater contaminated with VOCs,
semivolatiles, and PCBs/pesticides. Potential sites
for applying this technology to contaminated
groundwater include facilities with sources of
petroleum, wood treatment facilities, semiconductor
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manufacturing facilities, and other facilities with
sources of chlorinated or nonchlorinated solvents.
Economics
An economic analysis was performed which
examined 12 separate cost categories for three
treatment flow rates (20, 100, and 250 gpm). This
analysis assumed that the system would operate in a
continuous mode (24 hours a day, 7 days a week) for
one year. The economic analysis was carried out for
one year to provide a reliable estimate of annual
operation and maintenance (O&M) costs. Annual
O&M costs were estimated to be $63,100, $135,100,
and $240,400 for the 20-, 100-, and 250-gpm units,
respectively. Capital costs for these reactors ranged
from $70,000 for the smallest unit to $260,000 for the
largest. O&M costs are presented in the appendices
for several operating or demonstration systems. The
costs from the case studies presented in Appendix D
ranged from approximately $0.25 per 1,000 gallons of
treated wastewater, considering only oxidant and
energy costs, to more than $17 per 1,000 gallons of
treated water, if the/influent required extensive
pretreatment.
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Section 2
Introduction
This section provides background information about
the SITE Program, discusses the purpose of this
Applications Analysis Report, and describes the
Ultrox technology. A list of key contacts is provided
in Appendix A for additional information.
Purpose, History, and Goals of the Site
Program
In response to the Superfund Amendments and
Reauthorization Act of 1986 (SARA), EPA's Office of
Research and Development (ORD) and Office of Solid
Waste and Emergency Response (OSWER)
established a formal program to accelerate the
development, demonstration, and use of new or
innovative technologies to clean up Superfund sites
across the country. A second program fosters the
further investigation and development of treatment
technologies that are still at the laboratory scale.
ORD has also established a program to demonstrate
and evaluate new, innovative measurement and
monitoring technologies. These three program areas
are components of 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. Major goals of the SITE Program are to:
• Identify and remove impediments to the
development and commercial use of alternative
technologies
• Demonstrate the more promising innovative
technologies in order to establish reliable
performance and cost information for site
characterization and cleanup decision making
• Develop procedures and policies that encourage
selection of available alternative treatment
remedies at Superfund sites
• Structure a development program that nurtures
emerging technologies
EPA recognizes that a number of forces inhibit the
expanded use of alternative technologies at
Superfund sites. One of the objectives of the program
is to identify these impediments and remove them or
design methods to promote the expanded use of
alternative technologies.
Another objective of the SITE Program is to
demonstrate and evaluate selected technologies. This
is a significant ongoing effort involving ORD,
OSWER, EPA Regions, and the private sector. The
demonstration program serves to test field-ready
technologies and provide Superfund decision makers
with the information necessary to evaluate the use of
these technologies for future cleanup actions.
Another aspect of the SITE Program includes
developing procedures and policies that match
available technologies with wastes, media, and sites
for actual remediation.
The SITE Program also provides assistance in
nurturing the development of emerging innovative
technologies from the laboratory- or bench-scale to
the full-scale stage.
Technologies chosen for a SITE demonstration must
be pilot- or full- scale applications, innovative, and
offer some advantage over existing technologies.
Mobile technologies are of particular interest. Each
selected round of demonstrations includes at least 10
technologies.
Documentation of the Site Demonstration
Results
The results of each SITE demonstration are
incorporated in two documents: the Technology
Evaluation Report and the Applications Analysis
Report. The Technology Evaluation Report provides a
comprehensive description of the demonstration and
its results. A likely audience for the Technology
Evaluation Report is engineers responsible for
performing a detailed evaluation of the technology
for a specific site and waste situation. These technical
evaluators seek to understand, in detail, the
performance of the technology during the
demonstration and the advantages, risks, and costs of
the technology for the given application. This
information is used to produce conceptual designs in
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sufficient detail to enable preliminary cost estimates
for the demonstrated technology.
The Applications Analysis Report is intended for
decision makers responsible for implementing
specific remedial actions. The basic use of the
Applications Analysis Report is to assist in
determining whether the specific technology should
be considered further as an option 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 the factors, such as site and waste
characteristics, that have a major impact on cost and
performance. If the candidate technology appears to
meet the needs of the site engineers, a more thorough
analysis will be conducted, based on the Technology
Evaluation Report and the Applications Analysis
Report and information from remedial investigations
for the specific site.
Purpose of the Applications Analysis
Report
To encourage the general use of demonstrated
technologies, EPA will provide information on the
applicability of each technology to certain sites and
wastes, other than those already tested, and will
study the costs of these applications. Available
information and data are presented through the
Applications Analysis Reports. These reports
attempt to synthesize available information on the
technology and draw reasonable conclusions as to its
broad range applicability. The Applications Analysis
Report is very useful to those considering the
technology for Superfund cleanups and represents a
critical step in the development and
commercialization of the treatment technology.
Each SITE demonstration will evaluate the
performance of a technology in treating a particular
waste found at the demonstration site. To obtain data
with broad applications, attempts will be made to
select waste frequently found at other Superfund
sites. In many cases, however, the waste at other sites
will differ in some way from the waste tested. Thus,
the successful demonstration of a technology at one
site does not ensure that it will work equally well at
other sites. Data obtained from the demonstration
may have to be extrapolated to estimate the total
operating range over which the technology performs
satisfactorily. This extrapolation should be based
upon both demonstration data and other information
available 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 at pilot- or full-scale treatment systems. In
addition, there are limits to conclusions regarding
Superfund applications that can be drawn from a
single field demonstration. A successful field
demonstration does not necessarily ensure that a
technology will be widely applicable or fully
developed to a commercial scale.
Technology Description
The Ultrox UV radiation/oxidation technology is
suitable for destroying dissolved organic
contaminants, including chlorinated hydrocarbons
and aromatic compounds, in water with low
suspended solids levels. This technology uses UV
radiation, ozone, and hydrogen peroxide to oxidize
organics. The Ultrox treatment system can be skid-
mounted for easy transport on either a flatbed truck
or in an enclosed trailer. The treatment system can
be used either as a stand-alone unit or in combination
with other treatment units.
Principal Treatment Operations
The major components of the Ultrox system are the
UV radiation/oxidation reactor module, the air
compressor/ozone generator module, the hydrogen
peroxide feed system, and the ozone decomposer
(Decompozon) unit. An isometric view of the Ultrox
system is shown in Figure 2-1.
The UV radiation/oxidation reactor used in the
demonstration (Model PM-150) has a volume of 150
gallons and is 3 feet long by 1.5 feet wide by 5.5 feet
high. The reactor is divided by five vertical baffles
into six chambers to create a serpentine flow through
the unit. The reactor contains 24 UV lamps (65 watts
each) in quartz sheaths. The UV lamps are installed
vertically and are evenly distributed throughout the
reactor (four lamps per chamber). Each chamber also
has one stainless steel sparger that extends along the
width of the reactor. These spargers uniformly
diffuse ozone gas from the base of the reactor into the
water. Hydrogen peroxide is introduced in the
influent to the reactor from a storage tank. An in-line
static mixer is used to disperse the hydrogen peroxide
into the contaminated water in the influent feed line.
Acids can be added to the influent in a fashion
similar to that of the hydrogen peroxide feed.
During the Ultrox system operation, contaminated
water first comes in contact with hydrogen peroxide
as it flows through the influent line to the reactor.
The water then comes in contact with the UV
radiation and ozone as it flows through the reactor at
a specified rate chosen to achieve the desired
hydraulic retention time. The hydroxyl radicals
(OH°) are formed from ozone and catalyzed by UV
radiation and hydrogen peroxide. The hydroxyl
radicals, in general, are known to react with organics
more rapidly than ozone, hydrogen peroxide, and UV
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Treated Off Gas
Reactor Off Gas
Catalytic Ozone Decomposer
Treated
Effluent
to Storage
Water Chiller
Ultrox
UV/Oxidation Reactor
Makeup
Water
Dryer
•Compressed Air
Ozone
Generator
Groundwater
from Wastewater
Feed Tank
Hydrogen Peroxide
from Feed Tank
Air
Compressor
Figure 2-1. Isometric view of the Ultrox System.
radiation. The hydroxyl radicals are also much less
selective in oxidation reactions than the three other
oxidants.
Ozone that does not go into solution with the
contaminated water will be present in the reactor off-
gas. This ozone is subsequently destroyed by the
Decompozon unit (which contains proprietary
catalysts and is operated at about 140°F) before being
vented to the atmosphere. The treated water flows
from the reactor for appropriate discharge.
The flow rates at which the Ultrox system can be
operated depend on the influent waste characteristics
and the hydraulic retention time required to achieve
the target effluent concentrations. At the
demonstration site with all 24 lamps operating, a
hydraulic retention time of 40 minutes, an ozone dose
of 110 mg/L, and a hydrogen peroxide dose of 13 mg/L
were determined to be adequate for the treatment of
contaminated groundwater. Since a 150-gallon
reactor was used during the demonstration, 3.75
gallons of groundwater were treated per minute (flow
rate). However, if higher flow rates are desired, the
volume of the reactor will have to be increased
proportionally. For example, assuming that the
groundwater characteristics and operating
conditions are the same as those used in the
demonstration, a flow rate of 130 gallons per minute
could be achieved using a larger Ultrox reactor (5,200
gallons). The actual treatment capacity at another
site will likely be different, however, depending on
the waste characteristics and the operating
conditions.
Innovative Features of the Technology
The use of oxidants such as ozone, hydrogen peroxide,
and UV radiation to destroy organic contaminants
present in groundwater is gaining considerable
attention. However, the oxidation of organics by
ozone, hydrogen peroxide, or UV radiation alone is
known to have kinetic limitations and, therefore, has
yet to become a competitive treatment option.
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Several studies indicated that the kinetic limitations
could be overcome by using two oxidants
simultaneously (Glaze and others, 1980; Glaze, 1987;
Weir and others, 1987; Aieta and others, 1988; and
Glaze and Kang, 1988). However, these studies did
not address the relative performance of various
oxidant combinations or the simultaneous use of
three oxidants.
The chemistry of the oxidation processes in which
two or three oxidants are used simultaneously is not
well understood. However, according to Ultrox
International, the simultaneous use of these three
oxidants has a definite advantage over the
simultaneous use of two oxidants on waters
containing compounds such as methylene chloride. In
general, processes in which ozone is used in
combination with hydrogen peroxide or UV radiation
may be categorized as catalytic ozonation processes.
These processes accelerate ozone decomposition,
thereby increasing the hydroxyl radical (OH°)
concentration and promoting the oxidation rate of
organics.
Oxidation treatment of volatile organics has
advantages over conventional wastewater treatment
methods, such as air stripping, steam stripping,
carbon adsorption, and biological treatment
processes. Although effective, these processes have
certain limitations. For example, stripping and
adsorption merely transfer the contaminants from
one medium (water) to another (air or carbon),
whereas biological treatment processes generate
sludge which requires further treatment and
disposal. In addition, biological treatment processes
have slow reaction rates. Table 2-1 compares several
treatment options for VOC-contaminated waters.
Similar comparisons can be made for semivolatiles,
PCB, and pesticides, although air stripping is not
generally applicable to these types of contaminants.
Table 2-1. Comparison of Technologies for Treating VOCs in Water
Technology Advantages
Disadvantages
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
spent carbon disposal or regeneration;
relatively expensive
Inefficient at high concentrations; slow rates
of removal; sludge treatment and disposal
required
High energy consumption; process
mechanisms not well understood
Air stripping
Steam stripping
Air stripping with carbon adsorption of vapors
Air stripping with carbon adsorption of vapors
and spent carbon regeneration
Carbon adsorption
Biological treatment
Effective at high concentrations; mechanically
simple; relatively inexpensive
Effective at all concentrations
Effective at high concentrations
Air Effective at high concentrations; no
carbon disposal costs; can reclaim the
product
Low air emissions; effective at high
concentrations
Low air emissions relatively inexpensive
UWozorte/hydrogen peroxide oxidation (Ultrox No air emissions; effective at all
International) concentrations; VOCs destroyed; readily
available
Note: Based on Garland II, 1989.
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Section 3
Technology Applications Analysis
Introduction
This section addresses the applicability of the Ultrox
UV radiation/oxidation technology to treat hazardous
wastes. Its applicability is based on the Ultrox SITE
demonstration and other Ultrox applications test
data. Since the results of the SITE demonstration
provided an extensive data base, evaluation of the
technology's effectiveness and its applicability to
other potential cleanup operations is mainly based on
these results, which are presented in detail in the
Technology Evaluation Report (EPA, 1989). The
developer's claims regarding the applicability and
performance of the Ultrox technology are included in
Appendix B.
Technology Evaluation
The objectives of the Ultrox technology
demonstration performed under the SITE Program
were to:
• Evaluate the ability of the Ultrox system to treat
VOCs present in the groundwater at the LB&D
site
• Evaluate the efficiency of the Decompozon unit in
treating ozone in the reactor off-gas
• Develop capital and operating costs for the Ultrox
system that can be used in Superfund decision-
making processes at other sites
• Develop information useful to EPA Region IX for
site remediation
With these objectives in mind, a total of 13 test runs
were performed to evaluate the effectiveness of the
technology. A summary of the SITE demonstration
results, including site characteristics, waste
characteristics, and a review of the Ultrox system's
performance, is presented in Appendix C.
The effectiveness of the Ultrox technology is
summarized below. The technology's effectiveness
based on the SITE demonstration is presented first,
followed by a discussion of the results from other case
studies. A fuller discussion of performance,
maintenance requirements, and costs at seven case
studies is presented in Appendix D.
Effectiveness of the Ultrox Technology
The SITE demonstration was conducted at a former
drum recycling facility in San Jose, California, over a
2-week period in February and March of 1989.
Approximately 13,000 gallons of groundwater
contaminated with several VOCs were treated by the
Ultrox system during the 13 test runs. During the
first 11 runs, 5 operating parameters were adjusted to
evaluate the system: hydraulic retention time, ozone
dose, hydrogen peroxide dose, UV radiation intensity,
and influent pH level. The last 2 runs were conducted
to verify the reproducibility of the system's
performance at Run 9's operating conditions, which
had been found to be successful at treating the
contaminated groundwater.
To complete the demonstration within a 2-week
period, the concentrations of indicator VOCs in the
treated and untreated groundwater were analyzed
overnight. Only 3 of the 44 VOCs identified in the
groundwater at the site were selected as indicator
VOCs for analysis to evaluate the performance of
each run. These performance indicator VOCs were
trichloroethylene (TCE); 1,1- dichloroethane (1,1-
DCA); and 1,1,1-trichloroethane (1,1,1-TCA). TCE
was selected because it is a major volatile
contaminant at the site, and the latter two VOCs
were selected because they are relatively difficult to
oxidize.
The pH and alkalinity of the groundwater were 7.2
and 950 mg/L as CaCOa, respectively. These
measurements indicated that bicarbonate ion
(HCOs), which acts as an oxidant scavenger, was
present at high levels. Other oxidant scavengers such
as bromide, cyanide, and sulfide were not detected.
Organic contaminants such as semivolatiles, PCBs,
and pesticides were also not detected.
Key findings of the SITE demonstration are
summarized as follows:
• Under certain operating conditions, the
groundwater treated by the Ultrox system met
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the applicable NPDES standards, at the 95
percent confidence level, for discharge into
Coyote Creek, a nearby waterway. The Ultrox
system achieved removal efficiencies as high as
90 percent for the total VOCs present in the
groundwater. The removal efficiencies for TCE
were greater than 99 percent. The maximum
removal efficiencies for 1,1-DCA and 1,1,1-TCA
under optimal operating conditions were about
65 and 85 percent, respectively.
• One set of operating conditions that met
discharge standards was selected as the
"preferred", or optimal, set of operating
conditions. These "preferred" parameters were
selected for verification of subsequent runs
during the demonstration based on achieving
acceptable effluent at the lowest operating costs.
These conditions included a hydraulic retention
time of 40 minutes, ozone dose of 110 mg/L,
hydrogen peroxide dose of 13 mg/L, all 24 UV
lamps (65 watts each) operating, and influent pH
at 7.2 (unadjusted).
• Within the treatment system, the removals of
1,1-DCA and 1,1,1-TCA appear to be due to both
chemical oxidation and stripping. Specifically,
stripping accounted for 12 to 75 percent of the
total removals for 1,1,1-TCA, and 5 to 44 percent
of the total removals for 1,1-DCA. However,
stripping accounted for less than 10 percent of the
total removals for TCE and vinyl chloride.
Stripping was negligible for other VOCs, such as
1,1-dichloroethylene, 1,2- dichloroethylene,
benzene, acetone, and 1,1,2,2-tetrachloroethane.
VOCs present in the gas phase within the reactor
at levels approximately 0.1 to 0.5 ppm were
removed to below detection levels in the
Decompozon unit.
• The Decompozon unit destroyed ozone in the
reactor off-gas to levels less than 0.1 ppm (OSHA
standards). The ozone destruction efficiencies
were observed to be greater than 99.99 percent.
There were no VOCs detected in the exhaust from
the Decompozon unit.
• Based on the gas chromatography (GO, and GC
and mass spectrometry (MS) analyses performed
for VOCs, semivolatile organics, and
PCBs/pesticides, no new compounds were
detected in the effluent. In addition, very low
TOC removal occurred. Since VOCs made up less
than 2 percent of the TOC, complete conversion of
VOCs to carbon dioxide and water could not be
verified.
• The Ultrox system's average electrical energy
consumption was about 11 kilowatt-hours per
hour of operation.
Several other studies on the performance of the
Ultrox system have been carried out. The results of
these case studies at seven facilities are summarized
in Appendix D. A brief summary of the effectiveness
of Ultrox technology at three of those facilities is
presented below.
The Environmental Sciences Division of the Oak
Ridge National Laboratory performed a study that
focused on the removal of VOCs from groundwater at
the Department of Energy Kansas City Plant
(Garland II, 1989). A 725-gallon unit is being used to
treat the contaminated groundwater at the site. In
addition to VOCs, the groundwater also had bacteria,
total suspended solids (TSS), iron, manganese, and
oil and grease at levels that would reduce the
effectiveness of the operation. Therefore, the
groundwater was filtered prior to treatment. The
data indicated that: the effluent from the Ultrox
system met the applicable discharge standards for
VOCs; nitrogen (as ammonia and nitrite) was
oxidized to nitrate; about 98 percent of bacterial
removal was achieved within the Ultrox system; but,
very little oil and grease was removed by the system.
Plugging of ozone spargers and coating of UV lamps
was observed over a 3-month operation, due to the
precipitation of iron and manganese within the
Ultrox system. This required shutting down the
Ultrox unit for a short time, which indicates that an
effective pretreatment unit is also important for the
proper functioning of the Ultrox system.
Ultrox International performed a study at the
Hewlett Packard facility in Palo Alto, California. A
150-gallon unit was used at this facility. This study
focused on the removal of toxic organic compounds
such as benzene, toluene, ethylbenzene, and xylene
present in groundwater at approximate levels of
4,400, 3,300, 175, and 3,100 ug/L, respectively. The
study demonstrated that the Ultrox system could
achieve removal levels of 98 to 99.9 percent and also
that the treated effluent could meet discharge
standards. No data were reported on operation and
maintenance problems.
A 650-gallon unit was used by Ultrox International
at FEI Microwave in Sunnyvale, California, to
remove TCE present in the groundwater at levels as
high as 6,000 ug/L. Removals as high as 99.99
percent were achieved at this facility.
In summary, Ultrox International's UV radiation/
oxidation technology has been demonstrated to be
effective in removing chlorinated and nonchlorinated
organics. Although the removal of certain compounds
which are difficult to oxidize occurs significantly due
to stripping, no harmful air emissions were observed.
This is because VOCs present in the reactor off-gas
were destroyed by the Decompozon unit before the
reactor off-gas was emitted to the atmosphere.
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Factors Influencing Performance
Several factors influence the performance of the
Ultrox UV radiation/oxidation technology. These
factors can be grouped into three categories: (1) waste
characteristics, (2) operating parameters, and (3)
maintenance requirements. Each of these is
discussed below.
Waste Characteristics
If, under a given set of operating conditions, the
influent contaminant levels are higher than the
contaminant levels for which the operating
conditions were established, the effluent levels will
also increase, which might result in noncompliance.
However, treatment efficiency can be increased by
modifying the operating conditions to accommodate
increased influent contaminant levels. These
conditions are discussed in this section under
Operating Parameters. If the influent contaminant
levels are anticipated to fluctuate, an equalization
tank should be provided prior to treatment in order to
minimize fluctuations. Based on the studies
performed, no maximum limit on the influent
contaminant levels can be specified. Also, under a
given set of operating conditions, the removal
efficiencies will depend upon the characteristics of
the contaminants. Key contaminant characteristics
are as follows:
• Organics with double bonds, such as TCE,
tetrachloroethylene (PCE), and vinyl chloride,
and aromatic compounds, such as phenol,
toluene, benzene, and xylene, are easily removed
because they are readily oxidized.
• Organics without double bonds and with high
Henry's law constants, such as 1,1-DCA and
1,1,1-TCA, are also removed. Removal of these
compounds is primarily due to stripping because
they are difficult to oxidize. (Henry's law
constants for 1,1-DCA and 1,1,1-TCA are 0.0043
atm-m3/mol, and 0.014 atm-m3/mol,
respectively.)
• Organics without double bonds and with low
Henry's law constants, such as diethylamine and
1,4-dioxane, would be difficult to remove because
they are not easily oxidized or stripped. (Henry's
law constants for diethylamine and 1,4-dioxane
are 0.00009 atm-m3/mol and 0.00001 atm-
m3/mol, respectively.)
Since the Ultrox technology is an oxidation process
and is intended for the destruction of organic
contaminants, any other species that consume
oxidants are considered an additional load for the
system. These species are called scavengers and
include anions such as bicarbonates, carbonates,
sulfides, nitrites, bromides, and cyanides. Also,
metals present in their reduced states, such as
trivalent chromium, ferrous iron, manganous ion,
and several others, are likely to be oxidized. These
reduced metals, in addition to acting as scavengers,
cause additional concerns. For example, trivalent
chromium, when oxidized, will be converted to
hexavalent chromium, which is more toxic. Ferrous
iron and manganous ion are converted to less soluble
forms, which precipitate in the reactor and can cause
UV lamp scaling and suspended solids formation.
Organics (TOC) which are likely to be oxidized could
act as potential scavengers in this treatment
technology. Other parameters such as TSS, oil, and
grease reduce UV transmission and thereby decrease
the treatment efficiency.
Operating Parameters
Operating parameters are those parameters which
are varied during the treatment process to achieve
desired treatment efficiencies. Such parameters
include hydraulic retention time, ozone dose,
hydrogen peroxide dose, UV lamp intensity, influent
pH level, and gas-to-liquid flow rate ratio.
In general, increasing the hydraulic retention time
will increase treatment efficiency up to a certain
point. At this point, the system tends to proceed
toward equilibrium and increasing the hydraulic
retention time no longer plays an important role.
The higher the oxidants' doses (ozone and hydrogen
peroxide), the better the treatment rate. However,
systems which use ozone and hydrogen peroxide
together are affected by the molar ratio of the
oxidants' doses used. For example, the expected
stoichiometry for hydroxyl radical (highly reactive
oxidant) formation from ozone and hydrogen peroxide
is two, as shown by the following equation:
H2O2 + 2O3 ±> 2OH° + 3O2
In the treatment of water containing TCE and PCE,
researchers observed maximum removals at a molar
ratio of 2 or a 2.86 weight ratio of ozone to hydrogen
peroxide, which agrees with the expected
stoichiometry (the removals were significantly less
when the molar ratio was not 2). Although, in this
case the expected stoichiometry for pure water agreed
with the molar ratio at which optimum removal was
observed, several factors may influence the molar
ratio (Aieta and others, 1988). These factors are
summarized below:
• Hydrogen peroxide can act as a free radical
scavenger itself, thereby decreasing the hydroxyl
radical concentration if it is present in excess.
• Ozone can react directly with hydroxyl radicals,
consuming both ozone and hydroxyl radicals.
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• Ozone and hydroxyl radicals may be consumed by
other constituents, known as scavengers, in the
water being treated (see Waste Characteristics).
The optimum proportion of the oxidants for
maximum removals cannot be predetermined.
Instead, the proportion needs to be determined for the
waste under consideration using pilot-scale or
treatability tests.
UV photolysis of ozone in water yields hydrogen
peroxide, which in turn reacts with ozone to form
hydroxyl radicals. In addition, UV radiation
photolyzes compounds such as PCE, aromatic
halides, and pesticides to increase their removal
(Glaze and others, 1987).
The pH of water to be treated has a significant effect
on the treatment efficiency. If water has significant
bicarbonate and carbonate alkalinity (>400 mg/L as
CaCOs), lowering the pH to a range of 4 to 6 should,
in general, improve the treatment efficiency. This is
because carbonate and bicarbonate ions act as
scavengers for the oxidants. The concentration of
these scavengers is decreased by shifting the
equilibrium toward carbonic acid at low pH values. If
the carbonate and bicarbonate alkalinity is low, then
a high pH, in general, should improve the treatment
efficiency. This is because, at a high pH, hydroxyl
radical formation is increased due to the reaction
between ozone and the hydroxyl ion.
The ozone gas flow rate can also significantly
influence the treatment efficiency. In practice, once
the ozone dose is selected, it can be applied at several
combinations of ozone gas phase concentration and
ozone gas flow rate. According to Venosa and
Opatken (1979), the ratio of gas flow rate to liquid
flow rate will dictate the hydraulic characteristics of
the reactor, as shown in Figure 3-1. This figure shows
that, at low gas-to-liquid flow rate ratios, the mixing
regime in a reactor is close to that of a plug flow
reactor (shown as Curve A), whereas at high ratios,
the reactor mixing regime is close to that of a mixed
reactor (shown as Curve C). It is advantageous to
operate the reactor with plug flow mixing
characteristics rather than with mixed reactor
mixing characteristics because a higher treatment
efficiency is achieved for reactions with a positive
reaction order (Levenspiel, 1972). Since most
reactions have a positive reaction order, low gas-to-
liquid flow rate ratios should be considered in actual
operation of the unit. In addition to increasing the
treatment efficiency, stripping of volatile organics
can be reduced by choosing low gas-to-liquid flow rate
ratios.
Ma/nfenance Requirements
The maintenance requirements for the Ultrox system
summarized here are based on a literature review
60
50
J40
030
s.
Q
9
20
cc
oGas Flow = 0 LVmin
a Gas Flow = 20 L/min
A Gas Flow = 80 L/min
Liquid Flow = 75 L/min
A - Plug Flow Reactor
B - Combination Flow Reactor
C - Mixed Flow Reactor
10
468
Time, Minutes
Source: Venosa and Opatken, 1979.
10
12
Figure 3-1. Dye tests showing effects of gas flow rates on
the mixing characteristics of a bubble diffuser
ozone contact basin.
(Cheremisinoff and others, 1981; WPCF, 1986;
Tucker, 1986; Robson, 1987). Regular maintenance
by trained personnel is essential for the successful
operation of the Ultrox system. The following
components require maintenance: (1) ozonation
system, (2) UV lamp assembly, (3) ozone decomposer
unit, and (4) miscellaneous components. A brief
summary of the maintenance requirements for each
of these components is presented below.
Ozonation System
The main components of the ozonation system are the
air preparation system, the ozone generator, and the
ozone contacting and associated equipment.
The air preparation system consists of process
equipment that includes an air filter, an air
compressor, an optional water chiller, and a desiccant
drier. Replacement cycles for the air filter are site-
specific, depending on air purity and flow. However,
inspection intervals for the filter should not exceed 3
months. Air compressors should be checked as
recommended by the manufacturer to minimize any
feed air contamination by the compressor
components.
A water chiller can be used to recirculate cooling
water required for the ozone generator. Tap water
(potable, suitable process water, or groundwater) can
also be used'.as a cooling water source. If a water
chiller is used, inspections of refrigerant dryers
should be carried out at 3-month maximum intervals
by personnel skilled in the operation and
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maintenance of refrigeration equipment. Minimum
checks should include compressor belt tension and
refrigerant pressure measurement. The water lines
require annual inspection for scaling or deterioration
resulting from the passage of the cooling water
through the heat exchanger.
Desiccant dryers should be inspected weekly to
ensure proper operation of the unit. Maintenance of
the dryers is important to keep the unit in operation
and to prevent damage to the unit by fires, which can
occur if a desiccant tower runs for a prolonged period
in the regeneration mode. Ultrox uses heatless
adsorption dryers in most air systems. These heatless
adsorption dryers are reliable and do not cause fires.
Annual maintenance should include disassembly of
the unit and inspection of the desiccant. The media
normally lasts approximately 10 years, but may have
to be replaced sooner if the dryer has been overloaded
or poorly maintained.
The ozone generator is typically an unfamiliar unit to
maintenance personnel and may justify, at least
initially, having a maintenance contract with the
generator supplier for emergency assistance and
annual service. Specific personnel should be assigned
to generator maintenance to enable them to gain
sufficient familiarity and skills to perform tasks such
as fuse replacement and dielectric tube cleaning,
which will result in lower energy costs for a given
ozone output. Dielectric tube cleaning necessitates
manpower and inevitable breakage or damage to the
tubes during the cleaning process. Therefore, it is
necessary to carefully evaluate the frequency of
cleaning. It is recommended that the first cleaning
period of the dielectric tubes not exceed 12 months
after unit start-up. Depending on the condition of the
tubes at that time, the next period of cleaning can be
projected.
Inspection of the ozone contacting equipment should
address the functional as well as the structural
integrity of the components of the contactor. Pipings,
valves, fittings, supports, brackets, and spargers
should be checked at least once every 3 months for
the deterioration which results from exposure to a
highly oxidizing environment. Deteriorated material
should be replaced. Good records, including
photographs, of the conditions observed during the
inspection should be maintained. The gas spargers
should be checked for plugging due to solids
accumulation once changes in the gas bubble
diffusion pattern are noted. The spargers must be
immediately cleaned to minimize cracking of joints
and excessive power costs.
The instrumentation and controls of the ozonation
system must be maintained regularly. Flow meters,
temperature and pressure sensors, and ozone
analyzers must be kept in working order to enable
the operator to measure various parameters required
for efficient operation.
UV Lamp Assembly
The maintenance of the UV lamp assembly requires
periodic cleaning and eventual replacement of the
lamps. The frequency at which the lamps should be
cleaned depends on the type and concentration of
suspended solids present in the influent or formed
during treatment. The frequency may range from
once every month to once every 3 months. Several
cleaning procedures include the use of chemicals,
mechanical wipers, or ultrasonics.
The life of low-pressure UV lamps normally cited by
most manufacturers is 7,500' hours, based on a use
cycle of 8 hours. A number of factors combine to
effectively age the lamps, which limits their useful
life and requires their replacement. These factors
include failure of the electrodes, plating of the
mercury to the interior lamp walls (blackening), and
solarization of the lamp enclosure material (reducing
its transmissibility). These all cause steady
deterioration in the lamp's output at the effective
wavelength (253.7 um), such that its output at the
end of the lamp's life can be only 40 to 60 percent of
its normal output. This reduction in the output may
require more frequent replacement of the UV lamps
Ozone Decomposer (Decompozon) Unit
The Decompozon unit, including enclosure catalyst
and heating elements, should be inspected
thoroughly to ensure efficient operation. Replacing
the catalyst is a considerable expenditure that can be
deferred by following the manufacturer's
maintenance program.
Miscellaneous Components
Other components of the system, such as valves, flow
meters, pipelines, hydrogen peroxide feed tank, and
acid feed tank should be checked for leaks once a
month. In addition, the influent, hydrogen peroxide,
and acid feed pumps should be checked once a month
for proper operation and maintenance.
Site Characteristics
Site characteristics, in addition to influent
characteristics and effluent discharge requirements,
are important issues when considering using the
Ultrox technology. Site-specific factors have both
positive and negative impacts on the implementation
of the Ultrox technology and should be considered
before selecting this technology. These factors
include site preparation, site access, hydrogeology,
climate, utilities, and services and supplies.
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Site Preparation
Ultrox systems are available in several volumetric
sizes ranging in capacity from 60 to 5,200 gallons.
During the SITE demonstration, a 150-gallon unit
was used. A 20- by 20-foot area was adequate for the
Ultrox system and associated equipment. Larger
units would require slightly larger areas. For
example, for the 5,200-gallon unit, an area about 30
by 50 feet should be provided. Areas required for
influent and effluent storage tanks, if needed, may
vary depending on the flow rate, effluent
requirements, and turn-around time for any effluent
analysis required prior to its disposal.
The area containing the Ultrox unit and tanks should
be relatively level. It can be paved or covered with
compacted soil or gravel. A tent or some type of
shelter is needed for the Ultrox system to protect it
from inclement weather.
A 20- by 20-foot area is required for indoor office
space and any on- site laboratory work.
Site Access
Site access requirements for the 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
Ultrox unit and tanks.
Hydrogeoiogy
At sites that require remediation of contaminated
groundwater, extraction wells will be needed to
collect the contaminated groundwater. Since the
Ultrox system would be operated as a flow-through
system on a continuous basis during site
remediation, installation of several extraction wells
may be required to provide a continuous supply of
groundwater. When installing a groundwater
collection and storage system, preventative measures
should be considered that would reduce volatile
contaminant losses.
Climate
Below-freezing temperatures and heavy precipitation
could have an impact on the operation of the Ultrox
system. If below-freezing temperatures are expected
for a long period of time, the Ultrox system and
influent storage tanks should be insulated or kept in
a well-heated shelter, such as a building or shed. The
Ultrox unit, and particularly the ozone generator
which requires a high-voltage power supply, should
also be protected from heavy precipitation.
Utilities
The Ultrox system requires tap water and electricity.
Tap water is required for equipment cleanup and
personnel decontamination. In some cases, the Ultrox
system uses tap water as a source of cooling water for
its ozone generator.
A 480-volt, 3-phase electrical service is required for
the efficient operation of the Ultrox system. An
additional 110-volt power line will also be required
for other on-site uses.
A telephone connection is required to contact
emergency services and to provide normal
communications.
Services and Supplies
A number of services and supplies are required for
the Ultrox technology. Most of these services and
supplies can be readily obtained.
Tanks will likely be required for influent and effluent
storage. Extensive piping connections will be
required to assemble the groundwater collection
system.
In case any pumps or UV lamps malfunction, or any
flow meters, gas spargers, or lines crack, an adequate
on-site supply of spare parts or access to a nearby
industrial supply center is an important
consideration.
Chemicals such as hydrogen peroxide and sulfuric
acid are used in this process. An adequate supply or
proximity to a supply center carrying these chemicals
is essential.
Since the Ultrox technology is designed to treat
organics, including volatiles, semivolatiles, and
PCBs/pesticides, entering into a contract with a local
analytical laboratory would be prudent for an
ongoing monitoring program.
Materials Handling Required by the
Technology
Materials handling for the Ultrox Technology can be
divided into the pretreatment processing of the
influent before it enters the reactor unit and the
residuals handling of the air and liquid waste
streams as well as miscellaneous wastes generated
during the operation.
Pretreatment Processing
In general, the pretreatment requirements for this
technology are minimal. Depending on the waste
characteristics, pretreatment processing involves one
or more of the following: oil and grease removal,
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suspended solids removal, or pH adjustment to reduce
carbonate and bicarbonate levels.
Wastes containing emulsified oil and grease require
pretreatment to break down and remove emulsions. If
not treated, the emulsified oil and grease will coat the
UV lamps and reduce the UV transmission in the
Ultrox system, thereby making the process less
effective.
Pretreatment of wastes containing suspended solids
at levels greater than 30 mg/L may need to be
considered, as the suspended solids would also reduce
the UV transmission. In addition, pretreatment may
be necessary for wastes containing dissolved metals,
such as iron and manganese, which have lower
solubilities at higher oxidation states. The removal of
such metals is required because they will be oxidized
and precipitated in the Ultrox system, resulting in
the formation of suspended solids and, also, scaling of
the UV lamps.
pH adjustments may need to be considered for wastes
having bicarbonate and carbonate ions at levels
greater than 400 mg/L as CaCOa. These ions act as
oxidant scavengers and cause additional load to the
treatment system. If required, pH adjustments can be
performed in-line.
Even if no pretreatment is needed, the aqueous
organic wastes may still need to be pumped to an
equalization tank (such as bladder tanks to minimize
VOC losses) to reduce flow and concentration
fluctuations. If so, plumbing connections will be
needed.
Residuals Handling
Two major types of residuals are generated from the
Ultrox treatment system: (1) air emissions and (2)
treated effluent. The Ultrox system did not generate
any harmful air emissions during the demonstration.
The ozone decomposer unit in the Ultrox system
removed the ozone and VOCs present in the reactor
off-gas to environmentally safe levels. Therefore, no
special residual handling procedures were required
for the air emissions at the demonstration site.
However, periodic monitoring of air emissions for
ozone and VOCs is recommended.
Air emissions are treated by the Decompozon unit
(Model 3014 FF), which uses a nickel-based
proprietary catalyst and operates at about 140°F to
decompose reactor off-gas ozone to oxygen. The
Decompozon unit can accommodate flows of up to 10
standard cubic feet per minute and can destroy ozone
concentrations in ranges of 1 to 20,000 ppm (by
weight) to less than 0.1 ppm.
The treated water could be disposed of either on- or
off-site. Examples of on-site disposal options for the
effluent include groundwater recharge and
temporary storage on-site for sanitary usage.
Examples of off-site disposal options are discharge
into rivers, creeks, storm sewers, and sanitary
sewers. Bioassay tests may be required in addition to
routine chemical and physical analyses before the
effluent is disposed of. During the demonstration, the
treated water was stored in a 20,000-gallon metal
tank until laboratory analyses indicated that the
water met NPDES standards. Subsequently, the
effluent was discharged into Coyote Creek, a nearby
waterway.
In addition to these principal residuals, the operation
of the Ultrox system also requires the handling and
replacement of miscellaneous items related to the
operation. These items include UV lamps, spargers,
and filters which may be required to treat the
influent. To avoid excessive analytical costs to
determine whether or not these items are
nonhazardous, disposal of these items as hazardous
wastes seems warranted.
Personnel Requirements
Personnel trained to operate the Ultrox system are
needed to ensure a reliable operation. Operating
personnel requirements depend on the size of the
Ultrox system purchased, as well as the features
included on the unit. For example, the Ultrox system
(Model F-4000), which has been in operation at the
Sealed Power Corporation in Muskegon, Michigan, is
totally automated and, therefore, requires minimal
attention. This system has alarms to indicate power
failure, high ambient ozone levels, and any
malfunctioning of the system components, such as
the Decompozon unit and the air compressor. These
alarms can be connected to the control/security room,
where the facility operator or security personnel is
stationed. At the sound of an alarm, all system
components and the wastewater flow will be shut off,
and the problem area will be indicated on the control
unit for proper action. Typically with this type of
unit, a 15-minute routine inspection at the beginning
and end of each day by an operator with basic
mechanical skills is adequate. Typically, no operator
attention is needed in the evenings or on weekends.
A person capable of collecting samples from taps and
performing wet chemistry analysis (measuring pH,
oxidant concentrations, etc.) is required to monitor
the Ultrox system operation once a day. These
analyses may take about an hour. Samples for
organic analyses can be sent to a contract laboratory.
A project supervisor is required to provide general
technical guidance. This person should have an
understanding of the treatment process and be
capable of reviewing data to evaluate the system's
performance. About 2 hours per week of the project
supervisor's time should be adequate.
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The operating personnel are subject to OSHA
regulations. According to OSHA, the maximum
allowable ozone exposure for an 8-hour period is 0.1
ppm. When functioning properly, the Decompozon
unit reduces ozone levels in the reactor off-gas to
about 0.001 ppm and, therefore, alleviates this
concern. However, other health and safety issues due
to the contaminants present in the untreated aqueous
waste will be site-specific. Therefore, a site-specific
Health and Safety Plan should be prepared. This plan
should include the facility description, a list of
chemicals of concern and their concentrations, health
and safety zones, personnel protective clothing and
equipment, contaminant monitoring procedures,
hospital routes, and the personnel to contact in the
event of an emergency.
Potential Community Exposures
Contaminant emissions from the Ultrox system are
minimal. The Ultrox system, equipped with its
Decompozon air treatment system, destroys ozone
present in the reactor off-gas to nondetectable levels.
The SITE demonstration data indicated that the
Decompozon unit also reduced the VOC levels
present in the reactor off-gas to nondetectable levels
when the Decompozon unit functioned properly.
Therefore, no major potential for on- site personnel or
community exposure to air-borne contaminants is
anticipated. In case of any malfunctioning, all
components of the system and unit will shut off
automatically, leaving no threat to the community.
Regulatory Requirements
This subsection discusses the regulatory
requirements for the Ultrox system as they relate to
conducting a hazardous waste site remediation.
Comprehensive Environmental Response,
Compensation, and Liability Act
The Comprehensive Environmental Response,
Compensation, and Liability Act (CERCLA) of 1980,
authorizes the Federal government to respond to
releases or potential releases of any hazardous
substance into the environment, as well as to releases
of pollutants or contaminants that may present an
imminent or significant danger to public health and
welfare or the environment.
The Superfund Amendments and Reauthorization
Act of 1986 (SARA) amended CERCLA, and directed
EPA to:
• Use remedial alternatives that permanently and
significantly reduce the volume, toxicity, or
mobility of hazardous substances, pollutants, or
contaminants
• Select remedial actions that protect human
health and the environment, are cost-effective,
and involve permanent solutions and alternative
treatment or resource recovery technologies to
the maximum extent practicable
• Avoid off-site transport and disposal of untreated
hazardous substances or contaminated materials
when practicable treatment technologies exist
(Section 121 (b))
As part of the requirements of CERCLA, EPA has
prepared the National Contingency Plan (NCP) to
address responses to releases of hazardous
substances. The NCP (codified in 40 CFR Part 300)
delineates the methods and criteria used to
determine the appropriate extent of removal and
cleanup for hazardous waste contamination. The
NCP includes chemical oxidation as a direct waste
treatment method that can be considered a long-
term, permanent solution for remediating
contaminated groundwater at CERCLA sites (Part
300.70(B)(5)).
In general, there are two types of responses possible
under CERCLA: removal and remedial actions.
Chemical oxidation technologies can be part of a
CERCLA removal action. However, if the removal
action is part of a remedial action, the removal action
will be limited in the amount of time and money
spent to implement the response. Superfund-financed
removal actions cannot exceed 12 months in duration
or $2 million in cost in most cases (Section 104(c) (1)).
Remedial actions are governed by SARA
amendments to CERCLA. As stated above, these
amendments promote remedies that permanently
reduce the volume, toxicity, and mobility of
hazardous substances, pollutants, or contaminants.
Section 121(c), of CERCLA as amended by SARA,
requires EPA to review any remedial action in which
hazardous substances, pollutants, or contaminants
remain at the site.
Because each hazardous waste site is unique and has
specific contamination characteristics, a discussion of
all potential applicable or relevant and appropriate
requirements (ARAR) for a given remedial action
involving chemical oxidation cannot be covered in
this regulatory analysis. On-site remedial actions
must comply with Federal and more stringent state
ARARs that are determined on a site-by-site basis.
ARARs will dictate the degree of cleanup necessary
at CERCLA sites, and CERCLA provides only six
waivers to meeting ARARs during a remedial action
(Section 121(d)(4)). If chemical oxidation is chosen as
the sole technology for a remedial action, then the
chemical oxidation process must meet ARARs for
cleanup at the site.
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Section 121(e)(l) specifies that no Federal, state, or
local permit is required for the portion of any removal
or remedial action conducted entirely on-site.
However, the remediation must comply with all
substantive regulatory requirements.
Resource Conservation and Recovery Act
RCRA, an amendment to the Solid Waste Disposal
Act, was passed in 1976 to address the problem of how
to safely manage and dispose of municipal and
industrial solid wastes. RCRA specifically addresses
the identification and management of hazardous
wastes. The Hazardous and Solid Waste
Amendments of 1984 (HSWA) significantly expanded
the scope and requirements of RCRA, including
prohibiting the land disposal of hazardous wastes
that do not meet promulgated treatment standards.
RCRA regulations concerning hazardous waste
identification and management are specified in 40
CFR Parts 124, 260-272. EPA and RCRA- authorized
states implement and enforce RCRA and state
regulations.
The key to determining whether RCRA regulations
apply to the Ultrox process is whether the
contaminated media is a hazardous waste. EPA
defines hazardous waste in 40 CFR Part 261. If
hazardous wastes are treated by chemical oxidation,
the owner/operator of the treatment or disposal
facility must obtain a RCRA permit from EPA or
RCRA-authorized state. RCRA requirements for
permits are specified in 40 CFR Part 260.
Requirements for hazardous waste generators are
specified in 40 CFR Part 262, and include obtaining
an EPA identification number prior to treating
hazardous wastes. The requirements for a hazardous
waste generator will be applicable if contaminated
groundwater is determined to be a hazardous waste,
and is extracted for treatment, storage, or disposal.
In some situations, chemical oxidation may be used
as part of a pump and treat remediation method. In
these cases, the owner or operator of the treatment
system will have to comply with 40 CFR Part 265,
Subparts B (General Requirements) and Q
(Chemical, Physical, and Biological Treatment).
If hazardous wastes are generated in batches and
must be stored on-site prior to treatment, other
RCRA regulations may apply. These regulations may
include complying with 90-day accumulation limits
for facilities without hazardous waste storage
permits (40 CFR Section 262.34), complying with 40
CFR Part 264 or 265, Subpart I, if hazardous wastes
are stored in containers, and complying with 40 CFR
Part 264 or 265, Subpart J, if hazardous wastes are
stored in tanks. In addition, small quantity
generators cannot store more than 6,000 kg of
hazardous waste on-site without a permit (40 CFR
Section 262.34(D)).
Once hazardous wastes are treated by chemical
oxidation, the treated waste must be analyzed to
determine if it still contains any hazardous
properties or constituents. As such, subsequent
management of the treated waste may also be subject
to the above RCRA requirements, until these
analyses are performed. Other applicable RCRA
requirements could include the use of a Uniform
Hazardous Waste Manifest if the waste is transported
off-site and restrictions as to where the treated waste
can be discharged.
Currently, air emissions from hazardous waste
treatment operations are not addressed by RCRA
regulations. However, Section 3004(n) of RCRA
directs EPA to issue regulations concerning air
emissions from hazardous waste treatment, storage,
and disposal facilities.
RCRA Corrective Action
RCRA regulations (Sections 264.100 - 264.101)
require that a corrective action program be instituted
as necessary to protect human health and the
environment from all releases of hazardous waste or
its constituents from any solid waste management
unit. The corrective action program must be in
compliance with groundwater protection standards
and must begin within a reasonable amount of time
after the groundwater protection standard has been
exceeded. The contaminated water must be treated to
the levels determined in the corrective action order.
These levels can vary, depending on state and local
requirements (e.g., NPDES, publicly-owned
treatment works (POTW), or maximum contaminant
levels (MCL)).
Additionally, a groundwater monitoring program
must be implemented to prove that the corrective
action program has been effective. Corrective action
must be completed during the compliance period to
the extent necessary to ensure that the groundwater
protection standard is met. However, if corrective
action is being performed at the end of a compliance
period, that corrective action must continue for as
long as necessary to achieve compliance with the
groundwater protection standard.
Clean Air Act
The Clean Air Act requires that treatment, storage,
and disposal facilities comply with primary and
secondary ambient air quality standards. Since
volatile organic air emissions are possible during the
extraction or transfer of the contaminated water to
the treatment unit, steps need to be taken to prevent
or minimize the potential impact from organic
vapors. Preventative measures could include storing
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the contaminated water in an enclosed tank or
container.
During treatment, steps must be taken to minimize
the release of ozone into the atmosphere.
Furthermore, any release of ozone must be no more
than 0.12 ppm, in accordance with 40 CFR Section
50.9 (national primary and secondary ambient air
quality standards for ozone). Ultrox's Decompozon
unit is specifically used to destroy ozone in the
reactor off-gas.
State air quality standards may require additional
measures to prevent volatile organic air emissions,
including the release of ozone.
Clean Water Act
The Clean Water Act (CWA), as amended by the
Water Quality Act of 1987, describes standards and
enforcement for discharges, including toxic and
pretreatment effluent standards which are applied
primarily to protect surface water quality. The CWA
established the National Pollutant Discharge
Elimination System (NPDES), which requires that
(1) EPA publish water quality criteria for pollutants
and (2) each state set water quality standards, using
the EPA criteria, for every significant body of surface
water within its borders. States then issue permits
for discharges into these bodies of surface water.
NPDES requirements are specified in 40 CFR Part
122. Part 122 requires that contaminated water be
treated to appropriate levels prior to discharging into
a storm sewer or surface waterbody. If chemical
oxidation is used as part of an industrial process or as
a RCRA-corrective action and the treated water is
discharged to a surface waterbody, a NPDES
discharge permit must be obtained.
Safe Drinking Water Act
The Safe Drinking Water Act (SDWA) of 1974, as
most recently amended by the Safe Drinking Water
Amendments of 1986, requires EPA to establish
regulations to protect human health from
contaminants in drinking water. The legislation
authorized national drinking water standards and a
joint Federal- state system for ensuring compliance
with these standards.
The National Primary Drinking Water Standards
are found in 40 CFR Part 141. Under SDWA,
maximum contaminant levels (MCL), which are
enforceable standards for chemicals in public
drinking water supply systems, were established.
MCLs consider both health factors and the economic
and technical feasibility of removing a contaminant
from a water supply system. Treated water injected
into groundwater used as a public drinking water
source must meet the MCLs.
Toxic Substances Control Act
The Toxic Substances Control Act (TSCA) of 1976, as
codified in 40 CFR Parts 700 through 799,
established requirements and authorities for
identifying and controlling toxic chemical hazards to
human health and the environment. The disposal of
PCBs is specifically regulated under Section 6(e) of
TSCA, with PCB treatment and disposal regulations
specified in 40 CFR Section 761.60.
Soil contaminated with PCBs may be encountered
when boring groundwater extraction and monitoring
wells. PCBs in concentrations between 50 and 500
ppm may be disposed of in either a TSCA-permitted
landfill or destroyed at a TSCA-approved incinerator
(40 CFR Section 761.70).
TSCA does not regulate treatment or disposal of
water contaminated with PCBs at concentrations less
than 50 ppm, which is typically found during
groundwater remedial actions.
Occupational Safety and Health Act
Superfund remedial actions and RCRA-corrective
actions must be performed in accordance with the
Occupational Safety and Health Act (OSHA)
requirements codified in 29 CFR Parts 1900 through
1926. During site preparation, a pad, made of
compacted gravel or concrete, will likely have to be
constructed to place the Ultrox unit on. The
construction of this pad must be performed in
accordance with Part 1926 of OSHA (Safety and
Health Regulations for Construction).
A weather shelter to provide protection for the Ultrox
system from inclement weather and to provide
suitable work environment for on-site personnel
needs to be constructed. The complexity of this
shelter will depend on the climate where the site is
located and the duration of treatment. For the Ultrox
demonstration in San Jose, California, a large
awning proved sufficient. However, in areas without
year-round, mild climates, it may be necessary to
build a sturdy and durable enclosure.
Since the Ultrox unit operates on electricity, utility
hookups are needed. Construction of these hookups
must be performed in accordance with Part 1926,
Subpart K (Electrical) of OSHA. If the utility lines
are placed underground, the excavation performed
must follow the requirements specified in Part 1926,
Subpart P of OSHA.
Although the Ultrox system requires little personnel
involvement once it is operating under desired
conditions, technicians performing daily and weekly
monitoring and sampling must wear personnel
protective equipment, such as rubber gloves and eye
guards (Part 1910, Subpart I). Additional personnel
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protective equipment may be needed when handling
untreated waste.
State occupational safety and health requirements
may be significantly stricter than Federal standards.
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Section 4
Economic Analysis
Introduction
The costs associated with the Ultrox technology are
defined by 12 cost categories that reflect typical
cleanup activities at Superfund and RCRA-
corrective action sites. Each of these categories is
defined and discussed, thereby forming the basis for
the estimated cost analysis presented in Table 4-1 for
an Ultrox UV technology operation. Annual
operating and maintenance costs and one-time costs
are presented in Table 4-1 for three treatment flow
rates: 20, 100, and 250 gpm. The costs presented in
this analysis are order-of-magnitude (-30 to +50
percent) estimates, as defined by the American
Association of Cost Engineers.
Site-Specific Factors Affecting Cost
Several factors affecting the cost of the Ultrox system
are highly site-specific, and are difficult to calculate
without the benefit of data from an accurate site-
remedial investigation report. The factors most
affecting cost include: volume of aqueous waste to be
treated; extent of contamination; site condition (in
terms of necessary site preparation, such as
constructing access roads and regrading for a
treatment pad, etc.); treatment goals to meet
discharge requirements; and frequency of equipment
repair and replacement.
Basis of Economic Analysis
The Ultrox technology can be operated in a batch or
continuous mode depending upon treatment
requirements. For the purpose of this economic
analysis, it is assumed that the system will be
operated in a continuous mode, 24 hours a day, 7 days
a week, for one year. During this period the unit
should treat approximately 10.5 million gallons in
the 20-gpm unit, 52.5 million gallons in the 100-gpm
unit, and 131.5 million gallons in the 250-gpm unit.
One year was chosen as the period of time for this
Table 4-1. Estimated Costs Associated with Three Ultrox System Units
Estimated Costs (1990 $)
Item
Site Preparation Costs3
Permitting and Regulatory Costs3
Capital Equipment Costs3
Startup and Fixed Costs3
Labor Costsb
Supply and Consumable Costsb
Utility Costsb
Effluent Monitoring and Disposal Costsb
Residuals and Waste Shipping, Handling, and Transporting Costsb
Analytical Costs'3
Equipment Repair and Replacement Costs'5
Site Demobilization Costs3
20 gpm
36,000
3,500
70,000
32,000
6,600
10,500
12,000
3,000
1,000
24,000
4,000
2,000
1 00 gprn
55,000
7,500
150,000
32,000
6,600
16,500
58,000
3,000
5,000
24,000
22,000
3,000
250 gpm
75,000
13,000
260,000
32,000
6,600
20,800
145,000
3,000
7,000
24,000
33,000
4,000
Total One-Time Costs
Total Annual Operation and Maintenance Costs
143,500
61,100
247,500
135,100
384,000
239,400
3 One-time costs
b Annual operation and maintenance costs
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analysis so that reliable annual operating and
maintenance costs could be determined. However, it
should be noted that most groundwater remedial
actions require a significant amount of time (e.g., 5 to
30 years).
In addition, it is assumed that the groundwater is
contaminated with VOCs such as TCE and vinyl
chloride, at levels of 100 and 40 ug/L, respectively.
The operating conditions assumed for this analysis
are as follows: a hydrogen peroxide dose of 16 mg/L;
an hydraulic retention time of 60 minutes; an ozone
requirement of 14 Ibs/day at 2 percent weight in air;
and all UV lamps operating at 100 percent efficiency.
The contaminants were assumed to be treated to
meet NPDES standards for discharge into a storm
drain or nearby waterway.
The following is a list of assumptions used for this
analysis:
• Utility connections will be overhead
• Suitable access roads exist
• Contaminated water is in a shallow aquifer
• Installation of the Ultrox system at the site is not
included in the capital equipment cost
• One technician, one hour per day, seven days a
week will check and maintain the system
• One supervisor, two hours per week, will
supervise the technician
• Labor costs associated with major repairs are not
included
• Spent UV lamps from the treatment process are
considered a hazardous waste
• One treated water sample will be taken each
month and tested for organic compounds
• UV lamps will be replaced annually
• Site demobilization only includes transporting
the Ultrox unit off-site
• Decommissioning equipment and disposal costs
are not included.
A detailed discussion of each of the 12 cost categories
in Table 4-1 is provided below.
Site Preparation Costs
The costs associated with site preparation include
planning and management, system design, auxiliary
and temporary equipment and facilities, legal
searches, access rights, preparation for support
facilities, minor cleaning of the site, emergency and
safety equipment, utility connections, constructing
foundations, installing monitoring and extraction
wells if groundwater is the aqueous waste, startup,
and site support staff.
Site preparation costs will vary depending on the
type of site where the treatment operation takes
place and the condition of the site. Sites that require
major cleaning and regrading for the foundation will
significantly increase site preparation costs. Utility
connections can be either overhead or buried;
however, the latter option will require more design,
planning, and construction. For this analysis, it is
assumed that utility connections will be overhead. In
addition, some sites may require the construction of
access roads; however, this analysis, assumes that
suitable access roads already exist.
Installing monitoring and extraction wells are a
significant portion of site preparation costs,
depending on the depth of the groundwater to be
monitored and extracted. The Ultrox system can also
be used to treat contaminated surface water. In such
a case, a pump system may need to be installed,
including a filtration system to screen out debris and
any other solids. It is assumed for this analysis that
contamination is present in a shallow aquifer. Site
preparation costs are estimated to be approximately
the following: $36,000 for a 20-gpm unit; $55,000 for
a 100-gpm unit; and $75,000 for a 250-gpm unit.
Permitting and Regulatory Costs
Permitting and regulatory costs will vary depending
on whether treatment is performed on a Superfund or
a RCRA-corrective action site and on how the
effluent is disposed. Section 121(d) of CERCLA as
amended by SARA requires that remedial actions be
consistent with ARARs for environmental laws,
ordinances, regulations, and statutes. ARARs
include Federal standards and criteria as well as
more stringent standards or criteria promulgated
under state or local jurisdictions. Applicable
requirements are those for which the jurisdictional
prerequisites of the underlying statute are satisfied.
Relevant and appropriate requirements do not
legally apply to the situation or action planned, but
are none the less suitable because of the
characteristics of the remedial action, the pollutants
in question, or the physical circumstances at the site.
ARARs must be determined on a site-specific basis.
At RCRA-corrective action sites, analytical protocols
and annual monitoring records will have to be kept,
which will increase the regulatory costs. For these
situations, an additional 5 percent should be added to
the estimate rendered for this category.
Contaminated soil removed during the installation of
monitoring and extraction wells will have to be
stored in compliance with RCRA or state
requirements. Soil that will be disposed of at a
permitted landfill will have to meet Federal or state
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land disposal restriction requirements. This may be
very difficult and costly for PCB- contaminated soil.
and fixed costs are estimated to be approximately
$32,000.
Permitting and regulatory costs are assumed to be
approximately 5 percent of the capital equipment
costs for a treatment operation that is part of a
Superfund remedial action. This estimate does not
include annual discharge permit costs which may
vary significantly depending on state and local
requirements.
Capital Equipment Costs
Capital equipment costs include the cost of an Ultrox
reactor, an air compressor, an ozone generator, and a
hydrogen peroxide feed system. Based on information
provided by Ultrox International, these costs are
$70,000 for a 20-gpm unit, $150,000 for a 100-gpm
unit, and $260,000 for a 250-gpm unit. Installation
costs are not included in these estimates but are
assumed to be approximately 5 to 7 percent of the
capital equipment costs.
Startup and Fixed Costs
Startup costs include those required to establish
operating procedures, train operators, perform an
initial shakedown of the equipment and analysis,
construct a shelter to protect the system, and initiate
an environmental monitoring program.
To ensure safe, economical, and efficient operation of
the unit, a program to train operators is necessary.
The costs associated with this training program
include developing a health and safety program and
associated manuals, providing health and safety
training, and providing training for operating and
maintaining the system. At least three persons (i.e.,
two technicians and one supervisor) will need health
and safety training, with the supervisor receiving
health and safety supervisory training in addition.
These individuals will be responsible for daily
monitoring and will have to be instructed by Ultrox
personnel about operating and maintaining the
system. Startup training costs are estimated to be
approximately $7,500. This estimate is based on
three 40-hour health and safety training courses, one
health and safety supervisory training course, and
three weeks of instruction for the three individuals
from Ultrox's staff.
Mobilization and shakedown costs include the
transportation of the unit to the site, initial setup, on-
site checkout, construction of a weather shelter,
construction supervision, working capital, and
analysis to determine the proper operating
parameters for treatment. These costs are site-
specific and will vary depending on the location of the
site. Personnel travel costs to the site are not
included. For this analysis, equipment shakedown
and analysis are assumed to be $20,000. Total startup
Labor Costs
Once the Ultrox UV radiation/oxidation system is
assembled and shakedown has been completed, the
system requires very little labor for operation. Based
on information provided by the developer, from case
studies, and from the operation of other similar
groundwater treatment systems, it is assumed that a
skilled technician will be needed for one hour a day,
seven days a week, to check and maintain the
equipment and take routine water and air samples.
This analysis assumes that two individuals will split
this job (one during the week and one during the
weekend) and that they will be working on other
remediation efforts the remaining seven hours in
their workshift. In addition, a supervisor will be
needed for two hours per week, to oversee the work
performed by the technicians. It is assumed that the
technician will be paid $10 per hour and the
supervisor will be paid $20 per hour (fringe benefits
are not included). The annual operating labor costs
will be approximately $3,600 for the technician and
$2,100 for the supervisor. The two technicians and
the supervisor will require an annual health and
safety refresher course and it is estimated that this
will cost $900 annually. Total annual labor costs are
assumed to be $6,600. This estimate does not include
labor costs associated with major equipment repairs.
Supply and Consumable Costs
Supplies and consumables for the Ultrox UV
radiation/oxidation system include hydrogen
peroxide, acids for pH adjustment, and other
miscellaneous supplies. The quantities of hydrogen
peroxide and acid used depend upon the size of the
system employed and the level of organic
contamination in the waste stream. These costs are
assumed to be approximately 15 percent annually of
capital equipment costs for the 20-gpm unit, 11
percent for the 100-gpm unit, and 8 percent for the
250-gpm unit. These estimates represent the average
costs of these items incurred during implementation
of the Ultrox system at other sites. The cost of the
supplies is expected to significantly decrease with the
larger volume units, due to economies of scale.
Utility Costs
The Ultrox system runs on commercial electricity.
Utility costs reflect the amount of electricity needed
to operate the ozone generator, the UV
radiation/oxidation reactor with its lamps, and site
support facilities. The quantity of electricity used
depends on the quantity of groundwater treated, the
amount of ozone needed, the level of contamination,
and the retention time. It is estimated that the
electrical cost will be $1.10 per 1,000 gallons treated,
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based on averages from other case studies and
estimates from several utility companies.
Effluent Monitoring and Disposal Costs
This cost category consists of effluent monitoring and
a supply and storage or source of clean water for
personnel and equipment decontamination. Effluent
monitoring will be performed routinely by the
technician. The effluent will be discharged to a
nearby storm drain or reinjected into the
groundwater. The cost estimate for this category is
based on discharge to a storm drain and is
approximately $3,000 per year.
Residuals and Waste Shipping, Handling, and
Transportation Costs
The Ultrox UV radiation/oxidation process produces
very few residuals that require special handling.
Filters and UV lamps may need to be disposed of
following treatment due to a buildup of residuals and
corresponding reduction in effectiveness and
efficiency. Spent UV lamps are considered hazardous
because they contain mercury and will therefore
require disposal at a permitted facility. Residuals
shipping, handling, and transporting costs to a
hazardous waste disposal facility are assumed to be
between $1,000 and $7,000 per year for the 3 Ultrox
units, based on disposal costs of $500 per drum.
Analytical Costs
Analytical costs include laboratory analyses, data
reduction and tabulation, quality assurance/quality
control (QA/QC), and reporting. Monthly laboratory
analyses will cost approximately $1,250, while data
reduction and tabulation, QA/QC, and reporting
should cost $500 to $750 dollars per month. This
analysis assumes that one organic treated
water sample, will be taken each month. Total
estimated analytical costs are, therefore,
approximately $24,000 per year.
Equipment Repair and Replacement Costs
During the course of operation, certain parts of the
Ultrox system will need to be replaced. The most
common parts needing replacement are the UV
lamps, spargers, and influent feed line filters. The 20-
gpm unit contains 36 lamps, the 100-gpm unit has
288 lamps, and the 250-gpm unit has 432 lamps. UV
lamps will have to be replaced annually, at a cost of
$60 per lamp installed. Annual equipment repair and
replacement costs are estimated to be approximately
5.7 percent of the capital costs for the 20-gpm unit;
14.7 percent of the capital costs for the 100-gpm unit;
and 16 percent of the capital costs for the 250-gpm
unit. It is assumed for this analysis that the cost of
filters and spargers will decrease due to economies of
scale.
Site Demobilization Costs
Site demobilization will include operation shutdown,
site cleanup and restoration, permanent storage
costs, and site security. Site demobilization costs will
vary depending on whether the treatment operation
occurs at a Superfund site or at a RCRA-corrective
action site. Demobilization at the latter type of site
will require detailed closure and post-closure plans
and permits. Demobilization at a Superfund site does
not require as extensive post-closure care; for
example, 30-year monitoring is not required. This
analysis assumes site demobilization costs cover only
those items involved with transporting the Ultrox
units and are assumed to vary between $2,000 and
$4,000 for the different treatment units.
Decommissioning equipment and disposal costs are
not included in this estimate.
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References
Aieta, E.M., K.M. Reagan, J.S. Lang, L. McReynolds,
J.W. Kang, and W.H. Glaze, 1988. Advanced
Oxidation Processes for Treating Groundwater
Contaminated with TCE and PCE: Laboratory
Studies, Journal of the American Water Works
Association, 5:64.
Cheremisinoff, N.P., P.N. Cheremisinoff, and R.B.
Trattner, 1981. Chemical and Nonchemical
Disinfection, Ann Arbor Science Publishers, Inc.,
Michigan.
EPA, 1989. Technology Evaluation Report, SITE
Program Demonstration of the Ultrox
International Ultraviolet Radiation/Oxidation
Technology, EPA/540/5-89/012.
Fletcher, D.B., 1987. UV/Ozone Process Treats
Toxics, Waterworld News, 3:25.
Garland II, S. B., 1989. Annual Report, An
Evaluation of the Use of a Combination of Ozone,
Ultraviolet Radiation, and Hydrogen Peroxide to
Remove Chlorinated Hydrocarbons from
Groundwater at the Department of Energy
Kansas City Plant, Oak Ridge National
Laboratory Report, ORNL/TM-11056.
Glaze, W.H., G.R. Peyton, F.Y. Huang, J.L. Burleson,
and P.C. Jones, 1980. Oxidation of Water Supply
Refractory Species by Ozone with Ultraviolet
Radiation, EPA-600/2-80-110.
Glaze, W.H., 1987. Drinking Water Treatment with
Ozone, Environmental Science and Technology,
21:3:224.
Glaze, W.H., J.W. Kang, and D. H. Chapin, 1987. The
Chemistry of Water Treatment Processes
Involving Ozone, Hydrogen Peroxide, and
Ultraviolet Radiation, Ozone Science and
Engineering.
Glaze, W.H., and J.W. Kang, 1988. Advanced
Oxidation Processes for Treating Groundwater
Contaminated with TCE and PCE: Laboratory
Studies, Journal of the American Water Works
Association, 5:57.
Levenspiel, O., 1972. Chemical Reaction
Engineering, Second Edition, John Wiley & Sons,
Inc., New York.
Robson, C.M., 1987. Engineering Aspects of
Ozonation, Waterworld News, 3:18.
Tucker, A.L., 1986. Refining UV Systems,
Waterworld News, 4:16.
Venosa, A., and E.J. Opatken, 1979. Ozone
Disinfection - State of the Art. In: Proceedings,
Pre-conference Workshop on Wastewater
Disinfection, Atlanta, GA, Water Pollution
Control Federation.
Weir, B.A., D.W. Sundstrom, and H.E. Klei, 1987.
Destruction of Benzene by Ultraviolet Light-
Catalyzed Oxidation with Hydrogen Peroxide,
Hazardous Waste and Hazardous Materials,
4:2:165.
WPCF, 1986. Wastewater Disinfection, Manual of
Practice No. FD-10, Alexandria, Virginia.
25
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-------
Appendix A
Key Contacts for the SITE Demonstration
27
-------
Appendix A Contents
Page
The Ultrox Technology 29
The SITE Program 29
The Demonstration Site 29
28
-------
Appendix A
Key Contacts for the SITE Demonstration
Additional information on the Ultrox technology, the
SITE Program, and the demonstration site can be
obtained from the following sources.
The Ultrox Technology
David B. Fletcher
President
Ultrox International
2435 South Anne Street
Santa Ana, CA 92704
(714) 545-5557
The SITE Program
SITE Program, EPA Headquarters
Jim Cummings
U.S. Environmental Protection Agency
Office of Solid Waste and Emergency Response
Office of Policy, Management, and Technology
401 M Street, S.W.
Washington, DC 20460
(202) 382-4362
SITE Project Manager, Ultrox Demonstration
Norma M. Lewis
U.S. Environmental Protection Agency
Office of Research and Development
Risk Reduction Engineering Laboratory
26 West Martin Luther King Drive
Cincinnati, OH 45268
(513) 569-7665
Chief, SITE Demonstration and Evaluation Branch
Steve James
U.S. Environmental Protection Agency
Office of Research and Development
Risk Reduction Engineering Laboratory
26 West Martin Luther King Drive
Cincinnati, OH 45268
(513) 569-7877
Chief, Demonstration Section
John Martin
U.S. Environmental Protection Agency
Office of Research and Development
Risk Reduction Engineering Laboratory
26 West Martin Luther King Drive
Cincinnati, OH 45268
(513) 569-7758
The Demonstration Site
Joseph B. Healy, Jr.
U.S. Environmental Protection Agency
Superfund Remedial Branch (H-6-3)
Hazardous Waste Management Division
1235 Mission Street
San Francisco, CA 94103
(415) 777-3000
Director, Superfund Technology Demonstration
Division
Robert Olexsey
U.S. Environmental Protection Agency
Office of Research and Development
Risk Reduction Engineering Laboratory
26 West Martin Luther King Drive
Cincinnati, OH 45268
(513) 569-7861
29
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-------
Appendix B
Vendor's Claims for the Technology
31
-------
Appendix B Contents
Page
Introduction 34
Description of the ULTROX® Process 34
ULTROX® Equipment 35
Applications of the ULTROX® System 35
Selected Case Studies 39
Cost Information 40
Summary 40
32
-------
Figures
Number Page
B-l ULTROX® system flow diagram 36
B-2 Photograph of the ULTROX® unit 37
Tables
B-2
B-3
B-4
B-5
B-6
B-7
Contaminants Treated by the ULTROX® System
Treatability and Design Study Results Using Pilot Plants On-Site
Applications of Full-Scale ULTROX® Systems
Direct Operation and Maintenance Costs Using UV
Radiation/Oxidation for Water Supplies
Direct Operation and Maintenance Costs Using UV
Radiation/Oxidation at Industrial Installations
Typical Capital Costs for UV Radiation/Oxidation Systems
38
38
39
41
41
42
33
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Appendix B
Vendor's Claims for the Technology
Note: This appendix to the report is based upon
claims made by Ultrox International either in
conversations or in written or published materials.
These claims and interpretations of the regulations
are those made by the vendor and are not necessarily
able to be substantiated by test data. Many of
Ultrox's claims are compared in Appendix C with the
available test data.
Introduction
The removal of low levels of organic contaminants
from groundwaters and industrial wastewaters
presents a challenge to environmental professionals.
The ULTROX® (a registered trademark of Ultrox
International) ultraviolet (UV) radiation/oxidation
process is a cost effective treatment technique which
is applicable to the destruction of a wide range of
soluble organic contaminants in water. Other well-
known and commonly used treatment processes such
as granular activated carbon (GAG) and air stripping
transfer pollutants from one medium to another.
With increasing public and regulatory concern over
the fate of pollutants, such transferential
technologies are not optimal.
Conventional chemical oxidation has been used in
the treatment of various waters polluted by organic
chemicals for a number of years. Potassium
permanganate, chlorine, and chlorine dioxide have
been used for treating organics such as phenol and its
homologs in wastewaters. Hydrogen peroxide, with a
catalyst such as ferrous sulfate, has been used for
oxidizing phenol and other benzene derivatives.
Processes utilizing iron-catalyzed peroxides and
chlorine compounds are attractive because they use
relative low-cost treatment equipment. The
disadvantages of these processes are that they can
attack only a limited number of refractory organics,
and that they produce iron sludges or chlorinated
organics. Ozone alone has been used to treat phenolic
wastes, cyanides, and certain pesticides. Ozone
treatment is a very clean process but is limited in the
number of compounds which it can effectively treat.
The use of UV radiation-catalyzed ozone plus
hydrogen peroxide (UV radiation/oxidation) as a
water treatment technique is rapidly expanding. It
offers a means of solving many of the problems
created by the water soluble, toxic organic chemicals
that are found today in groundwater, wastewater,
leachate, and drinking water supplies without many
of the disadvantages of more conventional
techniques.
UV radiation/oxidation, when used as a stand-alone
treatment process or in tandem with a few of the
above mentioned processes, can cost-effectively
destroy the organic chemicals on EPA's priority
pollutant list or render the organics non-toxic.
This appendix describes the experience of Ultrox
International in developing and applying the
ULTROX® UV radiation/oxidation process to the
full-scale treatment of organics in wastewaters,
drinking waters, leachates, and groundwaters.
Ultrox International was issued a process-patent in
1988 covering the application of UV radiation, ozone,
and hydrogen peroxide to the treatment of a broad
range of organic compounds in water.
Description of the ULTROX® Process
The ULTROX® UV radiation/oxidation process was
developed over a 15-year period. UV radiation, when
combined with ozone and/or hydrogen peroxide,
produces a highly oxidative environment
significantly more destructive than that created with
ozone or hydrogen peroxide by themselves or in
combination.
UV radiation significantly enhances ozone and
hydrogen peroxide reactivity by:
• Transformation of ozone and hydrogen peroxide
to highly reactive OH° radicals
• Excitation of the target organic solute to a higher
energy level
• Initial attack of the target organic compound by
UV radiation
The importance of the conversion of the ozone and
hydrogen peroxide to OH° can be more easily
34
-------
understood after studying the relative oxidation
power of oxidizing species. Hydroxyl radicals have
significantly higher oxidation power than either
hydrogen peroxide or ozone. The oxidation potentials
and relative oxidation powers of several oxidants are
as follows:
Species
Fluorine
Hydroxyl radical (OH°)
Atomic Oxygen
Ozone (O3)
Chlorine dioxide
Hydrogen peroxide (H2O2)
Perhydroxyl radicals
Hypochlorous acid
Chlorine
Oxidation
Potential Value
3.06
2.80
2.42
2.07
1.96
1.77
1.70
1.49
1.36
Relative
Oxidation
Power
(Cl = 1.00)
2.25
2.05
1.78
1.52
1.44
1.30
1.25
1.10
1.00
The effect of UV-enhanced oxidation is illustrated in
Table B-l.
ULTROX® Equipment
ULTROX® UV radiation/oxidation equipment
treatment systems have very few moving parts,
operate at low pressure, require minimum
maintenance, operate full-time or intermittently in
either a continuous or batch-treatment mode, utilize
efficient, low-temperature, long-life UV lamps, and
can employ the use of a microprocessor to control and
automate the treatment process.
The ULTROX® UV radiation/oxidation system
consists of a UV radiation/oxidation treatment tank
and an oxidation source which can be either an ozone
generator with an air preparation system or a
hydrogen peroxide feed system. Figures 2-1 (see
Section 2), B-l, and B-2 are an isometric assembly
view, a drawing, and a photograph, respectively, of a
model F-150 system, which accommodates flow rates
up to 10 gpm or batches of 150 gallons.
The treatment tank is made of stainless steel. The
UV lamps are enclosed within quartz tubes for easy
replacement and are mounted vertically within the
tank. Depending upon the size of the tank and the
type of wastewater to be treated, the tank can have
four to eight chambers separated by baffles. Lamps
are installed either in all chambers or in designated
chambers, depending on the treatment specified.
When ozone is used as the oxidant, it is introduced at
the base of the chamber. The ozone is dispersed
through porous stainless steel diffusers. The number
of diffusers needed will depend upon the type of
organics being oxidized and the degree of removal
required.
Ozone is produced from either compressed air, dried
to a -60°F dewpoint by desiccarit columns, or produced
from compressed or liquid oxygen. Up to 2 percent (by
weight) ozone is generated from air, and up to 5
percent (by weight) ozone can be produced
economically from oxygen.
Commercial-grade hydrogen peroxide used in the
process, is directly metered into the influent line to
the reactor.
Water pumped into the treatment tank flows from
chamber to chamber in a sinusoidal path. When the
reactor uses ozone, the residual ozone in the off- gas is
decomposed back to oxygen by the use of a fixed-bed
catalytic unit operating at 150°F. The air is then
vented to the atmosphere.
Ozone generators with varying capacities are used
with the Model F-150 reactor. The size of the
generator depends upon the ozone dosage
requirements. Present installations use 28 to 140
pounds per day capacities.
Applications of the ULTROX® System
The UV radiation/oxidation equipment developed by
Ultrox in recent years has been used to treat a wide
variety of waste streams. Table B-2 lists toxic
compounds found in wastewaters and groundwaters
that have been successfully treated with the
ULTROX® system. Specific case histories of
treatability and design studies for private industries
and military installations are presented in Table B-3.
Contaminants oxidized included pesticides,
petroleum compounds, munitions waste, and
chlorinated solvents. In each of these cases, pilot
treatment plants were operated on-site to develop
treatment design and cost data.
Table B-4 illustrates projects where the treatability
and design studies were converted into permanent
on-site UV radiation/oxidation installations. Full-
scale ULTROX® units are currently treating
contaminated groundwater, wastewater, and process
water. Contaminants in these waters include
phenols, chlorinated solvents, hydrazine,
dimethylnitrosamine, tetrahydrofuran, and
formaldehyde. Commercial systems have been
designed, built, and installed to treat flows varying
from 10,000 to 300,000 gallons per day. A system to
treat 1.3 million gallons per day is under
construction.
Standard equipment designs are used in all of these
installations. Reactor size varies from 300 to 4,800
gallons. Ozone generators range from 21 to 140
pounds per day. In several cases, hydrogen peroxide
is used in place of, or with, ozone.
Specific design parameters are developed through
performance of treatability studies, pilot tests, and
35
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Table 8-1. Oxidations of Methylene Chloride and Methanol
Contact Time
(min.) Control UV
Melhyleno Chloride
0 100 100
15 100 59
25 100 42
Mothanol
0 75 75
30 75 75
Notes: i.
2.
Ozone
from Ozot
Generate
UV
(ty
j
All concentrations reported in mg/L.
NDA = No data available.
Rotameter
(typical)
Needle Valve gl \Fjl Fj
(typical) bat |zjt m
rB 3 !} 4
>
Lamp cx^^
pical) —• o
o
o
O
Stainless °
Reactor
CD-1
J J
Headspace
o/ ^ o o o
o o o o
o o o o
r o o r o o
0 00 0
o o o o
o • • e
Ozc
Hydrogen Peroxi
Feed Tank
i ,
de
r'Ov
$
O
o
o
o
UV/H2O2 O3/H2O2 UV/O3 UV/O3/H2O2
100 100 100 100
46 32 36 19
17 21 16 7.6
75 " NDA 75 75
75 NDA 31 1.2
C
)zone Manifold Catalytic
.. / ,_. Ozone
1 H Decomposer
< •{ ^
erflow Weir
pical)
— __ ~S>-L^ —
\ o o o
o o o
0 O 0
0 , 0 0
O O 0
o o o
r Sight Glass
,00 0
o o o
o o o - •'" 1 1
. I Treated
' . . * •„ I* I I U> Effluent
. . II Stora9e
^^ 1 9 Tank
r~hJ " 't><17~^
I
/ I
me Diffuser From Shallow 1
(typcal) I Groundwater ^ Effluent
^__| Monitoring Wells Sample Tap
XH-|-
Contaminated Water
Figure B-1. ULTROX® system flow diagram.
full-scale shakedowns. Treatability studies are
carried out first in the laboratory using bench-scale
peroxide. If the results are encouraging, the next step
in the study involves the installation of a skid-
equipment to evaluate the feasibility of treating the mounted, pilot-scale unit on-site. Sufficient design
water with UV radiation/ozone, UV radiation/ and cost data normally are collected within 2 weeks.
hydrogen peroxide, or UV radiation/ozone/hydrogen Specifications for the full-scale system are then
36
-------
Figure B-2. Photograph of the ULTROX® unit.
37
-------
Table B-2. Contaminants Treated by the ULTROX® System
Industrial Effluent Contaminants
Groundwater Contaminants
Amines
Analine
Benzene
Chlorinated solvents
Chlorobenzene
Complex cyanides
Creosote
Hydrazine compounds
Isopropanol
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
Methylene chloride
Polychlorinated biphenyl (PCB)
Pentachlorophenol
Pesticides
Phenol
Cyclonite (RDX)
2,4,6-Trinitrotoluene (TNT)
Toluene
Xylene
Polynitrophenols
Benzene, toluene, and xylene (BTX)
Bis (2-chloroethyl) ether
Creosote
1,2-Dichloroethane(1,2-DCA)
Dichloroethylene (DCE)
Dioxins
Dioxanes
Freon 113
Methylene chloride
Methyl isobutyl ketone (MIBK)
Polychlorinated biphenyl (PCB)
Tetrachloroethylene (PCE)
Pentachlorophenol
Pesticides
Polynuclear aromatic hydrocarbons (PAH)
1,1,1 -Trichloroethane (1,1,1-TCA)
Trichloroethylene (TCE)
Tetrahydrofuran (THF)
Vinyl chloride
Triglycol dichloride ether
Table B-3. Treatabllity and Design Study Results Using Pilot Plants On-Site
Customer
Application
Contaminants
Results
Bulk Chemical Transfer Depot
Municipal Water Producers
Aerospace Co.
Chemical Co.
Automotive Co.
Electronics Co.
Munition Plants
Army Bases
Semiconductor Co.
Petrochemical Mfr.
Semiconductor Mfr.
Contaminated groundwater
Contaminated drinking water
supply
Paint stripping wastewater
Wastewater
Contaminated groundwater
Wastewater/runoff, groundwater
Wastewater
Contaminated groundwater
Wastewater
Wastewater
Contaminated groundwater
TCE, PCE, methylene chloride
TCE, PCE, color
Methylene chloride
Misc. pesticides (including
DBCP)
TCE, Methylene chloride
PCBs, VC, DCA, and other
VOCs
TNT, RDX
DIMP, DBCP, VOCs
EDTA
Benzene
Benzene, toluene, ethylbenzene,
xylene
Water treated and reinjected
VOCs and color reduced to
below state action levels
Methylene chloride reduced from
4,000 ppm to less than 100 ppb
DBCP and other pesticides
reduced to less than i ppb
Reduced 10 ppm to 5.0 ppb
Reduced PCBs to less than 1
ppb; VOCs reduced to below
state action levels
TNT and RDX reduced from 100
ppm to less than 1 ppm
DIMP and DBCP reduced to less
than 10 ppb; VOCs reduced to
below state action levels
Reduced EDTA from 6,000 ppm
to 100 ppm
(acceptable discharge standard)
Reduced benzene from 10 ppm
. to 50 ppb
Reduced contaminants from 14.0
ppm to 4.0 ppb
Notes:
DCA: dtehtofoetnane; DBCP: dibromochloropropane; DIMP: diisopropyl methyl phosphonate; EDTA: ethylenediamine tetraacetic acid; PCB:
Polychlorinated biphenyl; PCE: tetrachloroethylene; RDX: cyclonite; TCE: trichloroethylene; TNT: 2,4,6-trinitrotoluene; VC: vinyl chloride;
VOC: volatile organic compound.
prepared. Standard reactors, ozone generators, and
hydrogen peroxide feed systems are utilized. Systems
are assembled and tested at Ultrox's facilities and
then shipped to the job site. The systems are then
installed, inspected, and turned over to the customer.
Full-service maintenance contracts are available.
38
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Table B-4. Applications of Full-Scale ULTROX® Systems
Customer
Application
Contaminants
Results
Wood Treatment Plants (2)
Closed Wood Treating Plant
Chemical Plant
Automotive Foundry
Aerospace Co.
Chemical Plant
Semiconductor Co.
Wood treatment wastewater
Contaminated groundwater
Fume scrubber waste
Contaminated groundwater
Contaminated groundwater
Wastewater
Contaminated groundwater
Phenol, pentachlorophenol
Phenol, pentachlorophenol
Hydrazine, monomethyl
hydrazine, unsymmetrical
dimethyl hydrazine
TCE, 1,2-trans-DCE
TCE, TCA, DCA, PCE,
methylene chloride
Phenol, formaldehyde
THF
Treated water discharged to
POTW
Treated water discharged to
POTW
Destroyed parent compounds to
not detected levels and dimethyl
nitrosoamine below 10 ppb
Treated water discharged to lake
Treated water dsicharged to
POTW
Treated water discharged to
POTW
Replaced a GAC system to
reduce THF from 1,000 ppb to
less than 5 ppb
Notes:
DCA: dichloroethane; DCE: dichloroethylene; GAC: granular activated carbon; PCE: tetrachloroethylene; POTW: publicly-owned treatment
works; TCA: trichloroethane; TCE: trichloroethylene; THF: tetrahydrofuran.
Full-scale systems, in most cases, are automated
using microprocessor control. The system usually
requires periodic monitoring (once per shift or once
per day). The systems are designed to operate in a
batch or continuous mode depending on treatment
requirements.
In a number of cases, UV radiation/oxidation is used
as part of a treatment train. For example, at wood
treatment sites, the wastewater or groundwater
requires breaking of oil/water emulsions, removal of
suspended matter, and adjustment of pH prior to the
UV radiation/oxidation treatment.
Selected Case Studies
Automotive Parts Manufacturer
Testing of groundwater at a Michigan automotive
parts manufacturing site revealed significant VOC
contamination. TCE levels of 5,000 to 10,000 ug/L
were recorded, as well as trace levels of other
chlorinated solvents. The Michigan Department of
Natural Resources required that the manufacturer
pump and treat the groundwater.
The manufacturer investigated air stripping with
GAC off-gas treatment, aqueous phase GAC, and
ULTROX® UV radiation/oxidation as possible
treatment alternatives. Bench-scale studies were
conducted at a GAC supplier and at Ultrox's
laboratory. While all treatment techniques could
provide the required removal levels, UV
radiation/oxidation was the most economical. Testing
of an ULTROX® P-75 pilot-scale treatment system
over a 2-week period confirmed the data obtained in
the laboratory. An ULTROX® F-3900 treatment
system was ordered and installed in May 1989. The
system is currently operating and achieving the
following results, which exceed Michigan
requirements:
210 gpm
5,500 ug/L TCE
1 ug/L TCE
$/l.OOP gallons
$0.119
0.188
0.133
0.44
0.29
$0.73
Flow Rate:
Influent Concentration:
Effluent Concentration:
Treatment Costs:
Ozone (@ 0.06/kWh)
H2O? (@ $0.75/lb)
UV (incl. power and
annual lamp
replacement)
O&M Cost
Capital Amortization
(16%/year)
Total Treatment Cost:
Semiconductor Manufacturer
In 1982, groundwater contamination was detected
beneath a Hewlett Packard facility in Palo Alto,
California. The contamination was due to leaks in
underground chemical storage tanks. Benzene,
toluene, ethylbenzene, and xylene (BTEX) levels of
4,000 to 15,000 ug/L were recorded.
In 1988, granular activated carbon (GAC) treatment
of groundwater was initiated as an interim measure.
In early 1989, under the sponsorship of the California
Department of Health Services Hazardous Waste
Reduction Grant Program, Ultrox brought a mobile
P-150 UV radiation/oxidation system to the site.
During 3 weeks of testing, Ultrox demonstrated the
treatment equipment's ability to treat the
39
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groundwater to publicly-owned treatment works
(POTW) or NPDES standards. Treatment costs for a 5
gpm flow were $60,000 per year with the GAC
system. Based on the field studies, projected
operation and maintenance (O&M) costs for an
ULTROX® system are less than $5,000 per year. The
treatment costs, scaled up to 50 gpm, to meet either
the POTW and NPDES standards are as follows:
Flow Rate:
Influent Concentration:
Effluent Concentration:
Treatment Costs:
Ozone (@0.06/kWh)
H2O? (@ $0.75/lb)
UV (incl. power and
annual lamp
replacement)
O&M Cost
Capital Amortization
(16%/year)
Total Treatment Cost:
50 gpm
ll.OOOppbBTEX
<5ppbBTEX
$71.000 gallons
98.66%
Removal
BTEX
$0.31
0.28
0.32
99.96%
Removal
BTEX
$0.38
0.38
0.64
0.91
1.40
0.91
$2.31
Wood Treatment Facility
The groundwater under a closed wood treatment
facility in Nashua, New Hampshire, had widespread
contamination due to leaking storage tanks and past
disposal practices. Contaminants included phenol
and POP. After extensive bench testing, the selected
treatment processes were filtration followed by
oil/water separation followed by UV radiation/
oxidation. An ULTROX®F-650 treatment system was
installed in April 1986 and has been operating on a
24 hour per day basis since then. Operating
conditions and treatment costs are as follows:
Flow Rate:
Influent Concentration:
Effluent Concentration:
Treatment Costs:
Ozone (@ 0.06/kWh)
UV (incl. power and
annual lamp
replacement)
O&M Cost
Capital Amortization
(16%/year)
Total Treatment Cost:
40 gpm
5 ppm phenol,
100 ppb PCP
< 0.1 ppm phenol,
< 0.1 ppb PCP
$/1.000 gallons
$0.50
0.35
0.85
0.75
$1.60
Cost Information
Table B-5 represents the direct O&M costs for
treatment of contaminants in groundwater at water
supply sites. The costs are based upon pilot plant
studies at four different sites in Southern California.
At three of the sites, PCE and TCE were the
contaminants with concentrations ranging from 20 to
200 ppb.
Table B-6 presents costs for treatment of wastewater
and groundwater at various permanent industrial
installations. Costs are presented as dollars per 1,000
gallons treated. For hydrazines, a small volume of
water is treated per day on a batch basis and a
comparatively long reaction time is needed. UV
radiation/oxidation was found to be the most cost-
effective method of destroying the three types of
hydrazines and the nitrosamine that is formed as a
by-product of the oxidation. The UV
radiation/oxidation system replaced a chlorination
unit, which produced chlorinated organic by-
products.
The price range of UV radiation/oxidation equipment
is presented in Table B-7. Capital costs for various
installations vary from $45,000 to $300,000
(uninstalled). Costs depend on the oxidants required,
their estimated dosages, the chemical structure of the
organic compounds treated, the number of UV lamps
required, and the retention time required to achieve
an acceptable discharge.
Summary
Over the last 15 years, UV radiation/oxidation has
progressed from research and development to
commercial operation. During these years, Ultrox
International has advanced its treatment system
design through applied bench testing, pilot studies,
and full-scale systems to remove contaminants from
a wide variety of wastewaters and groundwaters. UV
radiation/oxidation technology is not suitable for
every organic contamination problem. It can,
however, effectively address a wide range of cleanup
needs. This form of on-site chemical oxidation can
offer real advantages over conventional treatment
techniques and should be considered when
evaluating water treatment alternatives.
40
-------
Table B-5. Direct Operation and Maintenance Costs Using UV Radiation/Oxidation for Water Supplies
Type of Water
Contaminated potable
drinking groundwater
Contaminated potable
drinking groundwater
Contaminated potable
drinking groundwater
Contaminants
TCE, PCE
TCE, PCE
Color
Contaminant
Concentration
less than 20 ppb
200 ppb
70 color units
Discharge to
Drinking water supply
Drinking water supply
Drinking water supply
Direct O&M Cost Range
($/l,OOOgal)
0.10 to 0.20
0.20 to 0.30
0.10 to 0.1 5
Notes: 1. Assumes cost of electrical energy is $0.06/kWh.
2. PCE: tetrachloroethylene; TCE: trichloroethylene
Table B-6. Direct Operation and Maintenance Costs Using UV Radiation/Oxidation at Industrial Installations
Type of Waste
Wood treatment
wastewater
Contaminated
groundwater
Scrubber wastes
Contaminated
groundwater
Contaminated
groundwater
Contaminated
groundwater
Wastewater
Contaminants
Pentachlorophenol
and phenol
Pentachlorophenol
and phenol
Hydrazine,
monomethyl-
hydrazinee,
unsymmetrical-
dimethylhydrazine
TCE, trans-DCE,
methylene chloride
TCE, TCA, DCA,
PCE, methylene
chloride, VC
THF
Phenol
Total Contaminant
Concentration
50 ppm
5 ppm
5,000 ppm
5 ppm
600 ppb
1 ppm
90 ppm
Discharge to
POTW
POTW
Biotreatment plant
on-site
Surface Water
POTW
Ground
POTW
Daily Volume Treated
(gpd)
30,000
86,400
600 to 1 ,500
300,000
72,000
216,000
4,300
Direct O&M Cost
Range ($/1 ,000 gal)
1.25-1.35
0.90-1.00
86.
0.47
0.33
0.39
6.48
Notes: 1. Assumes cost of electrical energy is $0.06/kWh.
2. DCA: dichloroethane; PCE: tetrachloroethylene; POTW: publicly-owned treatment works; TCA: trichloroethane; TCE:
trichloroethylene; THF: tetrahydrofuran; trans-DCE: trans-dichloroethylene; VC: vinyl chloride.
41
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Table B-7. Typical Capital Costs for UV Radiation/Oxidation Systems
Type of Waste
Wood treatment
wastewater
Contaminated
groundwater
Scrubber wastes
Contaminated
groundwater
Contaminated
groundwater
Contaminated
groundwater
Wastewater
Contaminants
Pentachlorophenol, phenol
Pentachlorophenol, phenol
Hydrazines
TCE, trans-DCE,
methylene chloride
TCE, TCA, DCA, PCE,
methylene chloride, VC
THF
Phenol
Total Contaminant
Concentration
150 ppm
5 ppm
5,000 ppm
5 ppm
600 ppb
1 ppm
90 ppm
Water Flow Rate (gpd)
30,000
86,400
600-1,500
300,000
72,000
216,000
4,300
Price Range (uninstalled)
($)
125,000-150,000
175,000-200,000
125,000-150,000
225,000-275,000
130,000-150,000
250,000-300,000
45,000-55,000
Notes: 1. Assumes cost of electrical energy is $0.06/kWh.
2. DCA: dichloroethane; PCE: tetrachloroethylene; TCA: trichloroethane; TCE: trichlqroethylene; THF: tetrahydrofuran; Trans-DCE:
trans-dichloroethylene; VC: vinyl chloride.
42
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Appendix C
Site Demonstration Results
43
-------
Appendix C Contents
Page
Introduction 46
Site Characteristics 46
Waste Characteristics 47
Review of Technology and Equipment Performance 48
Review of Treatment Results 51
References 53
44
-------
Figures
Number
C-1 Lorentz barrel and drum site location
C-2 General geologic cross-section
Page
47
48
Tables
C-l Performance Data for Reproducible Runs 51
45
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Appendix C
Site Demonstration Results
Introduction
In 1947, Lorentz Barrel and Drum (LB&D) began
recycling drums at its facility in San Jose, Santa
Clara County, California. Other industrial uses at
the site included auto wrecking, roofing and
construction, sandblasting, and auto junkyard.
Drums for recycling were received from over 800
private companies, as well as military bases,
research laboratories, and county agencies in
California and Nevada. These drums generally
contained residual aqueous wastes, organic solvents,
acids, metal oxides, and oils.
As part of normal operations at the site, residual
wastes from drums and wastewaters from cleaning
drums were disposed of in an on-site drainage ditch.
From the ditch, these wastes were routed to a large
sump located in the northeast corner of the site. Prior
to 1968, wastewater from the sump was discharged to
the storm drain system. Sometime between 1968 and
1971, the discharge was diverted to the sanitary
sewer. This practice was discontinued between 1983
and 1984; subsequently, liquid wastes were
reportedly reduced in volume by evaporation and
then drummed and disposed of off-site as hazardous
waste (Ebasco, 1988).
In 1987, LB&D ceased operation at the site due to a
temporary restraining order from the Santa Clara
County District Attorney's Office. Later, the U.S.
EPA (Region IX) assumed lead agency responsibility
for site remediation and initiated a remedial
investigation/feasibility study.
The material presented in this appendix briefly
summarizes the work performed during the SITE
demonstration and the results presented in the
Technology Evaluation Report (EPA, 1989).
Ultrox Technology Evaluation and the SITE
Program
The Ultrox UV radiation/oxidation technology was
evaluated by Region IX as part of the engineering
evaluation/cost analysis of remedial alternatives and
through a treatability study. The treatability study
was successful in demonstrating that the technology
could treat the contaminated groundwater at the
LB&D site (Ebasco, 1988).
Ultrox International submitted a proposal under
EPA's SITE Program to demonstrate the Ultrox
technology at the LB&D facility. Because of the
promising results of the treatability study, and
because Region IX needed additional data to
complete its decision-making for Phase I remediation
of groundwater at the site, the Ultrox technology
demonstration was put on an accelerated schedule.
The field demonstration was conducted from
February 24 through March 9,1989.
Site Characteristics
When LB&D began operating, the site comprised
10.5 acres (Figure C-l). Since then, half of the
original property has been sold, resulting in the
current L-shaped site which covers 5.25 acres. This
area is suspected to contain the highest levels of
contamination. The site is surrounded by a chain-
link fence to prevent unauthorized access.
The site slopes gently from the southwest to the
northeast corner. The highest elevation at the
southwest corner is 106 feet, aruLthe lowest point at
the northeast corner is 102 feet above mean sea level.
The water table at the site is approximately 20 feet
below ground surface (Figure C-2). The actual
aquifer thickness, seasonal water table fluctuations,
and the hydraulic characteristics of the clay aquitard
are unknown. As is typical with water table aquifers,
the shallow groundwater flow appears to follow the
ground surface topography, flowing northeast toward
Coyote Creek, a local watercourse, less than 1/2 mile
east of the site.
The climate in the area is characterized by warm, dry
summers and cool, wet winters. Annual minimum
temperatures are generally a few degrees below
freezing, while maximum temperatures in excess of
100°F are common. Normal January and July daily
average temperatures are 49.5°F and 68.8°F,
respectively. The temperature at the site during the
demonstration varied from the upper 50°F to upper
60°F range. Normally, average annual rainfall in the
46
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•VJ
San Jose
Muni Baseball
Stadium
Figure C-1. Lorentz barrel and drum site location.
area is 13.9 inches, most of which occurs from
November through April. During the last few days of
the demonstration, there was intermittent rainfall at
the site.
The LB&D site is located in an area zoned for
manufacturing, at the southwest corner of East Alma
Avenue and South Tenth Street. The site is located
just south of land zoned as residential. This
residential zone includes San Jose State University's
(SJSU) football stadium (Spartan Field and Spartan
Stadium) and recreation fields, as well as the San
Jose Municipal Baseball Stadium. SJSU University
student housing (the closest residential area) is
located about a quarter mile north of the site.
Surface water runoff from the LB&D site is routed to
Coyote Creek via a 60-inch diameter storm drain at
the corner of East Alma Avenue and South Tenth
Street. This drain flows to Coyote Creek under Alma
Avenue. A secondary 18-inch storm drain runs
northwest under South Tenth Street and connects
with the 60-inch diameter storm drain.
Coyote Creek flow rates are regulated by the Coyote
and Anderson reservoirs. An average flow rate of 45
cubic feet per second (cfs) has been recorded between
1970 and 1983. A maximum flow rate of 5,000 cfs was
recorded in March 1983. Zero flow rate has been
recorded for short durations in the fall.
Waste Characteristics
The drum recycling operations over a 40-year period
are the principal causes for the site's contaminated
groundwater. Remedial investigations carried out by
state and Federal agencies from 1983 to 1987 have
indicated that the soils and the shallow groundwater
at the LB&D site are contaminated with VOCs,
pesticides, PCBs, and metals. These investigations
have also indicated that groundwater downgradient
of the site is contaminated with VOCs (Ebasco, 1988).
The organic contaminants measured in the on-site
groundwater from 1983 to 1987 range in
concentration from 0.2 ppb for chlordane, a pesticide,
to 2,108 ppb for TCE, a VOC. Organic contaminants
measured in the off-site groundwater range from 0.5
ppb for chloroform to 311 ppb for TCE (Ebasco, 1988).
Remedial activities at the site addressing soil
contamination have involved the excavation of four
major "hot spot" drainage and sump areas. Activated
carbon adsorption and UV radiation/oxidation
treatment technologies were evaluated to clean up
the groundwater. Since the Ultrox technology is best
suited for destroying dissolved organic contaminants,
such as chlorinated hydrocarbons and aromatic
compounds, found in groundwater or wastewater
with low levels of suspended solids, the shallow
groundwater at the LB&D site was selected as the
waste stream to demonstrate the Ultrox technology.
Groundwater Sampling for the SITE
Demonstration
In anticipation of the SITE demonstration,
groundwater samples were collected in December
1988 from wells at and near the LB&D site. Samples
were collected from three off-site wells and two on-
site wells near the location of the technology
demonstration. Several VOCs detected at relatively
high levels included acetone (160 ppb); 1,1-
dichloroethylene (180 ppb); 1,2-trans-
dichlorqethylene (200 ppb); TCE (920 ppb); and vinyl
chloride (240 ppb). VOCs detected in all five wells
included 1,1-dichloroethylene; 1,2-trans-
dichloroethylene; 1,1,1-trichloroethane (1,1,1-TCA);
and TCE. No semivolatiles, PCBs, or uncharacterized
pollutants were detected. Based on these results, four
extraction wells were installed in the northeastern
corner of the site to collect contaminated
groundwater for the SITE demonstration.
During the demonstration, influent samples collected
during the test runs were analyzed to characterize
groundwater contamination and measure removal
efficiencies. Laboratory analytical parameters
measured during the test runs included the
following: VOCs, TOG, metals, semivolatiles, PCBs,
and pesticides. Field testing parameters included pH,
alkalinity, conductivity, temperature, and turbidity.
47
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110—1
100—
90—
zs- 80 —
•8
5
-J 70-
CO
CD
Water Level •
Oct. 1986
Clay and Silt
60 —
50 —
40—
30 —
20—'
Figure C-2. General geologic cross-section.
Scale
H:1" - 50'
V: 1" = 10'
Clay
Sand and Gravel
The groundwater was contaminated primarily with
VOCs such as TCE and vinyl chloride, at levels of 100
and 40 ug/L, respectively. Other VOCs present at
relatively low concentrations (in the range of 5 to 15
ug/L) included 1,1-dichloroethane (1,1-DCA), 1,1,1-
TCA, 1,2,-dichloroethane (1,2-DCA), benzene,
chloroform, and tetrachloroethylene. No PCBs,
semivolatiles, or pesticides were detected in the
influent. During the demonstration period, there was
a 30 to 50 percent decrease in the influent VOC
concentrations. This decrease was probably due to
VOC volatilization, although bladder tanks were
used to minimize the VOC losses.
The TOG concentration of the groundwater was about
25 mg/L. However, the concentration of priority
pollutants (VOCs and semivolatiles) was only about 2
percent of the TOG concentration.
During the demonstration, the pH and alkalinity of
the groundwater were about 7.2 and 950 mg/L as
CaCOs, respectively. These measurements indicated
that the bicarbonate ion (HCO3"), which acts as an
oxidant scavenger, was present at high levels. Other
oxidant scavengers such as bromide, cyanide, and
sulfide were not detected. Since the Ultrox
technology is based on an oxidation process, any
other species present in the contaminated water
which consume oxidants were viewed as an
additional load for the system.
Review of Technology and Equipment
Performance
The technology demonstration was divided into three
phases: (1) site preparation (approximately 3 weeks),
(2) technology demonstration (approximately 2
weeks), and (3) site demobilization (approximately 3
weeks). The activities and a review of technology and
equipment performance during these phases are
described below.
Site Preparation
Site preparation included setting up major support
equipment, on-site support services, and utilities.
48
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These activities and equipment requirements are
described as follows.
To accommodate the demonstration program
schedule, Region IX installed four groundwater
extraction wells at the LB&D site in January 1989.
The wells were necessary to obtain sufficient
groundwater from the most contaminated area of the
LB&D site for the technology demonstration test
runs. Once installed and developed, the four wells
were pumped to estimate groundwater yields.
From February 20 to 23, 1989, approximately 13,000
gallons of contaminated groundwater from the LB&D
site were collected from the extraction wells. Only
three of the four wells installed were needed to obtain
the necessary groundwater for the demonstration.
Major Support Equipment
Two 7,500-gallon bladder tanks were used to hold the
groundwater collected from the site. These tanks
were flexible and made of a synthetic material
suitable for potable water storage. The bladder tanks
were selected to minimize VOC losses during the test
period.
Three dedicated, submersible pumps were used to
pump the groundwater into the bladder tanks. The
maximum and average pumping rates were
approximately 5 and 1 gpm per pump, respectively.
The bladder tanks and pumps were connected using
piping manifolds so that both tanks could be filled
simultaneously. From the bladder tanks, the
groundwater was pumped to the Ultrox unit.
A commercial-size (150-gallon) Ultrox unit, Model
PM-150, was delivered by truck van. This unit has
four skid-mounted modules designed for transport
with either a flatbed truck or in an enclosed trailer.
The unit was unloaded using a fork lift on February
21,1989.
A 21,000-gallon storage tank was used to store
effluent from the Ultrox system. The tank was steam
cleaned prior to delivery to the site. In addition,
several 55-gallon, open-top drums were used to store
wastewater generated during the sample collection
activities, laboratory analyses, and decontamination
procedures.
On-Site Support Services
On-site laboratory analyses were conducted in a field
trailer. The field trailer also served as an office for
field personnel, provided shelter and storage for
small equipment and supplies, and acted as a base for
site security personnel. Two chemical toilets were
located near the trailer.
Although the LB&D site perimeter is enclosed by a
fence, a commercial security service was hired to
provide additional protection from equipment
vandalism during evening hours and weekends.
Utilities
Utilities required for the Ultrox system
demonstration included telephone, water, and
electricity service. A single telephone line was
installed in the trailer. Telephone service was
required to order supplies, coordinate site activities,
and provide communication. Tap water was required
for equipment and personnel decontamination.
Water used for equipment and personnel
decontamination was provided using existing site
pipelines.
Electrical service was connected to the site from a
public utility. Electricity was required to operate the
Ultrox system, the office trailer, and the laboratory
equipment. The Ultrox system required 480-volt, 3-
phase electrical service, which was provided through
a 100-amp service using a dedicated meter and a
transformer. An additional 110-volt, 100-amp service
was connected to another dedicated meter to provide
power to the office and laboratory trailer.
Technology Demonstration
Approximately 13,000 gallons of contaminated
groundwater were treated by the Ultrox system in 13
test runs over a 2-week period, with 1 or 2 test runs
performed each day. During this period, there were
no significant variations from the proposed
demonstration schedule. This section discusses
operational and equipment problems and health and
safety issues associated with the SITE
demonstration.
Operational Problems
During the course of the field demonstration, two
operational problems with the electrical power
supply were encountered. These problems were a
wiring problem discovered during Run 2 which
affected electricity measurements and an electrical
power shutdown at the end of Run 9, which was
caused by a minor accident at the site.
During Run 2, it was discovered that both the trailer
and the Ultrox system were insidvertently wired to a
common meter. As a result, separate watt-hour
meters and service panels were installed for the
Ultrox system and the on-site trailer. An electrical
subcontractor rewired and set each meter properly,
and the electrical energy consumption for the first
two runs was estimated by analyzing the power
consumed on subsequent runs. Based on the
electrical energy consumption observed in Runs 3 to
49
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13, the electrical energy consumption by the trailer
appeared to be negligible.
At the end of Run 9, a trailer truck entered the site
and accidentally broke the wooden power pole that
supported the electric power lines by catching the
sagging lines with the trailer. Although the accident
did not cause any injury to the people working on-site
or damage any equipment, as a precautionary
measure, the power was shut off, and the electrical
subcontractor was contacted to install a new power
pole. A stronger pole was installed and power
restored the following morning.
To circumvent this accident, electrical lines could
have been buried at the site. Although the cost of the
demonstration would have increased, a safer work
atmosphere would have been provided. As an
alternative, the lines could have been placed clear of
any possible transportation routes or elevated to a
height necessary to accommodate truck clearance.
Portable electrical generators could also have been
provided as a backup.
Equipment Problems
During normal operations, the Decompozon unit,
which is equipped with a heater, is .designed to
destroy ozone in the reactor off-gas. After Run 8,
however, the heater malfunctioned. As a result, the
temperature in the unit, which should normally be
140°F for the unit to function properly, was about
80°F. The effect of this heater failure is reflected in
the ozone concentrations in the Decompozon unit
exhaust For Runs 1 through 8 there was greater
than 99.9 percent ozone destruction, and ozone
concentrations in the exhaust were quite low (<0.1
ppm). However, ozone concentrations in the exhaust
were approximately 1 ppm for Runs 9 and 10, and
greater than 10 ppmfor Runs 11,12, and 13.
At its permanent installations, Ultrox incorporates
interlocks for emergency automatic shut-off of the
treatment unit if the heater fails so that operating
personnel will not be exposed to ozone even for short
periods. This feature should be incorporated at other
similar demonstrations.
Health and Safety Considerations
Work zones were established to minimize the
transfer of hazardous materials and contaminated
debris from potentially contaminated areas to "clean"
areas at the site. For the demonstration, the
contaminant reduction zone was combined with the
exclusion zone. The work zone contained the Ultrox
system and associated equipment, power connections,
55-gallon drums used to separately store wastewater
and contaminated debris, the two 7,500-gallon
bladder tanks, and the 21,000-gallon steel storage
tank used for effluent wastewater storage.
In general, health hazards associated with the
demonstration resulted from exposure to the
contaminated groundwater. Although the treatment
system was entirely closed, the potential routes of
exposure during the demonstration were inhalation,
ingestion, and skin and eye contact from possible
splashes or spills during sample collection.
All personnel working in this 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-
toed safety boots were required in the exclusion zone.
Personnel working in direct contact with
contaminated groundwater wore modified Level D
protective equipment, including safety shoes, latex
inner gloves, nitrile or Viton outer gloves, and safety
glasses.
Equipment Demobilization
Groundwater remaining in the bladder tanks after
the final test run was treated by the Ultrox system
and pumped to the effluent storage tank. Similarly,
miscellaneous liquid wastes which had been stored in
55-gallon drums during the test period were treated
by the Ultrox system and pumped to the storage tank.
These miscellaneous liquids consisted of well
development water, excess sample volumes
generated during sampling operations, and spent
chemical reagent wastes produced from on-site
laboratory analyses.
All effluent was temporarily stored in the tank prior
to discharge. After the effluent was analyzed to
ensure that it met the applicable NPDES standards,
it was discharged into a storm drain which emptied
into Coyote Creek, a nearby waterway. All collected
effluent was held for approximately 2 weeks before
discharge, awaiting laboratory test results.
Contaminated materials, such as empty sample
containers, laboratory wastes, and disposable
protective equipment generated during the
demonstration, were placed in a 55-gallon, open-top
drum. These materials contained only residual
contamination. During the demobilization phase, the
wastes were packaged and stored before being
disposed of off-site by Region IX.
The Ultrox unit was loaded on a trailer truck and
transported to another site to treat contaminated
groundwater.
50
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Review of Treatment Results
The demonstration was designed to evaluate the
Ultrox technology by controlling the system's five
operating parameters: hydraulic retention time,
ozone dose, hydrogen peroxide dose, UV radiation
intensity, and influent pH level. During the test
runs, these operating parameters were varied and the
system's performance was evaluated under each
resulting set of operating conditions.
VOCs were selected as the critical parameters for
evaluating the effectiveness of the Ultrox technology,
because the Ultrox technology was developed
primarily to treat organics (such as VOCs,
semivolatiles, and PCBs/pesticides). Of these
organics, only VOCs were found in the groundwater
samples collected in December 1988. As such, the
performance of the Ultrox system for each test run
was evaluated based on its effectiveness at removing
indicator VOCs.
The three indicator VOCs selected were TCE, 1,1-
DCA, and 1,1,1-TCA. TCE was selected because it is
a major volatile contaminant at the site, and the
latter two VOCs were selected because, from Ultrox's
experience, they are relatively difficult to oxidize.
Only three indicator VOCs were selected because of
analytical time constraints to perform the tests over
the 2-week period. Full VOC analyses were also
performed for all test runs following completion of
the demonstration.
To assess the effectiveness of the technology
performance, the concentration of total VOCs was
estimated by adding the concentration of each VOC.
Since this study only uses the total VOC data for
qualitative interpretation, this approach is
considered practical and useful from an engineering
perspective.
"Preferred" Operating Conditions
As part of the technology demonstration, the system's
performance during Runs 1 through 11 was
evaluated to determine "preferred" operating
conditions, given the nature of contaminated
groundwater at the site. For the Ultrox technology
demonstration, the "preferred" operating conditions
were defined as the set of operating parameters
where the effluent concentrations of indicator VOCs
were below their respective NPDES limits and the
relative operating costs were the lowest.
The initial operating conditions selected for Run 1
were expected to approximate optimum operating
conditions, based on the results of the groundwater
treatability study. From Run 1, the selection of
operating conditions for Runs 2 to 11 proceeded in an
interactive manner, with the results of previous runs
setting operating conditions for subsequent runs.
To set operating conditions for subsequent runs, the
results from the overnight analysis of one-third of the
previous run's samples were evaluated. Specifically,
only two of the six replicate samples collected at each
of the three liquid sampling locations (influent,
midpoint, and effluent of the reactor) were analyzed
overnight by gas chromatography (GC), for the three
indicator VOCs. Only one-third of the samples could
be analyzed overnight, due to analytical time
constraints.
Based on the analyses of two replicate VOC samples
for each of the first 11 runs, only Runs 8 and 9 had
average effluent concentrations of indicator VOCs
that were below their respective NPDES limits. Of
Runs 8 and 9, a lower hydrogen peroxide dose was
used in Run 9. As a result, the operating conditions
for Run 9 were determined to be the "preferred"
operating conditions. These conditions included a
hydraulic retention time of 40 minutes, ozone dose of
110 mg/L, hydrogen peroxide dose of 13 mg/L, all 24
UV lamps (at 65 watts each) operating, and influent
pH of 7.2 (unadjusted).
Subsequently, Runs 12 and 13 were performed using
the "preferred" operating conditions determined from
Run 9. The results from these latter two test runs
were used to evaluate if performance levels were
reproducible. A summary of the results for
reproducible runs is presented in Table C-l.
Table C-1. Performance Data for Reproducible Runs
Run 9
TCE
1,1 -OCA
1,1,1-TCA
Total VOCs
Run 12
TCE
1,1 -DCA
1,1,1-TCA
Total VOCs
Run 13
TCE
1,1 -DCA
1,1,1-TCA
Total VOCs
Mean
Influent
(H9/L)
65
11
4.3
170
52
11
3.3
150
49
10
3.2
120
Mean
Effluent
(yg/L)
1.2
5.3
0.75
16
0.55
3.8
0.43
12
0.63
4.2
0.49
20
Percent
Removal
98
54
83
91
99
65
87
92
99
60
85
83
After the demonstration, complete analyses of all
replicate samples from the 13 test runs were
performed. From these results, the mean
concentration of 1,1-DCA in the effluent of Run 9 was
actually found to be slightly higher than 5 ug/L, the
discharge standard for the compound. However, these
51
-------
results were not available until after the
demonstration. Operating conditions for Run 9 are
still considered to be "preferred" since the mean
effluent concentration was quite close to the
discharge standard.
Quantifiable Results
The Ultrox process achieved removal efficiencies
(RE) as high as 90 percent for the total VOCs present
in the groundwater at the LB&D site. Based on the
data for individual VOCs, REs for TCE were greater
than 99 percent, and REs for 1,1-DCA and 1,1,1-TCA
were as high as 65 and 85 percent, respectively.
The REs for the three indicator VOCs were
dependent on the operating conditions. For example,
the REs for the three indicator VOCs generally
decreased considerably in Run 7. This decrease was
most likely due to the decreased ozone dose in that
run.
In Runs 9, 12, and 13, which were all run at the
"preferred" operating conditions, the REs for each
indicator VOC did not differ. That is, the technology
performance levels were reproducible under the same
operating conditions. In general, the REs for TCE
were higher than those for 1,1-DCA and 1,1,1-TCA.
This is expected, since 1,1-DCA and 1,1,1-TCA were
selected intentionally because they are relatively
difficult to oxidize.
A comparison of the 95 percent upper confidence
limit (UCL) values for effluent VOC concentrations
in Runs 12 and 13 with the discharge standards
indicated that the effluent met the discharge
standards for all regulated VOCs. However, in Run 9,
the effluent did not meet the discharge standards for
1,1-DCA and 1,2-DCA. This difference in
performance among Runs 9, 12, and 13 is negligible
and may be attributed to the higher influent VOC
concentrations in Run 9 than in Runs 12 and 13.
Since the mean effluent VOC concentrations of 1,1-
DCA and 1,2-DCA are higher than the discharge
standard, statistical inferences at other confidence
levels (such as 90 percent) will not be different.
VOC Removal Due to Stripping
The potential for VOC removal due to stripping was
evaluated since ozone gas was bubbled through the
groundwater treated by the Ultrox system. The VOC
air sampling data indicated that stripping
contributed significantly to the total removal,
(chemical oxidation plus stripping) of 1,1,1-TCA and
1,1-DCA. Specifically, stripping accounted for 12 to
75 percent of the total removals for 1,1,1-TCA, and
for 5 to 44 percent of the total removals for 1,1-DCA.
For compounds such as TCE and vinyl chloride,
stripping accounted for less than 10 percent of the
total removal, as oxidation was found to be the major
removal mechanism. For other VOCs such as 1,1-
dichloroethylene, 1,2-dichloroethylene, benzene,
acetone, and 1,1,2,2-tetrachloroethane, stripping was
negligible since only occasional traces of these
compounds were detected in the_off-gas.
Final Products of the Treatment Process
The developer claims that the final products of the
oxidation of organic compounds in water are salts,
water, carbon dioxide, and possibly some organic
products. However, during the demonstration, no
significant TOC removals were achieved in the
treatment system, which implies that only partial
oxidation occurred; as such, the predominant final
products were not carbon dioxide and water. In
addition, since no new VOCs were found by GC and
GC/mass spectrometry (MS) analysis of the effluent,
the final oxidation products do not appear to be new
VOCs. Instead, the final products may be organic
acids, which were analyzed as TOC in the TOC
analysis. Neither semivolatiles nor PCBs/pesticides
were detected in the effluent. Consequently, the
Ultrox unit did not generate any of these compounds.
Metals such as iron and manganese were detected in
the influent at low concentrations. After treatment,
no significant metal removal was observed.
Field Parameters
Field parameters measured during the test runs
included pH, alkalinity, conductivity, temperature,
and turbidity. The effect of the treatment process on
field parameters are described below.
The pH increased by 0.5 to 0.8 units after treatment.
The pH increase indicates that partial oxidation of
organics occurred to produce organic acids and that
complete oxidation to CO2 did not occur, which would
result in a pH decrease. However, the pH increase is
not surprising because the groundwater had high
alkalinity and an initial pH of about 7.2, at which the
predominant form of alkalinity was bicarbonate. The
reaction of hydroxyl radicals with bicarbonate or
carbonate ion yields hydroxyl ions (Hoigne and
Bader, 1975). The production of hydroxyl ions due to
this reaction would have caused an increase in pH.
No change in alkalinity was observed after the
treatment.
The temperature increased by approximately 2 to 3
degrees Celsius after the treatment. This increase
was mainly due to the heat from the UV lamps and
not the oxidation of organics, because the
temperature increase was higher than usual when
the hydraulic retention time was increased from 40
minutes to 1 hour (Run 5), and the increase was not
observed in Runs 10 and 11 when the UV lamps were
used in only three chambers.
52
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Turbidity usually increased by 1 to 4 units (NTU)
after the treatment. This slight increase in turbidity
may be due to the limited removal of metals by metal
oxidation and precipitation. No change in
conductivity was observed after the treatment.
Performance of the Decompozon Unit
The Decompozon unit destroyed ozone in the Ultrox
reactor off-gas to levels less than 0.1 ppm (OSHA
standards). The ozone destruction efficiencies were
observed to be greater than 99.99 percent.
Although the primary function of the Decompozon
unit is to remove ozone, significant VOC removals
occurred in the Decompozon unit when it functioned
as designed (Runs 1 through 8)..Specifically, volatile
organics present in reactor off-gas at levels of
approximately 0.1 to 0.5 ppm were reduced to below
detection levels in the Decompozon unit before air
was discharged to the atmosphere.
Electrical Energy Consumption
The average electrical energy consumption during
the demonstration was about 11 kWh/hour of
operation. It was noted that the electrical energy
consumption was higher in Run 7 (38 mg/L ozone
dose) than that in Run 6 (110 mg/L ozone dose), which
is contrary to what would be expected. This result
cannot be explained.
Accomplishing the Goals of the Technology
Demonstration
In addition to meeting the general objectives of the
SITE Program during the Ultrox technology
demonstration, four specific goals were identified to
serve the needs of both the SITE Program and Region
IX. These four goals, and an evaluation of how they
were met, are discussed as follows.
1. Demonstrate the ability of the Ultrox system to
treat VOCs present in the groundwater at the
LB&D site.
The Ultrox system successfully treated VOCs
present in the groundwater at the LB&D site to
meet regulatory discharge standards. REs as
high as 90 percent were achieved for the total
VOCs present in the groundwater at the LB&D
site. Specifically, for the three indicator VOCs,
REs for TCE were greater than 99 percent, and
REs for 1,1-DCA and 1,1,1-TCA were as high as
65 and 85 percent, respectively.
2. Evaluate the efficiency of the ozone decomposer
unit in treating ozone in the reactor off-gas.
The Decompozon unit destroyed ozone in the
Ultrox reactor off-gas to levels less than 0.1 ppm
(OSHA standards). The ozone destruction
efficiencies were observed to be greater than
99.99 percent.
3. Develop capital and operating costs for the Ultrox
system that can be used in Superfund decision-
making processes at other sites.
The cost of conducting the Ultrox technology
demonstration was approximately $633,000. This
cost includes site characterization and
preparation, demonstration planning and field
work, chemical analyses, and report preparation.
The developer's portion of this cost was $23,000
and the balance of $610,000 was allocated to the
SITE Program. The cost of the Ultrox unit used in
the demonstration was approximately $140,000.
4. Develop information useful to Region IX for site
remediation.
The SITE demonstration provided additional
data that will assist Region IX in completing its
decision-making for Phase I remediation of
groundwater at the LB&D site. Specifically, as a
result of the demonstration, the contaminated
groundwater was further characterized, and
actual information regarding the "preferred"
operating parameters for the Ultrox system was
obtained.
References
Ebasco Services, Inc., 1988. Various reports on the
Lorentz Barrel and Drum Site, San Jose,
California, work performed for EPA under REM
III Program, Remedial Planning Activities at
Selected Uncontrolled Substance Disposal Sites.
EPA, 1989. Technology Evaluation Report, SITE
Program Demonstration of the Ultrox
International Ultraviolet Radiation!Oxidation
Technology, EPA/540/A5-89/012.
Hoigne, J., and H. Bader, 1975. Ozonation of Water:
Role of Hydroxyl Radicals as Oxidizing
Intermediate's, Science, 190,782:784.
PRC Environmental Management, Inc., 1989. Final
Report, SITE Program Demonstration Plan for
the Ultrox International UV Radiation/Oxidation
Process, prepared for U. S. Environmental
Protection Agency, Office of Research and
Development and Office of Solid Waste and
Emergency Response.
53
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-------
Appendix D
Case Studies
55
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Appendix D Contents
Page
Introduction 58
Case Study D-l, Department of Energy, Kansas City Plant, Missouri 58
Introduction 58
Plant Description 58
Methodology 59
Results 59
Conclusions and Recommendations 60
Case Study D-2, Hewlett Packard Facility, Palo Alto, California 60
Introduction 60
Plant Description 60
Methodology 60
Results 62
Case Study D-3, FEI Microwave, Sunnyvale, California 63
Introduction 63
Plant Description 64
Methodology • • • 64
Results 64
Case Study D-4, Golf Course, City of South Gate, California 65
Introduction 65
Results 66
Case Study D-5, Xerox Facility, Webster, New York 66
Introduction 66
Plant Description 68
Methodology 68
Results 68
Case Study D-6, Koppers Industries, Denver, Colorado 68
Introduction 68
Results 68
Case Study D-7, General Electric Company, Lanesboro, Massachusetts 69
Introduction 69
Plant Description 69
Methodology 69
Results 69
References 69
56
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Tables
Number Page
D-l-1 Groundwater Treatment Plant Monitoring Plan,
Flow-Through Mode 59
D-l-2 Groundwater Treatment Plant, Batch Results 60
D-l-3 Groundwater Treatment Plant Flow Data 60
D-l-4 Groundwater Treatment Plant Total Inorganic Halogen Results ... 61
D-l-5 Groundwater Treatment Plant VOC Results 61
D-2-1 Groundwater Quality Results for Extraction Well Sampling 62
D-2-2 Operating Conditions and Analytical Results for
TestRun 1 (Batch) 63
D-2-3 Operating Conditions for Test Runs 2 through 12 (Continuous) 63
D-2-4 Analytical Results for Test Runs 2 through 12 (Continuous) 63
D-2-5 O&M Cost Estimates for Test Runs 2 through 12 (Continuous) 64
D-3-1 Groundwater Treatment Results During the Air Stripper Study ... 65
D-3-2 Operating Conditions and Analytical
Results for the Ultrox System 66
D-3-3 Oxidant Cost Estimates 66
D-4-1 Operating Conditions and Analytical Results 67
D-4-2 Daily O&M Cost Estimates for 1,250-gpm System 67
D-4-3 Capital Cost Estimates for 1,250-gpm Pressurized System 67
D-4-4 Capital Cost Estimates for 1,250-gpm Nonpressurized System 67
D-6-1 O&M Cost Estimate 69
57
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Appendix D
Case Studies
Introduction
This appendix summarizes several case studies on
the use of the Ultrox UV radiation/oxidation process.
These cases involve pilot-scale units as well as full-
scale operating units treating contaminated
groundwater and industrial wastewaters. No data on
VOC stripping are available from any of these case
studies. The information provided for these studies
varied widely with scant data available for some
operations and comprehensive analytical and
economic information for others. This appendix
summarizes the following case studies:
Case
Study Facility and Location
D-l Department of Energy, Kansas City
Plant, Missouri
D-2 Hewlett Packard Facility, Palo Alto,
California
D-3 FBI Microwave, Sunnyvale, California
D-4 Golf Course, City of South Gate,
California
D-5 Xerox Facility, Webster, New York
D-6 Koppers Industries, Denver, Colorado
D-7 General Electric Company, Lanesboro,
Massachusetts
Case Study D-1, Department of Energy,
Kansas City Plant, Missouri
Introduction
This case study presents the results of full-scale
testing of an Ultrox unit at the Allied-Signal facility
in Kansas City, Missouri. The testing is currently
being performed under contract by the U.S.
Department of Energy. Over the years, the operation
of the facility has resulted in the contamination of
groundwater by total organic halogens (TOX),
including trichloroethylene (TCE). One of the
contaminated groundwater plumes, the tank farm
plume, was selected for remediation using UV
radiation, ozone, and hydrogen peroxide. Since this
process is new and information on its performance,
costs, and operating experience is not documented,
the Oak Ridge National Laboratory was requested to
evaluate the treatment process.
Testing began during 1988, and the project is
scheduled to continue into 1990. Data from the first
year's effort are presented in a report prepared by the
Oak Ridge National Laboratory (Garland II, 1989).
The report discusses the mechanisms involved in the
treatment process, describes the treatment plant,
presents the testing methodology, evaluates the
results, and offers recommendations. Portions of this
appendix are taken directly from the report.
Plant Description
Based on results of bench-scale studies conducted by
Ultrox, a 725- gallon reactor, divided by baffles into 6
stages, was selected to treat the site groundwater at a
flow rate of 25 gpm. Ozone is supplied by a generator
capable of producing 21 Ib per day at 2 percent ozone
by weight. The air dryer provides clean, dry air to the
ozone generator at 12-15 psig.
The reactor is equipped with 72 quartz-sheathed,
low-pressure, 65-watt UV lamps located throughout
the reactor chamber. The lamps are arranged in rows
of 6, with 12 lamps in each stage. In addition, each
stage is equipped with a sight glass and a sample
port.
Up to 50 pounds per day of hydrogen peroxide can be
supplied from either of two 55-gallon storage drums.
The hydrogen peroxide is mixed with the influent
groundwater with an in-line static mixer.
Three wells are used to extract contaminated
groundwater from the tank farm plume at a rate of
approximately 6 gpm. To enhance performance by
reducing loads on the equipment, one in-line
cartridge filter is located on the influent line.
Following treatment, the plant effluent is discharged
into Kansas City's municipal sewer system.
58
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Methodology
The performance evaluation tests were conducted in
accordance with a study plan that included
monitoring the plant performance, determining the
operation and maintenance costs for the plant,
comparing the costs with other technologies,
evaluating contaminant removal mechanisms, and
assisting in optimization of the process. Initially, the
treatment plant was operated in a batch mode so that
all of the effluent could be contained and analyzed
prior to discharge. Four batch tests were performed to
demonstrate that the effluent criteria could be met.
The parameters monitored during these tests
included pH, biochemical oxygen demand, total
suspended solids, oil and grease, 13 inorganics, 34
organics, and total organic halogens.
Following the batch tests, the treatment plant was
operated in a continuous, flow-through mode with
different samples collected at various frequencies.
The monitoring plan for the flow-through mode
showing the frequencies, parameters, and sample
locations is shown on Table D-l-1.
Results
Batch Operations
The results of the batch operations for TOX indicate
that the influent had been adequately treated to meet
the discharge standard after passing the first
chamber. Most of the VOCs in the effluent were
reported at concentrations below detection limits.
The process of filtering the influent reduced all
measured VOCs to less than reportable values in
three of the four batch runs. Table D-l-2 contains the
average results from all four batch runs for a variety
of parameters that are listed in the plant's discharge
permit.
Flow-Through Operations
Although the test protocol examined numerous
parameters, only a few of the results are presented in
this discussion. The flow data for the treatment plant
are presented in Table D-l-3. Tables D-l-4 and D-l-5
contain the TOX and VOC results, respectively.
Samples were collected of the influent, before and
after the filter, of the effluent, and at all six sample
ports. The values are monthly averages of weekly
grab samples except for the single 24- hour composite
effluent sample collected once a month for TOX.
Costs
In general, cost data only reflect the period of time
that the plant was treating groundwater in the flow-
through mode of operations. During this period, the
costs totaled approximately $8,600 for routine
sampling and analysis, electricity, filters, and
Table D-1-1. Groundwater Treatment Plant Monitoring Plan,
Flow-Through Mode
Frequency Parameter3 Sample Locations'5
Continuous
Daily
Weekly
Monthly
One Time
PH
Flow
BOD
TSS
Sulfate
Sulfite
Sulfides
Nitrate
Nitrite
Ammonia
Ferrous ion
Manganous ion
TOX
VOC
TOG
Iron
Manganese
Cadmium
Chromium
Copper
Lead
Nickel
Zinc
Boron
Arsenic
Oil and grease
Total cyanide
Total plate count
Off-gas TOX
Calcium
Magnesium
Sodium
Potassium
Chloride
Fluoride
Phosphate
Carbonate
Bicarbonate
E
IBF
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E, RC
IBF, IAF, E, RC
IBF, IAF, E, RC
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
Tap
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
IBF, IAF, E
Notes: a Parameters: BOD—biochemical oxygen demand; TSS—
total suspended solids; TOX—total organic halogens;
VOC—volatile organic compounds; TOG—total organic
carbon.
b Sample Locations: E—effluent; IBF—influent before filter;
IAF—influent after filter; Tap—gas vent from reaction
chamber; RC—all six stages in reaction chamber.
hydrogen peroxide. An additional $65,500 was spent
during the entire testing program for sampling and
evaluation. The capital costs for the bench scale
study, pilot plant study, and construction of the
treatment plant were $304,000. Considering only the
operation and maintenance costs of $8,600 and the
total volume of 586,000 gallons of groundwater
treated during the 5-month flow-through mode, the
cost per volume treated is approximately $15 per
1,000 gallons.
Operations
When the plant was operating in the flow-through
mode, several shutdowns occurred. From May
through September the plant was shut down nearly
50 days primarily due to excessive ozone in the
exhaust or due to the necessity of cleaning or
59
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Table D-1-2. Groundwater Treatment Plant, Batch Results*
Parameter
BODb
Chloride
PH
TSSb
Sulfida
Arsenic
Barium
Boron
Cadmium
Chromium
Copper
Iron
Lead
Manganese
Nickel
Zinc
Cyanide
Oil and grease
Unfiltered
Influent
(mg/L)
6
45
6.9
230
0.3
0.006
—
2.11
0.007
0.016
0.67
47.6
0.63
5.07
0.022
3.81
< 0.001
6.5
Stage 1
(mg/L)
3
—
8.3
382
<0.1
0.048
0.23
0.30
0.004
0.065
0.067
32.5
0.05
13.6
0.043
0.49
< 0.001
0.7
Effluent
Stage 6
(mg/L)
2.5
8.0
8.1
71
<0.1
0.015
—
0.19
0.009
0.047
0.12
15.3
0.042
6.8
0.023
0.34
< 0.001
0.6
Standard
(mg/L)
«
—
6-10
—
10.0
0.25
—
1.0
0.69
2.77
3.38
100
0.69
20.00
3.98
2.61
2.0
10
Notes: a These are average values for the four batch tests.
bBOD—biochemical oxygen demand; TSS—total suspended
solids.
Table D-1-3. Groundwater Treatment Plant Flow Data
Month
May
June
July
August
September
Average
Flow (gal)
145,760
133,041
92,929
157,080
57,652
117,292
Flow Rate
(gpm)
5.9
5.4
5.4
7.3
10.0
6.8
Percentage of
Design Flow3
24
22
22
29
40
27
Note: "The design flow rate is 25 gpm.
replacing the spargers. On the average, an operator
at the plant spent an hour a day on monitoring and
maintenance.
Conclusions and Recommendations
The effluent standards were met consistently, and
the VOCs were eliminated in the reaction chamber.
However, the TOX concentrations in the plant
effluent were higher than those in the sixth stage of
the reaction chamber, and the TOX removal was not
as high as expected. Since the flow rate was
approximately 27 percent of the design flow rate,
while the operating parameters varied from 50
percent to full treatment capacity, higher removals of
TOX were anticipated.
A demand on the treatment chemicals was exerted by
ammonia, ferrous ion, manganous ion, and bacteria
as well as by the VOCs.
A pretreatment system is an important aspect of the
treatment plant to reduce ozone demand by removing
scavengers and to minimize the downtime caused by
clogged ozone diffusers. Precipitation in the reaction
chamber, coating of the UV lamps, and frequent
replacement of the prefilter increased the operation
and maintenance time over that expected. The plant
was out of operation 30 percent of the time, primarily
due to excessive ozone in the exhaust or for
maintenance and repair.
Operation and maintenance costs are much higher
than those predicted. The report also suggests that
the economic analysis should include costs associated
with personnel maintenance and monitoring as well
as those costs incurred by regulatory compliance
monitoring.
Case Study D-2, Hewlett Packard Facility,
Palo Alto, California
Introduction
This case study describes Ultrox's UV
radiation/oxidation project that took place at the
Hewlett Packard facility in Palo Alto, California, in
the fall of 1988. The pilot study project was part of the
state's Department of Health Services grant to
demonstrate the removal of toxic organic compounds
such as benzene, toluene, xylene (BTX), and
ethylbenzene from the groundwater. Organic
compounds such as these are solvents typically used
in electronic and other manufacturing facilities.
Groundwater contamination at the Hewlett Packard
facility was discovered in 1982 and was traced to
leaking underground chemical storage tanks. In
1988, a GAG filter system was installed to treat
groundwater from three wells.
Plant Description
To accommodate the existing GAC treatment system,
the Ultrox unit was installed upstream of the carbon
filters so that the usual treatment system could
operate when the Ultrox unit, was not being tested. A
security fence was erected to protect the equipment
from tampering, and a tent was provided to shelter
the equipment from inclement weather.
Prior to treatment, groundwater was stored in a 450-
gallon tank where some volatilization could have
occurred. After the water was treated by the Ultrox
reactor, it was pumped through the GAC system and
discharged into a sewer.
Methodology
The main objective of this pilot demonstration was to
meet the same discharge limitations as specified by
regulatory agencies. These requirements were to
reduce the level of total toxic organics (TTO) to less
than 1,000 ug/L with no specific constituent greater
than 750 ug/L and to reduce the BTX, 1,1,1-TCA, and
1,2-DCA contaminants to less than 5 ug/L.
60
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Table D-1-4. Groundwater Treatment Plant Total Inorganic Halogen Results
Total Inorganic Halogens (mg/L)a
Reaction Chamber Stages
Effluent
% Removal15
Month
May
June
July
August
September
Average
Standard
IBF<=
0.351
0.383
0.186
0.296
0.318
0.307
NAo
lAFc
0.304
0.218
0.173
0.340
0.268
0.261
NA
1
0.159
0.107
0.110
0.188
0.177
0.148
NA
2
0.087
0.064
0.100
0.141
0.145
0.107
NA
3
0.134
0.061
0.087
0.069
0.110
0.092
NA
4
0.094
0.052
0.110
0.062
0.114
0.086
NA
5
0.063
0.042
0.061
0.059
0.103
0.066
NA
6
0.067
0.028
0.051
0.053
0.095
0.059
NA
Grab
0.073
0.064
0.040
0.081
0.120
0.076
0.16
Comp.
0.090
0.085
0.048
0.147
—
0.09
0.16
Grab
76
71
77
76
55
71
NA
Comp.
70
61
72
60
66
NA
Notes: a All samples are weekly grab samples (averaged monthly) except for the composite effluent sample, which is a single 24-hour
composite sample.
b Percent removal values use the IAF values for initial concentrations.
c IBF = influent before filter; IAF = influent after filter; NA = not applicable.
Table 0-1-5. Groundwater Treatment Plant VOC Results
Volatile Organic Compounds (mg/L)a
Reaction Chamber Stages
Parameter
IAF»
EFFb
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
1 ,1 -Dichloroethylene
1,1-Dichloroethane
1 ,2-Dichloroethylene (Total)
Chloroform
1 ,2-Dichloroethane
2-Butanone
1,1,1 -Trichloroethane
Carbon Tetrachloride
Vinyl Acetate
Bromodichloromethane
1 ,2-Dichloropropane
cis-1 ,3-Dichloropropene
Trichloroethylene
Dibromochloromethane
1,1 ,2-Trichloroethane
Benzene
trans-1 ,3-Dichloropropene
Bromoform
4-Methyl-2-pentanone
2-Hexanone
Tetrachloroethylene
7,1 ,2,2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Xylene (Total)
<0.010
< 0.010
0.015
<0.010
0.021
< 0.005
< 0.005
0.014
0.019
0.714
0.007
< 0.005
< 0.005
0.014
< 0.005=
< 0.005
< 0.005
< 0.005
< 0.005
0.520
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.042
< 0.005
0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.010
< 0.010
0.010
< 0.010
0.007
< 0.005
< 0.005
0.017
0.020
0.856
0.006
< 0.005
< 0.005
0.013
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.573
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.050
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
<0.010
<0.010
0.010
<0.010
0.016
< 0.005
< 0.005
0.005
0.010
0.113
0.005
< 0.005
< 0.005
0.008
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.088
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.011
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
<0.010
<0.010
< 0.010
<0.010
0.014
< 0.005
< 0.005
0.005
0.007
0.034
0.006
< 0.005
< 0.005
0.006
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.025
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.005
0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
<0.010
< 0.010
0.010
< 0.010
< 0.005
< 0.005
< 0.005
< 0.005
0.006
0.011
0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.008
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.010
< 0.010
0.010
< 0.010
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.008
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.006
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.010
<0.010
0.010
<0.010
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
<0.010
< 0.010
0.010
< 0.010
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.010
< 0.010
0.010 v
< 0.010
< 0.005
< 0.005
< 0.005
< 0.005 ,
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005 .
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
0.005
< 0.005
< 0.005
< 0.005
< 0.005
< 0.005
Notes: a Values are averages for all analyses performed from May through August 1988. No analyses were performed in September. All
samples were weekly grab samples.
b BF—influent before filter; IAF—influent after filter; EFF—effluent.
« Carbon tetrachloride was below detectable limits in all analyses except one, in which it was at the detectable limit (0.005 mg/L).
The results of analytical testing on the three
extraction wells used to collect the groundwater are
shown on Table D-2-1. From this list of compounds,
benzene, ethylbenzene, xylene, and toluene were
selected for further examination in the pilot study
because they had higher concentrations than 1,2-
61
-------
Table D-2-1. Groundwater Quality Results for Extraction Well Sampling
Sample
Location
EW-1
EW-2
Well No. 29
Combined
Influent
Date
1-19-88
1-20-88
1-21-88
2-19-88
1-19-88
1-20-88
1-21-88
2-19-88
1-19-88
1 -20-88
1-21-88
2-19-88
2-19-88d
3-22-88
4-07-88
4-19-88
5-24-88
Acetone3
34,000
27,000
28,000
43,000
28,000
15,000
19,000
62,000
ND
5,100
44,000
23,000
43,,000
61,000
35,000
51,000
36,000
1,2-DCA3
510
440
380
310
870
820
830
480
350
350
450
710
420
NDe
NDe
290
NDe
TCE3
260
ND
ND
ND
890
890
980
1,500
ND
ND
ND
ND
460
NDe
NDe,
460
NDe
Benzene3
7,800
6,900
6,100
4,400
8,100
7,900
8,000
5,800
7,400
6,900
7,800
12,000
6,100
5,000
• 4,100
3,800
. 3,200
Toluene3
1,200
1,100
830
730
1,800
1,900
1,700
1,400
7,500
7,700
8,700
11,000
. 2,800
2,000
1,900
NDe
Xylenes3
2,300
2,000
1,800
1,100
2,200
1,900
1,900
1,200
4,000
3,300
3,600
4,600
1,800
NDe
1,300
NDe
Ethyl-
benzene3
ND
ND
ND
ND
ND
ND
ND
ND
580
640
720
140
NDe
ND
NDe
TPH3
NA<=
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
ft | A
IMA
3,000
6,000
NA
Notes: "Concentrations reported in ppb.
bNot detected above reporting limit.
-------
Table 0-2-2. Operating Conditions and Analytical Results for Test Run 1 (Batch)
Operating Conditions
Contact Time (min)
Reactor Volume (gal)
Gas Flow Rate (scfh) (Ozone 2%)
Ozone Dosage (mg/L)
Percent UV Lamps
Laboratory Analysis
Benzene (ug/L)
Toluene (pg/L)
Ethylbenzene (iig/L)
Xylene (g/L)
Total
Total Removal (%)
0
—
--
--
-
2,250
540
69.5
1,075
3,934.5
--
15
150
115
116
100
8
2
2
2
14
99.64
30
150
115
233
100
0
2
2
2
6
99.85
45
150
115
349
100
0
2
0
0
2
99.95
60
150
115
466
100
0
2
0
0
2
99.95
Table D-2-3. Operating Conditions for Test Runs 2 through 12 (Continuous)
Test Number 2 3 4 .5 6
10
11
12
Flow Rate (gpm)
Retention Time (min)
Ozone Flow Rate (scfh)
Ozone (wt %)
Ozone Dosage (rng/L)
H202 Rate (mL/min)
H2O2 Dosage (mg/L)
Total Oxidants (mg/L)
Percent UV Lamps On
5
30
90
2.16
98.29
0.00
0.00
98.29
100
5
30
45
2.16
49.14
2.00
44.39
93.53
too
5
30
68
2
68.76
0.0
0.00
68.76
100
5
30
45
0
0.00
4.00
88.77
88.77
100
5
30
45
2.16
49.14
2.00
44.39
93.53
100
5
30
45
2.15
48.92
2.00
44.39
93.30
50
5
30
40
2.05
41.46
1.70
37.73
79.19
100
7.5
« • 20
60
2.01
40.65
2.70
39.95
80.60
100
6
25 ,
50
2.04
42.98
2.14
39.58
82.55
100
4
37.5
30
2.05
38.87
1.47
40.78
79.65
100
5
30
60
2.02
61.28
2.76
61.25
122.53
100
Table O-2-4. Analytical Results for Test Runs 2 through 12 (Continuous)
Test Number
Benzene
Toluene
Ethylbenzene -
Xylene
Total
% Removed
Influent
Effluent
Influent
Effluent
Influent
Effluent
Influent
Effluent
Influent
Effluent
2
2,250
0
500
2
75
0
1,190
31
4,265
33
99.23
3
2,250
0
520
1
68
0
1,100
0
3,888
1
99.97
4
2,250
6
520
2
70
2
1,115
2
3,955
12
99.70
5
4,400
137.5
3,800
88.5
185
72.5
3,200
82.2
11,585
380.7
96.71
6
4,400
23
3,800
8.5
185
2
3,200
2
11,585
35.5
99.69
7
4,400
80
3,550
52
183.5
13.5
3,137.5
5
11,271
150.5
98.66
8
4,400
44
3,550
23
183.5
7.8
3,137.5
21.8
11,171
96.6
99.14
9
4,400
143.2
3,550
87.5
183.5
19.8
3,137.5
84.8
11,271
335.3
97.03
10
4,400
115
3,550
7.5
183.5
61
3,137.5
67
11,271
250.5
97.78
11
4,400
85
3,300
51
175
31.2
3,100
46
10,975
213.2
98.06
12
4,400
0
3,300
2
175
1
3,100
1
10,975
4
99.96
Notes: 1. Influent and effluent concentrations are reported in
2. For the purpose of calculating, zero value was entered for the analysis of samples that were non-detectable. Also, a < 5 ug/L sample
was approximated as 2 ug/L.
3. On a few selected samples, duplicates were taken and therefore average values were entered.
Case Study D-3, FEI Microwave,
Sunnyvale, California
Introduction
This case study describes Ultrox's demonstration at
the FEI Microwave site in Sunnyvale, California in
the spring of 1989. The pilot study was part of the
California Hazardous Waste Reduction Program
administered by the state's Department of Health
Services grant to demonstrate the removal of
groundwater contaminants such as trichloroethylene
(TCE).
63
-------
Table D-2-5. O&M Cost Estimates for Test Runs 2 through 12 (Continuous)
Test Number 234567
10
Note: Cost estimates are reported in $/l ,000 gallons.
11
12
Ozone
H2O2
UV
Total
0.492
0.00
0.955
1.45
0.246
0.241
0.955
1.45
0.344
0.000
0.955
1.30
0.000
0.481
0.955
1.44
0.246
0.241
0.955
1.44
0.245
0.241
0.478
0.96
0.207
0.204
0.955
1.37
0.203
0.216
0.637
1.06
0.215
0.214
0.796
1.23
0.194
0.221
1.194
1.61
0.307
0.332
0.955
1.59
The contamination of groundwater on the FEI
Microwave site resulted from a leaking underground
storage tank holding chemicals used in
manufacturing electronic components.
Contamination of the site was discovered when FEI
acquired the property. After a site characteristics
study, a groundwater extraction system was installed
to prevent the contaminated groundwater plume
from leaving the property. The existing groundwater
contamination and treatment system consists of nine
extraction wells of varying depth and an air stripping
unit to reduce the toxic contaminant concentrations
to the regulatory discharge limit of 0.5 ug/L for TCE
or any other toxic organic compounds.
Plant Description
The Ultrox UV radiation/oxidation system was
installed avoiding interference with the existing air
stripping process. A fence was erected around the
equipment to prevent tampering, and a tent was
provided to protect the equipment from the elements.
Prior to treatment, the groundwater was stored in a
6,500-gallon temporary storage tank in quantities of
no greater than required for each test (2,000 gallons).
After treatment the effluent was pumped to another
6,500-gallon tank. Following each day of testing, the
effluent was piped to the air stripper for additional
treatment prior to discharge.
Methodology
The principal goals of this pilot demonstration were
to reduce TCE below detectable limits and other
constituents to concentrations less than 5 ug/L. These
criteria were prescribed by the local California
Regional Water Quality Control Board for discharges
to sewers. The results of analytical testing of the
groundwater samples from the influent and effluent
ports on the air stripper are presented in Table D-3-
l.From this list of compounds, TCE was selected for
further examination in the pilot study. This
compound was targeted because it was a major
contaminant in the groundwater and because it had
been a standard component of the chemicals used for
the manufacture of electronic hardware on the site.
Thirteen tests were performed over a two-week
period with one or two tests run each day. The
samples were analyzed the day following the test
runs. All tests were conducted while the unit was
operating in a continuous mode with the.;flow rate
varying between 22 and 37 gpm.
Results
Test Operations
The operating conditions and analytical results of the
13 tests are shown on Table D-3-2. The influent
concentration of TCE varied from 150 to 7,750 ug/L.
The removal efficiencies varied from 77.3 to 100
percent.
The first three test results showed that TCE was
oxidized to a nondetectable level (<5 ug/L). Tests 4,
5, 7, and 13 were run with less than all of the UV
lamps operating to assess this aspect of the
treatment. Tests 4, 5, and 13 werie run with 50
percent of the UV lamps operating while varying
ozone and hydrogen peroxide. Test 7 was conducted
without any UV lamps operating and achieved the
lowest removal of TCE (77.3 percent and 500 ug/L).
Tests 8 and 10 were run without any ozone to
measure the effect of different hydrogen peroxide
dosages. The higher hydrogen peroxide dosage in
Test 8 resulted in TCE concentrations in the effluent
below the detection level. Overall, 7 of the 13 test
runs achieved acceptable effluents where TCE was
less than the analytical detection limit of 5 ug/L.
Costs
The costs for oxidants were estimated for all test runs
with the Ultrox unit operating with various oxidant
dosages. The costs per 1,000 gallons of groundwater
treated are shown in Table D-3-3. Test 9 has the
lowest total cost for any test run which achieved
acceptable discharge limits. These costs do not
include costs associated with any operator who
oversees the equipment nor do they include such
items as amortization costs of the equipment, or
replacement of filters or spargers, or analytical
testing. The budgetary capital cost for the Ultrox UV
radiation/oxidation equipment to treat groundwater
at this facility at 40 gpm is $120,000 (not installed).
64
-------
Table D-3-1. Groundwater Treatment Results During the Air Stripper Study
Sample
Location
Date
TCEa 1,1-DCA3 1,1-DCEa 1,2-DCE3 PCE3
1,1,1- Vinyl
TCAa 1,2-DCB3 Chloride3
Freona
Methyl
Chloride3
Total
VOCs3
Dw.Str. 01/28/88 2,000
<10 <10 320 20 <10 <10 10 19 <10 2,373
02/12/88 15 <0.5 <0.5 0.7 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 ' 15.7
06/02/88 3.8 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 4.3
08/30/88 3.2 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 2.2
11/15/88 1.2 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.8 2.0
Outlet
01/20/88
02/08/88
02/12/88
03/07/88
04/12/88
06/01/88
06/02/88
07/05/88
08/30/88
09/30/88
10/25/88
11/15/88
11/15/88
12/07/88
150
39
17
8.8
6.5
4.4
5.3
3.6
3.7
6.6
1.1
1.9
1.8
<0.5
<1.0
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<1.0
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
21
3.0
0.7
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<1.0
<0.5
<0.5
0.6
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<1.0
<0.5
<0.5
<0.5
<0.5
<0.8
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<1.1
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<1.0
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<1.5
<0.9
<0.5
<0.5
<0.5
0.8
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<1
<0.5
<1.0
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
0.7
<5
<0.5
173.6
42.9
17.7
9.4
6.5
6.0
5.3
3.6
3.7
6.6
1.1
2.6
1.8
<0.5
Inlet
01/28/88
02/08/88
03/07/88
06/02/88
08/30/88
11/15/88
5,400
4,500
4,900
6,200
11,000
3,700
<100
<50
<50
<50
<200
<50
<100
<50
<50
<50
<200
<50
210
190
170
90
<200
<50
<100
78
58
<50
<200
<50
<100
<50
<50
<50
<200
<50
<100
<50
<50
<50
<200
<50
<100
<50
<50
<50
<200
<50
<100
<50
180
260
<200
200
<100
<50
<50
150
<200
<50
5,610
4,768
5,308
6,700
11,000
3,900
Dw.Str. 01/10/89
Outlet 01/10/89
01/10/89
02/16/89
03/14/89
2.4
<5.0
<5.0
2.5
3.8
0.5
<5.0
<5.0
0.5
0.5
<0.5
<5.0
<5.0
<0.5
<0.5
<0.5
<5.0
<5.0
<0.5
<0.5
<0.5
<5.0
<5.0
<0.5
<0.5
<0.5
<5.0
<5.0
<0.5
<0.5
--
-
--
<0.5
<0.5
<1.0
<5.0
<5.0
<0.5
<0.5
<1.0
--
-
<0.5
<0.5
<5.0
<25
<25
<0.5
<0.5
2.4
<25
<25
2.5
Inlet
01/10/89 2,900
02/16/89 2,000
<250
<250
<250
<250
<250
<250
<250
<250
<100
<250
<250
<100
<250
<250
1,200
<250
2,900
2,900
Notes: Concentrations reported in ppb.
1,1-DCA: 1,1-dichloroethane; 1,2-DCB: 1,2-dichlorobenzene; 1,1-DCE: 1,1-dichloroethylene; 1,2-DCE: 1,2-dichloroethylene; Dw.Str.:
down stream; PCE: tetrachloroethylene; 1,1,1-TCA: 1,1,1-trichloroethane; and TCE: trichloroethylene.
Case Study D-4, Golf Course, City of
South Gate, California
introduction
This case study describes Ultrox's UV
radiation/oxidation project conducted at a par-3 golf
course in the City of South Gate, California, at the
end of 1987. This demonstration, supported by the
California Department of Health Services, consisted
of a series of tests to treat groundwater contaminated
with PCE and TCA. A 675-gallon Ultrox Model P-675
reactor was operated in the continuous, flow-through
mode at 50 gpm during the test runs. The test
program was conducted over a 6-day period to define
operating, maintenance, and equipment costs for full-
scale equipment.. This is the only case study
presented in this report with estimated costs for
65
-------
Table 0-3-2. Operating Conditions and Analytical Results for the Ultrox System
Test Number
Operating Conditions
Flow Rate (gpm)
Retention Time (min)
Gas Flow Rate (scfh)
(Ozone)
Ozone (wt %)
Ozone Dosage (mg/L)
HjO, Rate (ml/min)
H2Oj Dosage (mg/L)
TotarOxidants (mg/L)
Percent UV Lamps On
Laboratory Analysis
Inf. TCE Cone. (mg/L)
Elf. TCE Cone. (mgA.)
Removal (%)
1
37
16
150
1.97
18.3
16
48
66.3
100
6.375
ND
100
2
30
20
120
0.86
7.9
13
48
55.9
100
6.75
ND
100
3
33
18
150
2.33
24.3
14
47
71.3
100
5.75
ND
100
4
37
16
150
1.97
18.3
16
48
66.3
50
7.75
0.06
99.2
5
37
16
150
1.39
12.9
11.5
34.5
47.4
50
7.5
0.052
99.3
6
37
16
150
0.73
6.78
17
51
57.8
100
1.5
ND
100
7
37
16
150
1.57
14.6
3.3
9.9
24.5
0
2.2
0.5
77.3
8
37
16
0
0
0
16
48
48
100
1.3
ND
100
9
37
16
150
1.97
18.3
6
18
36.3
100
3.3
ND
100
10
37
16
150
0
0
8.3
25
25
100
0.15
0.02
86.7
11
37
16
150
2.94
27.3
8.3
25
52.3
100
0.229
ND
100
12 13
37 , 22
16 27
150 150
1.7 1.62
15.8 25.3
5 8.3
15 25
30.8 50.3
100 50
0.625 2.25
0.049 0.054
99.2 97.6
Note: ND : Not detected.
Table D-3-3. Oxldant Cost Estimates
Test Number
1
2
3
4
5
6
7
8
9
10
11
12
13
TCE Effluent Cone.
(mg/L)
ND"
ND
ND
0.06
0.052
ND
0.50-
ND
ND
0.02
ND
0.049
0.054
Ozone3
, 0.09
0.04
0.12
0.09
0.06
0.03
0.07
0.00
0.09
0.00
0.14
0.08
0.13
H202a
0.29
0.28
0.27
0.28
0.20
0.30
0.06
0.28
0.10
0.14
0.14
0.09
0.14
UVa
0.39
0.48
0.44
0.19
0.19
0.39
0.00
0.30
0.30
0.31
0.30
0.42
0.14
Total3
0.76
0.80
0.83
0.56
0.46
0.72
0.13
0.58
0.50
0.45
0.58
0.58
0.41
Note: a Cost estimates reported in $/1,000 gallons
b ND: Not detected.
pressurized and nonpressurized systems. Twelve
tests were run in which the oxidant doses were varied
while attempting to achieve the desired treatment
standard of 2 ug/L for PCE. The untreated
concentration of TCA, ranging from nondetectable to
3 ug/L, was less than the level of concern.
Results
Operations
A description of the operating conditions and the
analytical results are presented in Table D-4-1. As
shown, the influent water PCE concentrations varied
between 14 and 18 ppb with the average being 17
ppb. Six tests (Nos. 2, 3, 5, 7, 9, and 11) produced
water with a PCE concentration of less than 2 ppb,
which was the desired treatment standard.
TCA was also detected in the water at concentrations
of nondetectable to 3 ppb, which is below present
drinking water standards. The various operating
conditions did not significantly reduce the TCA with
the exception of Test No. 9, which used UV-hydrogen
peroxide.
Costs
The projected O&M costs per day for a continuously
operating system at 1,250 gpm for the successful test
runs are presented on Table D-4-2. Test No. 11, run
without UV or hydrogen peroxide, shows the lowest
O&M costs. Tables D-4-3 and D-4-4 present capital
costs estimated for pressurized (80 psig) and
nonpressurized systems. The lowest capital costs for
both systems are those associated with Test No. 11.
Test No. 7 had the next least expensive capital costs.
Case Study D-5 Xerox Facility, Webster,
New York
Introduction
This case study describes Ultrox's UV
radiation/oxidation testing of an approximately one-
quarter scale unit on contaminated groundwater at
the Xerox Corporation, Salt Road site. The
contaminants include TCE and vinyl chloride with
total volatile organics ranging in concentrations from
1 to 10 mg/L. The information contained in this
appendix is based on a draft, interim report by Xerox
66
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Table D-4-1. Operating Conditions and Analytical Results
Test No.
1
2
3
4
5
6
7
8
g
10
11
12
Ozone Dosage
Med.
High
High
0
0
0
Med.
0
0
Low
Med.
Low
H2O2 Dosage
0
0
Med.
High
Med.
0
Med.
Med.
Med.
Low
0
0
Operating UV
Lamps
All
All
0
0
1/3
All
0
1/4
1/2
0
0
0
PCE
Influent
14
20
17
17
17
17.5
18
16
16
18
—
18
Effluent
4
0.2
0.4
14
0.1
4
0.2
13
1.3
2.2
0.32
4.4
TCA
Influent
3
ND
ND
ND
ND
0.4
0.5
1.3
1.2
ND
ND
ND
Effluent
2.4
ND
ND
ND
ND
0.5
0.4
1.3
0.3
ND
ND
ND
Note: 1. All tests run at 50 gpm.
2. ND: Not detected.
3. Concentrations reported in ppb.
Table 0-4-2. Daily O&M Cost Estimates for 1,250-gpm System
Test No.
2
3,
5
7
9
11
Ozone
164
164
0
110
0
110
H2O2
0
54
54
51
54
0
UV Power
235
0
78
0
118
0
UV Maint.
80
0
27
0
40
0
Total
479
218
159
161
212
110
Note: 1. All values reported in dollars.
2. Assumes cost of electrical energy is at $0.085/kWh.
3. An additional $21/day O&M costs is required for 80-psig pressurized systems.
Table D-4-3. Capital Cost Estimates for 1,250-gpm Pressurized System
Test No. Ozone Generator H2O2 Supply
Reactor
Total
2 162,000
3 162,000
5 0
7 125,000
9 0
11 125,000
0
10,000
10,000
10,000
10,500
0
400,000
85,000
300,000
85,000
350,000
85,000
562,000
257,000
310,000
220,000
360,000
210,000
Note: All values reported in dollars.
Table D-4-4. Capital Cost Estimates for 1,250-gpm Nonpressurlzed System
Test No.
2
3
5
7
9
11
Ozone Generator
122,000
122,000
0
100,000
0
100,000
H2O2 Supply
0
10,000
10,000
10,000
10,000
0
Reactor
360,000
50,000
260,000
50,000
315,000
50,000
Total
482,000
182,000
270,000
160,000
325,000
150,000
Note: All values reported in dollars.
67
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and personal communication. No cost data were
provided.
Plant Description
A 650-gallon Ultrox reactor was installed at the site
in March 1989 for a series of pilot tests. Recovery well
pumps provide the hydraulic pressure necessary for
process flows. A 5-micron fiber bag filters the
groundwater prior to treatment. During the pilot
tests, effluent from the Ultrox system was sent to a
storage tank and subsequently pumped to an air
stripper to guarantee effluent discharge
requirements. The effluent, currently discharged to a
sanitary sewer, will later be sent to a surface stream
from the air stripper during full-scale operation.
Methodology
During the test period, the groundwater flow rate
varied from 30 to 50 gpm, with an additional 10 gpm
acting as cooling water for the air compressor and
ozone generator. A 50 percent solution of hydrogen
peroxide was added to the influent at a dose of 30
mg/L. The ozone dosage was set at 58 mg/L with a
constant pressure of 15 psig. The feed mixture was
calibrated to deliver 2 percent ozone in the reactor.
All 72 U V lamps were operating during the test runs.
Twenty-four sampling events were conducted during
the test period, with daily samples collected during
the first week of operation and twice weekly
thereafter. Influent was sampled prior to the
hydrogen peroxide injection; effluent was sampled
from the sixth cell sampling port of the reactor.
Results
Analytical
For the test runs, the average contaminant
concentration for total volatile organics was 3,048
ug/L. The removal efficiency averaged 93 percent
with 3 constituents below 90 percent and 21
compounds above 90 percent. The removal
efficiencies for specific compounds were as follows:
Compound
Vinyl Chloride
Toluene
Tetrachloroethylene
1,2-Dichloroethylene
Trichloroethylene
1,1,1-Trichloroethane
1,1-Dichloroethane
Removal Efficiency (%)
100
100
100
98.6
92.2
36
0.0
Maintenance
Daily inspection during the test period revealed that
periodic adjustments are required to maintain peak
operating efficiency. The groundwater at the site
contains relatively high concentrations of iron which
affected the UV lamps. Based on the tests,
inspections would be prudent to replace lamps and
clean the quartz sleeves. Additional maintenance
would be required to check and change the
compressor oil and filter as well as inspect and
change the ozone decomposer catalyst.
Case Study D-6 /Coppers Industries,
Denver, Colorado
Introduction
This case study briefly presents treatment results of
an Ultrox system employed by Koppers Industries,
Inc., on wastewater from a wood processing facility.
An Ultrox unit, operating since December 1985 with
UV and ozone, is used to treat the organic
contaminants, phenol and pentachlorophenol (PCP),
from the plant's wastewater. A pretreatment system
consists of pH adjustment, oil removal, and
flocculation and settling of heavy metals.
The organic concentrations of the influent typically
range between 150 to 200 mg/L for phenol and are
about 1 mg/L for PCP. Oil and grease are measured at
about 3 percent in the raw wastewater.
Results
Analytical
The results of effluent testing from several months of
operation based on 1-day composites are presented as
follows:
5/88
8/88 11/88 3/89
7.2 7.0
0.18 0.5
145.0 65.0
15.0 78.0
11.6 12.2
0.44 0.15
38.0 45.0
<1.0 24.0
Constituent
pH
PCP (mg/L)
Phenol (mg/L)
Oil (mg/L)
The flows in March 1989 were reported to be 5,211
gpd on an average daily basis, with a maximum daily
How of 16,047 gpd.
Costs
The operating and maintenance costs per 1,000
gallons of treated wastewater for the entire system
are presented in Table D-6-1. The capital cost of the
68
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Table D-6-1. O&M Cost Estimate
Item
Flocculating agents
Sulfuric acid
Caustic soda
Defoamer
Electricity
Labor
Analysis
Effluent disposal
$/l,OOOgal
5.79
.39
.81
.42
2.11
1.40
1.83
4.64
Total
$17.39/1,000 gal
principal VOCs and PCBs to levels below the
analytical detection limits. Both oxidants, in
conjunction with UV radiation, achieved VOC
reductions greater than 99.9 percent. These tests also
indicated that hydrogen peroxide alone could achieve
substantial VOC and PCB removals. Trans-1,2-
dichloroethylene, the VOC with the highest influent
concentration, was more difficult to treat than vinyl
chloride. Another VOC, 1,1,2-TCA, present in low
concentrations in the influent, appeared to be
resistant to oxidation, or a product of degradation.
entire treatment system installed was $550,000, of
which $200,000 was for the Ultrox UV
radiation/oxidation portion.
Case Study D-7 General Electric
Company, Lanesboro, Massachusetts
Introduction
This case study describes the Ultrox technology's
performance in a treatability study that took place at
General Electric Company's Rose Site, Lanesboro,
Massachusetts in the fall of 1987. In addition to UV
radiation/oxidation, the project evaluated the
effective use of air stripping and carbon adsorption in
treating groundwater contaminated with several
volatile compounds including vinyl chloride and
trans-l,2-dichloroethylene, and trace concentrations
of PCBs.
References
Case
Study
1.
2.
Garland II, S.B., 1989. Annual Report, An
Evaluation of the Use of a Combination of
Ozone, Ultraviolet Radiation, and Hydrogen
Peroxide to Remove Chlorinated
Hydrocarbons from Groundwater at the
Department of Energy Kansas City Plant,
Oak Ridge National Laboratory Report,
ORNL/TM-11056.
Ultrox International, 1989. The
Demonstration of the Ultrox UV/Oxidation
Treatment of Contaminated Groundwater at
the Hewlett Packard Facility, Palo Alto,
California.
Plant Description
An Ultrox Model P-75 pilot system, with a wet
volume of 75 gallons, 6 cells, and 30 UV lamps, was
used in the study. The unit was supplied with
groundwater from a single well that passed through a
10-micron cartridge filter prior to treatment.
Methodology
Tests were performed on the Ultrox system to
evaluate the use of UV-ozone and UV-hydrogen
peroxide. All UV lamps remained operating while
the hydraulic retention times and oxidant dosages
were varied. UV-ozone test conditions had flow rates
between 1.5 and 2 gpm with ozone dosages between
160 and 600 mg/L at concentrations of approximately
3 percent. UV-hydrogen peroxide test conditions had
flow rates between 0.75 and 1 gpm with hydrogen
peroxide dosages between 53 and 580 mg/L. Batch
tests preceded continuous-flow operations for each
phase of study.
Results
Both treatment combinations, UV-ozone and UV-
hydrogen peroxide, were able to reduce the two
3. Ultrox International, 1989. Report on the
Demonstration of the UV/Oxidation
Treatment of Groundwater at FBI
Microwave, Sunnyvale, California.
4. Ultrox International, 1988. Ultrox Pilot
Plant Treatment Demonstration Report for
the City of South Gate, California.
5. Xerox Corporation, 1989. Draft Interim
Report, Ultrox Performance Summary and
personal communication between Dr. Robert
Heeks, Xerox Corporation, and Dr. Gary
Welshans, PRC.
6. Koppers Industries, 1989. Personal
communication between Mr. Marvin Miller,
P.E., Koppers Industries, and Dr. Gary
Welshans, PRC.
7. Blasland & Bouck Engineers, P.C., 1988.
Draft Report, Ground-Water Treatability
Report, Rose Site, Lanesboro,
Massachusetts.
69
•frU.S. GOVERNMENT PRINTING OFFICE: 1990-751-429
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