EPA/540/AR-93/506
September 1993
CWM PO*WW*ER™
Evaporation-Catalytic
Oxidation Technology
Applications Analysis Report
Risk Reduction Engineering Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
> Printed on Recycled Paper
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Notice
The information in this document has been prepared for the U.S. Environmental Protection
Agency (EPA) Superfund Innovative Technology Evaluation (SITE) program underContractNo. 68-
CO-0047. This document has been subjected to EPA peer and administrative reviews and has been
approved for publication as an EPA document. Mention of trade names or commercial products does
not constitute an endorsement or recommendation for use.
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Foreword
The Superfund Innovative Technology Evaluation (SITE) program was authorized by the 1986
Superfund Amendments and Reauthorization Act (SARA). The SITE program is a joint effort
between the EPA Office of Research and Development (ORD) and the Office of Solid Waste and
Emergency Response (OSWER). The purpose of the program is to accelerate the development and
use of innovative cleanup technologies applicable to Superfund and other hazardous waste sites
through field technology demonstrations designed to provide performance and cost data on selected
technologies.
A field demonstration was conducted under the SITE program to evaluate the Chemical Waste
Management, Inc. (CWM), PO*WW*ER™ technology. The technology demonstration took place
at CWM's Lake Charles Treatment Center (LCTC) site in Lake Charles, Louisiana. The purpose of
the demonstration effort was to obtain information on the performance and cost of the technology and
to assess its use at this and other uncontrolled hazardous waste sites. Documentation of the
demonstration consists of two reports: (1) a Technology Evaluation Report, which describes field
activities and laboratory results; and (2) this Applications Analysis Report, which interprets the
demonstration data and discusses the technology's potential applicability.
A limited number of copies of this report will be available at no charge from the EPA Center for
Environmental Research Information, 26 West Martin Luther King Drive, Cincinnati, Ohio 45268.
Requests for this report should include the EPA document number on the report's cover. When the
limited supply is exhausted, additional copies may be purchased from the National Technical
Information Service, Ravensworth Building, Springfield, Virginia 22161, telephone number (703)
487-4600. Reference copies of this report will be available at EPA libraries as part of the Hazardous
Waste Collection. Information about the availability of reports can be obtained by calling ORD
Publications in Cincinnati, Ohio, at (513) 569-7562.
E. Timothy Oppelt, Director
Risk Reduction Engineering Laboratory
111
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Abstract
This reportevaluates the Chemical Waste Management, Inc. (CWM), PO*WW*ER™ technology' s
ability to remove volatile organic compounds (VOC), semivolatile organic compounds (SVOC),
ammonia, cyanide, metals, and other inorganic contaminants from aqueous wastes. This evaluation
is based on treatment performance and cost data obtained from the Superfund Innovative Technology
Evaluation (SITE) demonstration and 11 case studies conducted by CWM.
The PO*WW*ER™ system reduces the volume of an aqueous waste and catalytically oxidizes
volatile contaminants. The PO*WW*ER™ system consists primarily of (1) an evaporator that
reduces influent wastewater volume, (2) a catalytic oxidizer that oxidizes the volatile contaminants
in the vapor stream from the evaporator, (3) a scrubber that removes acid gases formed during
oxidation, and (4) a condenser that condenses the vapor stream leaving the scrubber.
The PO*WW*ER™ system demonstration was conducted under the SITE program at CWM's
Lake Charles Treatment Center (LCTC) site in Lake Charles, Louisiana. The SITE demonstration
was conducted in September 1992. During the demonstration, the PO*WW*ER™ system treated
landfill leachate, an F039 hazardous waste, contaminated with VOCs, SVOCs, ammonia, cyanide,
metals, and other inorganic contaminants. During the development of the PO*WW*ER™ system,
CWM conducted bench- and pilot-scale tests and collected treatability data for the following aqueous
wastes: (1) landfill leachate, (2) contaminated well water, (3) contaminated lagoon water, (4) fuels
decant water, (5) oil emulsion wastewater, and (6) wastewater contaminated with nitrogen-containing
organic compounds and cyanide. During these tests, the PO*WW*ER™ system processed aqueous
wastes containing VOCs, SVOCs, pesticides, herbicides, solvents, heavy metals, cyanide, ammonia,
nitrate, chloride, and sulfide.
Based on the results of the SITE demonstration and other case studies, the following conclusions
can be drawn:
• The PO*WW*ER™ system can process a wide variety of aqueous wastes with differing
contaminant concentrations.
• During the SITE demonstration, the PO*WW*ER™ system achieved a total solids (TS)
concentration ratio of about 32 to 1. During other case studies conducted by CWM, a TS
concentration ratio ranging from 35 to 1 to 50 to 1 was achieved.
• During the SITE demonstration, the TS concentration in the brine ranged from 50 percent to
56 percent. During other case studies conducted by CWM, the TS concentration in the brine
ranged from 28 to 80 percent.
• Concentrations of VOCs and SVOCs in the product condensate exiting the PO* WW*ER™
system condenser were below their respective detection limits of 5 to lOug/Land lOto 130
ug/L.
IV
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Abstract (continued)
• During the SITE demonstration, ammonia and cyanide concentrations in the product
condensate samples were below the detection limits of 0.1 and 0.01 mg/L, respectively.
Results from other case studies show that the product condensate contained ammonia and
cyanide at similar low concentrations.
• The product condensate contained trace levels of metals.
• The product condensate may contain nitrate resulting from the hydrolysis of nitrogen dioxide.
• During the SITE demonstration, the brine, which is an F039-derived hazardous waste, was
also found to be hazardous based on toxicity characteristic leaching procedure (TCLP) test
results. The brine also had relatively high levels of cyanide. Under acidic conditions, the brine
could exhibit the hazardous waste characteristic of reactivity.
• During the SITE demonstration, the noncondensible gas stream met proposed regulatory
requirements for the LCTC site. The noncondensible gas emissions may contain VOCs,
SVOCs, ammonia, cyanide, nitrogen oxides (NOx), sulfur dioxide (SO2), carbon monoxide
(CO), and carbon dioxide (CO2), generally at low concentrations determined by treatment
conditions and the type of contaminants present in the feed waste.
• The PO*WW*ER™ system removes sources of feed waste toxicity, such as VOCs, SVOCs,
ammonia, and cyanide. The feed waste was acutely toxic, with LCSOs consistently below 10
percent. The product condensate was nontoxic, with LCSOs consistently greater than 100
percent, but only after the product condensate was cooled and its pH, dissolved oxygen level,
and hardness or salinity were increased to meet demonstration objectives and as allowed in
EPA acute toxicity testing procedures.
• Economic data indicate that the capital cost for a 50-gallon per minute PO* WW*ER™ system
is approximately $4 million on a turnkey basis. The capital cost includes treatability study
costs; design costs; all necessary components of a PO* WW*ER™ system; all interconnecting
piping, controls, and monitoring equipment; and assembly and installation costs. Annual
operating and maintenance (O&M) costs, including labor, consumables, utilities, analytical
services, and waste disposal costs at a Superfund site are estimated to be about $3.3 million.
Waste disposal costs account for about 70 percent of the annual cost. The total cost of aproject
lasting 15 years was estimated to be about $100 per 1,000 gallons of aqueous waste treated;
and the total cost of a project lasting 30 years was estimated to be about $73 per 1,000 gallons
of aqueous waste treated.
This report also discusses the applicability of the PO*WW*ER™ system based on compliance
with regulatory requirements, implementability, short-term impact, and long-term effectiveness. In
addition, factors influencing the technology's performance in meeting these criteria and evaluation
limitations are discussed.
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Contents
Notice ii
Foreword iii
Abstract iv
Acronyms, Abbreviations, and Symbols xi
Conversion Factors xiv
Acknowledgements xv
1. Executive Summary 1
1.1 Conclusions 1
1.2 Results 2
2. Introduction 5
2.1 Purpose, History, and Goals of the SITE Program 5
2.2 Documentation of the SITE Demonstration Results 6
2.2.1 Technology Evaluation Report 6
2.2.2 Applications Analysis Report 6
2.3 Technology Description 6
2.3.1 Feed System 6
2.3.2 Evaporator 6
2.3.3 Catalytic Oxidizer 8
2.3.4 Scrubber 8
2.3.5 Condenser 8
2.4 Innovative Features and Limitations of the PO*WW*ER™ Technology 8
2.5 Key Contacts 8
3. Technology Applications Analysis 11
3.1 Treatment Effectiveness for Volume Reduction 11
3.2 Treatment Effectiveness for Toxicity Reduction 12
3.2.1 VOC Removal 12
3.2.2 SVOC Removal 13
3.2.3 Ammonia and Cyanide Removal 14
3.2.4 Noncondensible Gas Emissions 14
3.2.5 Acute Toxicity 15
3.3 Compliance With Regulatory Requirements 16
3.3.1 CERCLA 16
3.3.2 RCRA 16
3.3.3 CWA .is
3.3.4 SDWA 18
3.3.5 CAA 18
3.3.6 TSCA 18
3.3.7 Radioactive Waste Regulations 19
vn
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Contents (continued)
3.3.8 Mixed Waste Regulations 19
3.3.9 OSHA 20
3.4 PO*WW*ER™ System Implementation 20
3.4.1 Site Preparation 20
3.4.2 Operation and Maintenance Requirements 20
3.4.3 Reliability 21
3.4.4 Personnel Requirements 21
3.5 Short-Term Impact 22
3.5.1 Worker Safety 22
3.5.2 Potential Community Exposure 22
3.6 Long-Term Effectiveness 22
3.6.1 Permanence of Treatment 22
3.6.2 Residuals Handling 22
3.7 Factors Influencing Performance 23
3.7.1 Waste Characteristics Influencing Performance 23
3.7.2 Operating Parameters Influencing Performance 24
3.8 Evaluation Limitations 25
3.8.1 Testing Limitations 25
3.8.2 Confidential Information Limitations 25
4. Economic Analysis 27
4.1 Site-Specific Factors Affecting Costs 27
4.2 Basis of Economic Analysis 27
4.3 Cost Categories 29
4.3.1 Site Preparation Costs 29
4.3.2 Permitting and Regulatory Requirements Costs 29
4.3.3 Capital Equipment Costs 30
4.3.4 Startup Costs 30
4.3.5 Labor Costs 30
4.3.6 Consumables and Supplies Costs 30
4.3.7 Utilities Costs 31
4.3.8 Effluent Treatment and Disposal Costs 31
4.3.9 Residuals and Waste Shipping and Handling Costs 32
4.3.10 Analytical Services Costs 32
4.3.11 Maintenance and Modifications Costs 32
4.3.12 Demobilization Costs 32
4.4 Summary 33
5. References 35
Appendix A Developer's Claims for the PO*WW*ER™ Technology 37
A.1 Developer's Claims 37
A.I.I Introduction 37
A.1.2 Technology Description 37
A.1.3 Benefits 37
A. 1.4 Applications 38
A.1.5 Design Options 39
A.I.6 Cost Economics 39
A.2 Summary 39
via
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Contents (continued)
Appendix B Site Demonstration Results 41
B.I Site Description 41
B.2 Technology Demonstration Testing and Sampling Procedures 41
B.3 Treatment Results '• 43
B.3.1 Summary of Results for Critical Parameters 43
B.3.2 Summary of Results for Noncritical Parameters 56
B.4 References 60
Appendix C Case Study Results 61
IX
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Figures
2-1 PO*WW*ER™ pilot plant flow diagram 7
B-l Volume of feed waste and brine during the unspiked and spiked test runs 44
B-2 TS concentration of feed waste and brine during the unspiked and spiked test runs 45
B-3 Cyanide and ammonia evaporation efficiencies during unspiked and spiked test runs 52
B-4 Acute toxicity of leachate feed and product condensate during unspiked run 2 and
spiked run 2—condition 1 55
B-5 Product condensate pH predicted and median pH measured during unspiked and
spiked test runs 59
Tables
4-1 Costs Associated with the PO*WW*ER™ Technology 28
A-l Capabilities of PO*WW*ER™ 38
A-2 Contaminants and Pollutants Treatable by PO*WW*ER™ 39
A-3 Design Options for the PO*WW*ER™ System 39
B-l SITE Demonstration Test Conditions 41
B-2 Operating Temperatures and Flow Rates of the PO*WW*ER™ Pilot System
During the SITE Demonstration 42
B-3 Summary of TSS, TDS, and TS Concentrations in Feed Waste, Product
Condensate and Brine During Unspiked Test Runs 44
B-4 Summary of TSS, TDS, and TS Concentrations in Feed Waste, Product
Condensate and Brine During Spiked Test Runs 45
B-5 Concentration Ratios During Unspiked and Spiked Test Runs 46
B-6 Critical VOC Concentrations During Unspiked and Spiked Test Runs 47
B-7 Critical SVOC Concentrations During Unspiked and Spiked Test Runs 49
B-8 Critical Inorganic Contaminants During Unspiked and Spiked Test Runs 51
B-9 Noncondensible Gas Average and Maximum Concentrations and Mass
Emissions Rates 53
B-10 Acute Toxicity of Feed Waste Measured as Percent LC50 Under
Condition 1 54
B-l 1 Acute Toxicity of Product Condensate after Hardness Adjustment—
Condition 1 54
B-l2 LC50 Values of Product Condensate at Hardness of 1 mg/L as Calcium
Carbonate Under Condition 2 56
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Acronyms, Abbreviations, and Symbols
ACL
AEA
ARAR
ARI
BPR
Btu
CAA
CEM
CERCLA
CFR
CN-
co
C02
CWA
CWM
dscm
DOE
EP
EPA
ES
ft
ft2
ft3
gal.
gpm
gr
HC1
HCN
in.
kg
kg/cm2
kJ
km
kWh
L
Ib
Ib/hr
Microgram
Micrograms per liter
Alternate concentration limits
Atomic Energy Act
Applicable or relevant and appropriate requirement
ARI Technologies, Inc.
Boiling point rise
British thermal unit
Clean Air Act
Continuous emissions monitoring
Comprehensive Environmental Response, Compensation, and Liability Act
Code of Federal Regulations
Cyanide
Carbon monoxide
Carbon dioxide
Clean Water Act
Chemical Waste Management, Inc.
Dry standard cubic meter
Department of Energy
Extraction procedure
U.S. Environmental Protection Agency
Engineering-Science, Inc.
Foot
Square feet
Cubic feet
Gallon
Gallons per day
Gallons per hour
Gallons per minute
Grain
Hydrochloric acid
Hydrogen cyanide
Inch
Kilogram
Kilogram per square centimeter
Kilojoule
Kilometer
Kilowatt-hour
Liter
Pound
Pounds per hour
XI
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Acronyms, Abbreviations, and Symbols (continued)
LCTC
LC50
LDR
m
m2
m3
MCL
mi
mg
mg/L
MJ
N2
NH3-N
NH/
NOx
NPDES
NRC
02
O&M
ORD
OSHA
OSWER
PCB
PCE
PIC
POTW
PPE
ppm
ppmv
PRC
psi
QA
QC
RCRA
RREL
SARA
scfh
scfm
SDWA
SITE
S02
svoc
TCE
TCLP
TDS
TS
TSS
Lake Charles Treatment Center
Median lethal concentration
Land Disposal Restrictions
Meter
Square meters
Cubic meters
Maximum contaminant level
Mile
Milligram
Milligrams per liter
Megajoule
Nitrogen
Ammonia nitrogen
Ammonium ion
Nitrogen oxides
National Pollutant Discharge Elimination System
Nuclear Regulatory Commission
Oxygen
Operation and maintenance
Office of Research and Development
Occupational Safety and Health Act
Office of Solid Waste and Emergency Response
Polychlormated biphenyl
Tetrachloroethene
Product of incomplete combustion
Publicly owned treatment works
Personal protective equipment
Parts per million
Parts per million by volume
PRC Environmental Management, Inc.
Pounds per square inch
Quality assurance
Quality control
Resource Conservation and Recovery Act
Risk Reduction Engineering Laboratory
Superfund Amendments and Reauthorization Act
Standard cubic feet per hour
Standard cubic feet per minute
Safe Drinking Water Act
Superfund Innovative Technology Evaluation
Sulfur dioxide
Semivolatile organic compound
Trichloroethene
Toxicity characteristic leaching procedure
Total dissolved solids
Total solids
Total suspended solids
XII
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Acronyms, Abbreviations, and Symbols (continued)
TNMHC Total nonmethane hydrocarbon concentration
TOC Total organic carbon
TOX Total organic halides
TSCA Toxic Substances Control Act
UIC Underground injection control
UST Underground Storage Tank
Versar Versar, Inc.
VOC Volatile organic compound
VOST Volatile organic sampling train
WET Whole effluent toxicity
Xlll
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Conversion Factors
Length:
Area:
Volume:
Mass:
English
1 inch (in.)
1 foot (ft)
1 mile (mi)
1 square foot (ft2)
I gallon (gal.)
1 cubic foot (ft3)
1 grain (gr)
1 pound (Ib)
1 ton (t)
Pressure:
Energy:
Temperature: (°F - 32)
1 pound per square inch (psi)
1 British Thermal Unit (Btu)
1 kilowatt hour (kWh)
x
x
x
x
x
Factor
2.54
0.305
1.61
0.0929
0.0703
1.05
3.60
0.556
Metric
centimeter (cm)
meter (m)
kilometer (km)
square meter (m2)
X
X
X
X
X
3.78
0.0283
64.8
0.454
907
liter (L)
cubic meter (m3)
milligram (mg)
kilogram (kg)
kilogram (kg)
kilogram per square centimeter (kg/cm2)
kilojoule (kJ)
megajoule (MJ)
°C
xiv
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Acknowledgements
This report was prepared under the direction and coordination of Mr. Randy Parker, U.S. Environmental Protection
Agency (EPA) Superfund Innovative Technology Evaluation (SITE) Project Manager at the Risk Reduction Engineering
Laboratory (RREL) in Cincinnati, Ohio. The efforts of Mr. Matt Husain and Mr. Brian Eichlin of Chemical Waste
Management, Inc. (CWM), were essential to the project's success.
This report was prepared for the EPA SITE program by Dr. Chriso Petropoulou, Mr. Stanley Labunski, Mr. Jeffrey
Swano, Ms. LouAnn Unger, Ms. Jean Michaels, Mr. Ron Riesing, Mr. David Liu, and Ms. Carol Adams of PRC
Environmental Management, Inc. (PRC). Technical input was provided by Mr. Donald Decker, Mr. Dean Ritz, and Mr.
David Badio of Engineering-Science, Inc. (ES), and Ms. Suzanne Smidt of Versar, Inc. (Versar). The report was edited
by Ms. Shelley Fu of PRC. Peer reviewers were Mr. Gordon Evans, Mr. Paul dePercin, and Mr. Robert Stenburg of RREL.
xv
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Section 1
Executive Summary
This report summarizes the findings of an evaluation
for the PO* WW*ER™ technology developed by Chemical
Waste Management, Inc. (CWM). This study was conducted
under the U.S. Environmental Protection Agency (EPA)
Superfund Innovative Technology Evaluation (SITE)
program. A series of demonstration tests of the technology
were performed by EPA as part of this program. The
demonstration tests were conducted in September 1992 at
the CWM Lake Charles Treatment Center (LCTC) site in
Lake Charles, Louisiana. The evaluation of the
PO*WW*ER™ technology was based on the results of the
SITE demonstration and 11 case studies performed by
CWM for several private clients.
The PO*WW*ER™ technology reduces the volume of
an aqueous waste and catalytically oxidizes volatile
contaminants. The PO*WW*ER™ system consists
primarily of (1) an evaporator that reduces influent
wastewater volume, (2) a catalytic oxidizer that oxidizes
the volatile contaminants in the vapor stream from the
evaporator, (3) a scrubber that removes acid gases formed
during oxidation, and (4) a condenser that condenses the
vapor stream leaving the scrubber. Conclusions drawn and
results of the SITE demonstration tests and case studies are
summarized below.
1.1 Conclusions
Based on the SITE demonstration and several other
case studies, the conclusions presented below may be
drawn on the applicability of the PO*WW*ER™ system.
• The PO*WW*ER™ system can process a wide
variety of aqueous wastes with differing
contaminant concentrations. Bench-and pilot-scale
tests effectively treated aqueous wastes such as
(X) landfill leachate, (2) contaminated well water,
(3) contaminated lagoon water, (4) fuels decant
water, (5) oil emulsion wastewater, and
(6) wastewater contaminated with nitrogen-
containing organic compounds and cyanide. During
these tests, the PO*WW*ER™ system effectively
treated aqueous wastes containing volatile organic
compounds (VOC), semivolatile organic
compounds (SVOC), pesticides, herbicides,
solvents, heavy metals, cyanide, ammonia, nitrate,
chloride, and sulfide.
During aqueous waste treatment in the
PO*WW*ER™ system, all volatile contaminants
present are vaporized depending on the relative
volatility of each compound and the waste mixture.
Contaminant removal mechanisms in the
PO*WW*ER™ system include evaporation,
catalytic oxidation, and absorption in a scrubber, if
required. Contaminants that do not vaporize
concentrate in the brine.
The PO*WW*ER™ system evaporates VOCs and
certain SVOCs from the feed waste. As expected,
VOC evaporation efficiencies are greater than
SVOC removal efficiencies. Among SVOCs,
compounds with lower boiling points and higher
vapor pressures have higher evaporation
efficiencies than compounds with higher boiling
points and lower vapor pressures.
Brine wasted from the PO*WW*ER™ system is
not treated on site and requires off-site treatment
by stabilization and disposal. When process
wastewater is treated in the PO * WW*ER™ system,
brine characteristics may be suitable for brine to be
reused or recycled.
Ammonia and cyanide evaporation efficiencies
are a function of the feed waste pH and the type of
metal ions present in the feed waste. Depending on
the type of metals present and the feed waste pH,
ammonia and cyanide may be either free or
complexed. Free ammonia evaporation efficiency
increases at pH values greater than 9, while free
1
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cyanide evaporation efficiency increases at pH
values less than 9.
The quality of the product condensate does not
vary with feed waste characteristics and total
contaminant loading at the levels measured during
the SITE demonstration. However, total
contaminant loading may affect the contaminant
evaporation efficiency, which in turn affects the
contaminant concentrations in the brine.
Contaminant loading may also result in slight
increases in the concentrations of contaminants in
the noncondensible vent gas.
The PO*WW*ER™ system removes sources of
feed waste toxicity. The feed waste was acutely
toxic with LCSOs consistently below 10 percent.
The product condensate was nontoxic with LCSOs
consistently greater than 100 percent, but only
after the product condensate was cooled and its
pH, dissolved oxygen level, and hardness or salinity
were increased, to meet demonstration objectives
and as allowed in EPA acute toxicity testing
procedures.
The PO*WW*ER™ system operated reliably
during the SITE demonstration. However, some
minor operational problems with the
PO*WW*ER™ system were observed during
shakedown and startup operations. Operational
problems resulted from an electrical power outage
and brine sampling line clogging.
Factors affecting the performance of the oxidizer
include: (1) oxidizer temperature, (2) percent
excess oxygen (O2), and (3) oxidizer residence
time.
According to CWM, the catalyst used in the
PO*WW*ER™ system oxidizer is a proprietary
nonprecious metal oxide catalyst that withstands
fouling, activity suppression, and poisoning. Also,
according to CWM, the catalyst requires periodic
make-up to replace attrition losses.
During treatment of aqueous wastes in the
PO*WW*ER™ system, total solids (TS)
concentration ratios ranging from 32 to 1 to 50 to
1 can be achieved. TS concentrations in the brine
may range from 28 to 80 percent.
• The evaporator boiling point is an important
operatingparameterforthePO*WW*ER™system
because it determines contaminant removal
efficiencies. The evaporator boiling point
corresponds to a specific BPR, which depends on
the TS concentration in the brine.
• The physical-chemical characteristics of the brine
may have a fouling effect on heat transfer surfaces.
Periodic system cleaning may be required to
maintain high heat transfer coefficients.
• The PO*WW*ER™ technology can effectively
treat concentrated as well as dilute wastewaters.
For dilute wastewaters volume reduction will be
greater and the energy consumption per unit volume
of feed wastewater will be higher. However, as a
result, less brine will be produced and disposal
costs will be lower.
• For some applications, the PO* WW*ER™ system
may need to be constructed of corrosion resistant
material.
• Treatability studies are recommended when large-
scale applications of the technology are considered.
Preliminary treatability studies may help determine
approximate process rates and feed waste
adjustments required, allowing an assessment of
the PO*WW*ER™ system's applicability for a
specific site waste. Treatability studies can also
determine whether final product condensate
polishing treatment is required to meet discharge
requirements.
1.2 Results
This section summarizes the results of the
PO*WW*ER™ system's performance during the SITE
demonstration and during several case studies conducted
by CWM for private clients. The SITE demonstration was
conducted using a pilot-scale (pilot) PO*WW*ER™ plant
at CWM's LCTC site. Observations made during the SITE
demonstration should be used with critical engineering
judgement when projecting full-scale PO*WW*ER™
system performance.
During the SITE demonstration, the evaluation of the
PO*WW*ER™ system was restricted by testing limitations
imposed by CWM for protection of proprietary know-how.
Therefore, the following parameters were not evaluated
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during the SITE demonstration: (1) oxidation efficiency,
(2) boiling point rise, (3) heattransfercoefficients,(4) brine
characteristics (for the determination of thermal by-product
formation), and (5) scrubber blowdown characteristics.
During the SITE demonstration, the PO*WW*ER™
system treated landfill leachate, an F039 hazardous waste,
contaminated with VOCs, SVOCs, ammonia, cyanide,
metals and other inorganic contaminants. The SITE
demonstration was conducted under one set of operating
parameters, which were established by CWM based on past
experience with the PO*WW*ER™ system. These
operating parameters were applied in two sets of test runs:
one set of three replicate test runs using unspiked LCTC
landfill leachate and one set of three replicate test runs
using LCTC landfill leachate spiked with VOCs, SVOCs,
and metals. Each demonstration test required about 9 hours
of PO*WW*ER™ system operation in order to conduct
sampling and monitoring. During the tests, landfill leachate
was processed at an average rate of 0.18 gallons per minute
(gpm). Key findings of the SITE demonstration at the
LCTC site are presented below.
• The ability of the PO*WW*ER™ system to
concentrate aqueous wastes was evaluated by the
volume reduction and concentration ratio achieved.
Brine was wasted and sampled only once during
each 9-hour test run, although the PO*WW*ER™
system operated continuously. The volume of brine
wasted and sampled during each 9-hour test period
consisted of about 5 percent of the feed waste
volume processed during the 9-hour period. The
concentration ratio, defined as the ratio of TS
concentration in the brine over the TS concentration
in the feed waste, was about 32. The TS
concentration in the brine ranged from 50 to 56
percent.
• The feed waste contained average concentrations
of critical VOCs ranging from 350 to 110,000
micrograms per liter (ug/L); critical SVOCs ranging
from 6,000 to 23,000 ug/L; ammonia ranging from
140 to 160 milligrams per liter (mg/L); and cyanide
ranging from 24 to 33 mg/L. No VOCs, SVOCs,
ammonia, or cyanide were detected in the product
condensate.
• The noncondensible gas vent emissions had the
following characteristics: (1) the average carbon
monoxide (CO) emission rates ranged from 1. IxlO'3
to 3.92x 1Q-3 pounds per hour (Ib/hr); (2) the average
sulfur dioxide (SO2) emission rates were less than
5.5xlO'4 Ib/hr; and (3) the average nitrogen oxide
(NOx) concentrations emission rates ranged from
3.46xlO-2 to 5.03xlO-2 Ib/hr. The noncondensible
vent gas emissions for these parameters met the
proposed regulatory requirements for the LCTC
site.
• The PO*WW*ER™ system removes sources of
feed waste toxicity. The feed waste was acutely
toxic, with median lethal concentrations (LC50)
consistently below 10 percent. The product
condensate was nontoxic, with LCSOs consistently
greater than 100 percent, but only after the product
condensate was cooled and its pH, dissolved oxygen
level, and hardness or salinity were increased, to
meet demonstration objectives and as allowed in
EPA acute toxicity testing procedures.
• Economic data indicate that the capital cost for a
50-gpm PO*WW*ER™ system is approximately
$4 million on a turnkey basis. The capital cost
includes treatability study costs; design costs; all
necessary components of aPO*WW*ER™ system;
all interconnecting piping, controls, and monitoring
equipment; and assembly and installation costs.
Annual operating and maintenance (O&M) costs,
including labor, consumables, utilities, analytical
services, and waste disposal costs at a Superfund
site are estimated to be about $3.3 million. Waste
disposal costs account for about 70 percent of the
annual costs. The total treatment cost of a project
lasting 15 years was estimated to be about $ 100 per
1,000 gallons of aqueous waste treated; and the
total cost of aproject lasting 30 years was estimated
to be about $73 per 1,000 gallons of aqueous waste.
Key findings from 11 other case studies conducted by
CWM for several private clients are presented below.
• In six case studies, landfill leachate spiked with
VOCs, SVOCs, ammonia, and cyanide was treated
in the PO*WW*ER™ system pilot plant. The
results show that a TS concentration ratio ranging
from 38 to 1 to 40 to 1 was achieved. All of the
spiking VOCs were effectively evaporated from
the brine. Only the SVOCs originally present, or
added to the landfill leachate during spiking,
remained. Oxidation efficiencies of greater than
-------
99 percent were achieved for all spiking VOCs.
Ammonia was effectively evaporated from the
brine. At pH 11, the ammonia evaporation
efficiency was significantly higher than at
approximately pH 7 or 8. Ammonia oxidation was
more effective at higher temperatures than at lower
temperatures. In the product condensate, both
metals and organics were removed to below
National Pollutant Discharge Elimination System
(NPDES) storm water discharge limits without
further treatment.
In the seventh case study, contaminated lagoon
water was treated in the PO*WW*ER™ system
pilot plant. A concentration ratio of 50 to 1 was
achieved. The oxidation efficiency ranged from 90
to 97 percent.
In the eighth case study, fuels decant water was
treated. A concentration ratio of 42 to 1 was
achieved in the evaporator. The TOC removal
efficiency was greater than 99 percent.
In the ninth case study, well water spiked with
cyanide at 139 mg/L was treated. The well water
was acidified to cause the release of hydrogen
cyanide (HCN) gas. Cyanide was evaporated from
the brine to below detection limits. The cyanide
level in the product condensate was also below
detection limits.
In the tenth case study, oil emulsion wastewater
was treated in a bench-scale system. The
concentration ratio achieved was 35 to 1. The
oxidized product condensate contained 0.1 mg/L
ammonia, 55 mg/L chloride, and had a pH of 3.1.
In the eleventh case study, wastewater contaminated
with nitrogen-containing organic compounds and
cyanide was treated in the PO*WW*ER™ pilot
plant. The cyanide removal efficiencies ranged
from 96.9 to 99.99 percent. Cyanide oxidation
efficiencies ranged from 93.5 to 99.96 percent.
Ammonia removal efficiencies ranged from 91.6
to greater than 99.6 percent. Ammonia oxidation
efficiencies ranged from 83.8 to greater than
99.6 percent. Brine TS concentration ranged from
28 to 80 percent.
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Section 2
Introduction
This section provides background information on the
purpose, history, and goals of the Superfund Innovative
Technology Evaluation (SITE) program; discusses
documentation of the SITE demonstration results; describes
the PO*WW*ER™ technology developed by Chemical
Waste Management, Inc. (CWM); discusses innovative
features and limitation of the PO*WW*ER™ technology;
and provides a list of key contacts.
2.1 Purpose, History, and Goals of the SITE
Program
The SITE program is a unique international effort
dedicated to advancing the development, evaluation, and
implementation of innovative treatment technologies
applicable to hazardous waste sites. The SITE program was
established in response to the 1986 Superfund Amendments
and Reauthorization Act (SARA), which recognized the
need for an alternative or innovative treatment technology
research and development program. The SITE program is
administered by the U.S. Environmental Protection Agency
(EPA) Office of Research and Development (ORD) Risk
Reduction Engineering Laboratory (RREL).
The SITE program consists of four component
programs: (1) the Demonstration Program, (2) the Emerging
Technology Program, (3) the Monitoring and Measurement
Technologies Program, and (4) the Technology Transfer
Program. This Applications Analysis Report was produced
as part of the SITE Demonstration Program. The objective
of the Demonstration Program is to provide reliable
performance and cost data on innovative technologies so
that potential users can assess a technology' s suitability for
specific site cleanups. To produce useful and reliable data,
demonstrations are conducted at hazardous waste sites or
under conditions that closely simulate actual waste and site
conditions.
Data collected during a demonstration are used to
assess the performance of the technology, the potential
need for pretreatment and post-treatment processing of the
waste, treatable types of waste and media, potential operating
problems, and approximate capital and operating costs.
Demonstration data can also provide insight into a
technology' s long-term operating and maintenance (O&M)
costs and long-term application risks.
Technologies are selected for the SITE Demonstration
Program primarily through annual requests for proposals.
Proposals are reviewed by ORD staff to determine which
technologies are most promising for use at hazardous waste
sites. To be eligible, technologies must be developed to the
pilot- or full-scale stage, must be innovative, and must offer
some advantage over existing technologies. Mobile
technologies are of particular interest.
Cooperative agreements between EPA and the
developer determine responsibilities for conducting the
demonstration and evaluating the technology. The developer
is responsible for demonstrating the technology at the
selected site and is expected to pay the costs of transporting,
operating, and removing its equipment. EPA is responsible
for project planning, sampling and analysis, quality
assurance (QA), quality control (QC), preparing reports,
and disseminating information.
Each SITE demonstration provides information
necessary to evaluate the performance of a technology in
treating a particular waste at the demonstration site. To
obtain data with broad applications, EPA and the technology
developer try to choose a waste frequently found at other
contaminated sites. In many cases, however, waste
characteristics at other sites will differ in some way from
the waste tested. Thus, a successful demonstration of the
technology at one site does not ensure that it will work as
well at other sites. Data obtained from the SITE
demonstration may have to be extrapolated and combined
with other information about the technology to estimate
site-specific operating ranges and limits of the technology.
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2.2 Documentation of the SITE Demonstration
Results
The results of each SITE demonstration are presented
in two documents, the Technology Evaluation Report and
the Applications Analysis Report, each with a distinct
purpose. These documents are described below.
2.2.1 Technology Evaluation Report
The Technology Evaluation Report provides a
comprehensive description of the SITE demonstration and
its results. It is intended for engineers making a detailed
evaluation of the technology's performance for the
demonstration 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 a specific application.
The report also provides a detailed discussion of QA and
QC measures followed during the demonstration.
2.2.2 Applications Analysis Report
To encourage wider use of technologies demonstrated
under the SITE program, the Applications Analysis Report
provides information on a technology's costs and its
applicability to other sites and wastes. Before a SITE
demonstration is conducted, the amount of data available
for an innovative technology may vary widely. Data may
range from limited laboratory tests on synthetic wastes to
performance data on actual wastes treated in pilot- or full-
scale treatment systems. The Applications Analysis Report
synthesizes available information on the technology and
draws reasonable conclusions about its broad-range
applicability. This report is intended for those considering
a technology for hazardous site cleanups; it represents a
critical step in the development and commercialization of
a treatment technology.
The principal use of the Applications Analysis Report
is to assist in determining whether a technology should be
considered further as an option for a particular cleanup
situation. The Applications Analysis Report is intended for
decision makers responsible for implementing remedial
actions. The report discusses advantages, disadvantages,
and limitations of the technology. Costs for different
applications may be estimated using 12 cost categories
based on available data from pilot- and full-scale
applications. The report also discusses specific factors,
such as site and waste characteristics, that may affect
performance and cost.
2.3 Technology Description
The PO*WW*ER™ technology can be applied to
reduce the volume of an aqueous waste and to catalytically
oxidize volatile contaminants. Figure 2-1 shows a flow
diagram of the PO*WW*ER™ pilot-scale (pilot) plant.
The PO*WW*ER™ system consists primarily of an
evaporator to reduce the influent wastewater volume, a
catalytic oxidizer to oxidize the volatile contaminants hi
the vapor stream from the evaporator, a scrubber to remove
acid gases produced during oxidation, and a condenser to
condense the vapor stream leaving the scrubber.
The following sections describe the individual
components of the LCTC PO*WW*ER™ pilot plant
including: (1) the feed system, (2) the evaporator, (3) the
catalytic oxidizer, (4) the scrubber, and (5) the condenser.
2.3.1 Feed System
Wastewater to be treated by the PO*WW*ER™ pilot
plant at the LCTC site is delivered to the plant by a tanker
truck. Wastewater is pumped from the tanker truck through
a hose into the 500-gallon stainless steel feed tank. The feed
pump, which is gravity fed from the tank, pumps the feed
to the evaporator. The amount of wastewater in the tank is
determined by a level indicator on the side of the feed tank.
The feed tank is also equipped with an agitator mounted on
the top of the tank to mix additives into the wastewater
(feed waste). To control foaming in the vapor body, an
antifoaming agent can either be added to the wastewater in
the feed tank or injected directly into the vapor body. The
feed waste pH is monitored and adjusted in the feed tank
before being treated in the evaporator. The feed rate depends
on the type of waste to be treated.
2.3.2 Evaporator
The first step in the PO*WW*ER™ process is volume
reduction, which is achieved through evaporation. All
volatile compounds are vaporized depending on the relative
volatility of each compound and the composition of the
feed waste. The PO*WW*ER™ technology utilizes this
lack of specificity to treat complex wastewater mixtures.
The evaporator consists of three main pieces of
equipment: the heat exchanger, the vapor body, and the
entrainment separator. As feed waste is pumped to the
evaporator, it combines with heated process liquor. The
liquid waste is then further heated in a vertical shell-and-
tube heat exchanger, which has two passes, four tubes per
-------
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LEGEND
(T) Feed waste sample point
(2) Product condensate sample point
(5) Brine sample point
(4) Noncondensible gas sample point
Figure 2-1. PO*WW*ER™ pilot plant flow diagram.
pass. Heat is supplied by steam generated in a boiler. Liquid
waste flows through the tube side of the heat exchanger and
steam passes through on the shell side. In the heat exchanger,
the liquid is heated to boiling, but boiling does not occur in
the tubes because of the back pressure in the system. In the
pilot plant, this back pressure is created by a designed
gravity head assisted by a valve between the heat exchanger
and the vapor body.
After passing through the heat exchanger, the liquid
waste enters the vapor body, where boiling occurs, and
vapor is released. The vapor consists of mostly water and
volatile contaminants, both organic and inorganic. The
liquid level in the vapor body is monitored through sight
glasses located on the side of the vapor body vessel. The
liquid level is controlled by the feed rate and brine purge
rate. A portion of the concentrated brine is removed
periodically from the vapor body in batches. When the
brine temperature reaches a value corresponding to a
specific brine boiling point resulting from a specific brine
concentration, a valve at the bottom of the vapor body is
opened and some of the brine is drained by gravity into a55-
gallon waste brine drum. The vapor exits the vapor body to
an entrainment separator, and the remaining heated process
liquor is recirculated.
Depending on the nature of the feed waste, foaming
may occur in the vapor body. If foaming is not controlled,
foam can pass through the mesh pad of the evaporator,
leave deposits in the catalytic oxidizer, plug the catalyst
tray, and contaminate the product water. 'An antifoaming
agent can be injected directly into the vapor body.
The vapor that exits the vapor body may contain mist
droplets from the process liquor. The mist droplets from the
boiling liquid waste could be carried through the process
and deposit on the catalytic oxidizer, causing scaling, or
contaminate the product condensate, if not removed. The
entrainment separator is designed to remove these droplets
from the vapor stream. The entrainment separator is
periodically rinsed with water, and the rinse water is
drained into the recirculation line of the system.
-------
2.3.3 Catalytic Oxidizer
The second step in the PO*WW*ER™ process is
oxidation of volatile organics and inorganics in the vapor
stream from the evaporator. The process is designed to
operate with a catalyst in either a fluidized or static bed
mode. The fluidized bed mode ensures sufficient contact
between the catalyst and the vapor. However, because the
pilot plant has been operated successfully in a static bed
mode, this mode was used during the demonstration.
In a full-scale PO*WW*ER™ system, the oxidizer
consists of three main pieces of equipment: the recuperative
heat exchanger, the oxidizer heater, and the catalytic
oxidizer. In a full-scale system, the inlet vapor is preheated
along with oxidation air in a recuperative heat exchanger,
with vapor exiting the catalytic oxidizer. The preheated
vapor from the evaporator is further heated to oxidation
temperature by the oxidizer heater, a direct-fired propane
burner. Air is fed to the system by a blower. The heated
vapor then enters the catalytic oxidizer and passes through
the catalyst bed where oxidation takes place. The pressure
drop across the catalyst bed is monitored at all times for
clogs in the catalyst bed. Possible oxidation products
include carbon dioxide (CO2), water, hydrochloric acid
(HC1), sulphur dioxide (SO2), nitrogen oxides (NOx), and
products of incomplete combustion (PIC).
The PO*WW*ER™ pilot-scale plant at CWM' s LCTC
sitediffers from the full-scale systemin two aspects: it does
not have a recuperative heat exchanger and air is fed to the
system by a compressor.
2.3.4 Scrubber
The third step of the PO*WW*ER™ technology
involves scrubbing the vapor stream to neutralize the acid
gases produced in the oxidizer. The scrubber consists of a
packed bed in which the vapor passes countercurrently
through caustic solution. The scrubber neutralizes and
removes the acid gases produced by oxidation.
2.3.5 Condenser
Vapor exiting the scrubber is cooled and condensed in
a shell-and-tube condenser. Vapor is cooled on the shell
side by noncontact cooling water passing through the tube
side. During the SITE demonstration, the temperature of
the product condensate was about 125 °F. The condenser is
equipped with a vent to remove noncondensible gases. The
product condensate is collected in a condensate holding
tank, where it remains until it is transferred to a 250-gallon
stainless steel product tank. This product liquid can either
be reused as boiler or cooling tower makeup water, or
discharged to surface water, if appropriate.
2.4 Innovative Features and Limitations of the
PO*WW*ER™ Technology
ThePO*WW*ER™systemcombinestwoconventional
technologies typically used in the chemical, petroleum,
electronics, and hazardous waste industries, in a novel
arrangement. Evaporation is a nonspecific separation
process; all volatile material is vaporized depending on the
relative volatility of each compound and the composition
of the feed waste. The PO*WW*ER™ technology uses this
lack of specificity advantageously to completely treat
wastewaters.
ThecatalystusedinthePO*WW*ER™systemoxidizer
is the main innovative feature of the system. The catalyst is
a proprietary nonprecious metal oxide contained in a specific
support medium. According to CWM, the catalyst is not as
expensive or limited in versatility as a precious metal
catalyst. The catalyst has been designed to withstand
problems common to precious metal catalysts such as
fouling, activity suppression, and poisoning. Due to the
nature of the catalyst, periodic make-up is required to
replace attrition losses.
The PO* WW*ER™ technology can treat concentrated
and dilute aqueous wastes. Treatment of dilute aqueous
wastes may require increased energy requirements, however,
brine disposal costs will be significantly lower. In addition,
the PO*WW*ER™ technology is advantageous for treating
process wastewaters that produce recyclable brine. If brine
cannot be recycled, it needs off-site treatment and disposal.
2.5 Key Contacts
Additional information on the PO*WW*ER™
technology and SITE program can be obtained from the
following sources:
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The PO*WW*ER™ Technology
Technology Developer Representative
Mr. Myron Reicher
Chemical Waste Management, Inc.
,c/o ARI Technologies, Inc.
1501 E. Woodfield Road
Schaumburg, IL 60173
(708) 706-6900
Technology Licenser Representative
Annamarie B. Connolly
ARI Technologies, Inc.
1501 E. Woodfield Road
Schaumburg, IL 60173
(708) 706-6900
The SITE Program
Mr. Randy Parker
U.S. Environmental Protection Agency
Office of Research and Development
Risk Reduction Engineering Laboratory
26 West Martin Luther King Drive
Cincinnati, OH 45268
(513)569-7271
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Section 3
Technology Applications Analysis
This section addresses the applicability of the
PO*WW*ER™ system in treating aqueous wastes
containing volatile organic compounds (VOC), semivolatile
organic compounds (S VOC), cyanide, ammonia, andmetals.
CWM's claims regarding the applicability and performance
of the PO*WW*ER™ system are included in Appendix A.
The applicability of the PO*WW*ER™ system was
evaluated in terms of technical criteria used to select
actions at Superfund sites. These criteria, which can also be
applied to RCRA, underground storage tank (UST), and
other corrective action decisions, include the following:
(1) treatment effectiveness for volume reduction,
(2) treatment effectiveness for toxicity reduction,
(3) compliance with regulatory requirements,
(4) implementability, (5) short-term impact, and (6) long-
term effectiveness. These criteria are discussed in the
following sections. Factors influencing the system's
performance and reliability in meeting these criteria and
evaluation limitations are discussed at the end of this
section.
The discussion presented below is based on results of
the PO*WW*ER™ system SITE demonstration at the
LCTC site (see Appendix B) and several other case studies
conducted by CWM for various private clients (see
Appendix C). The technology demonstration was conducted
under one set of operating parameters, which were
established by CWM based on past operating experience
with the PO*WW*ER™ system. These operating
parameters were used in two sets of test runs: one set of
three replicate test runs using unspiked LCTC landfill
leachate and one set of three replicate test runs using LCTC
landfill leachate spiked with VOCs, SVOCs, and metals.
Each demonstration test run required about 9 hours of
PO*WW*ER™ system operation in order to conduct
sampling and monitoring. During the SITE demonstration,
the evaluation of the PO*WW*ER™ system was restricted
by testing limitations imposed by CWM. These limitations
are discussed in Section 3.8.
The SITE demonstration and case study results indicate
that the PO*WW*ER™ system can process a wide variety
of wastewaters with different contaminant concentrations.
According to CWM, the PO*WW*ER™ system can
effectively treat the following: landfill leachate,
contaminated well water, contaminated lagoon water, fuels
decant water, oil emulsion wastewater, and wastewater
contaminated with nitrogen-containing organic compounds
and cyanide. CWM also states that the PO*WW*ER™
system can treat wastewater containing VOCs, SVOCs,
pesticides, herbicides, solvents, heavy metals, cyanide,
ammonia, nitrate, chloride, and sulfide.
Although an extensive data base has been generated on
the PO*WW*ER™ system's effectiveness in treating
various wastewaters, the technology's performance is best
predicted by bench-scale testing. Certain contaminants
may behave differently in association with other compounds
and under different pH conditions. Therefore, preliminary
testing is important in determining the technology's
applicability to meet treatment objectives. Preliminary
treatability studies may also help determine approximate
process rates and feed waste adjustments required, allowing
assessment of the PO*WW*ER™ system's site-specific
applicability.
At the LCTC site, the SITE demonstration was
conducted using a pilot-scale PO*WW*ER™ system.
Therefore, observations made during the SITE
demonstration should be used with critical engineering
judgement when projecting full-scale PO*WW*ER™
system performance.
3.1 Treatment Effectiveness for Volume
Reduction
The PO*WW*ER™ system reduces the volume of an
aqueous waste by evaporation and concentrates nonvolatile
contaminants in the brine. During each 9-hour test run, the
PO*WW*ER™ system processed about 98 gallons of feed
waste. Brine was wasted and sampled only once during the
11
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9-hour test period. The total amount of brine wasted during
each 9-hourtestrun was about4.8 gallons, orabout5 percent
of the total feed waste volume.
The PO* WW*ER™ system's effectiveness for volume
reduction was evaluated based on the concentration ratio,
which is defined as the ratio of total solids (TS) concentration
in thebrine over the TS concentration in the feed waste. The
concentration ratio based on TS was estimated to be about
31 to 1 during the unspiked tests and 32 to 1 during the
spiked tests. To confirm this estimate, the concentration
ratio was also estimated based on the ratio of chloride and
metals in the brine and feed waste. The chloride
concentration ratio was 33 to 1 during the unspiked tests
and 31 to 1 during the spiked tests. The metals concentration
ratio was 33 to 1 during the unspiked tests and 30 to 1 during
the spiked tests.
Results from other case studies (see Appendix C) sho w
that the PO*WW*ER™ system achieved TS concentration
ratios ranging from 35 to 1 to 50 to 1. Brine TS concentrations
ranged from 28 to 80 percent.
3.2 Treatment Effectiveness for Toxicity
Reduction
The PO* WW*ER™ system's effectiveness for toxicity
reduction was evaluated based on the following criteria: (1)
VOC removal, (2) S VOC removal, (3) ammoniaand cyanide
removal, (4) noncondensible gas emissions, and (6) acute
toxicity. These criteria are discussed below.
3.2.1 VOC Removal
The PO*WW*ER™ system effectively removes VOCs
from the feed waste during evaporation. The VOCs are
subsequently oxidized in the catalytic oxidizer. The product
condensate contains nondetectable amounts of VOCs.
During the SITE demonstration, VOC oxidation efficiencies
were not determined (see Section 3.8 for details).
Acetone, 2-butanone, methylene chloride,
tetrachloroethene (PCE), toluene, and vinyl chloride were
identified as critical VOCs for the PO*WW*ER™ system
SITE demonstration. However, vinyl chloride was not
detected in any samples analyzed and therefore is not
discussed further. During the spiked tests, feed waste was
spiked with the following VOCs, each at levels of
100 milligrams per liter (mg/L): methylene chloride, PCE,
and toluene. The purpose of spiking the feed waste was to
test the effect of contaminant loading on VOC treatment
efficiency.
During the unspiked test runs, the acetone concentration
in feed waste samples ranged from 8,200 to
12,000 micrograms per liter (ug/L); in brine samples it was
less than the detection limit of 100 ug/L during the first and
second unspiked test runs and 140 ug/L during the third
unspiked test run; and in product condensate samples it was
less than the detection limit of 10 ug/L. During the spiked
test runs, the acetone concentration in feed waste samples
ranged from 13,000 to 18,000 ug/L; in brine samples it
ranged from 180 to 220 ug/L. The results indicate that
during the spiked test runs, acetone was not completely
removed from the brine. Because acetone was not one of
the spiking compounds, the results suggest that total
contaminant loading, which increased during spiking, had
a measurable effect on the acetone evaporation efficiency.
However, the concentration of acetone in product
condensate samples during the spiked test runs was less
than the detection limit of 10 ug/L, indicating that total
contaminant loading had no measurable effect on product
condensate quality.
During the unspiked test runs, the 2-butanone
concentration in feed waste samples ranged from 1,500 to
2,200 ug/L; in brine samples it was less than the detection
limit of 100 ug/L; and in product condensate samples it was
less than the detection limit of 10 ug/L. During the spiked
test runs, the 2-butanone concentration in feed waste samples
was less than the detection limit of 10,000 ug/L; in brine
samples it was less than the detection limit of 100 ug/L; and
in product condensate samples it was less than the detection
limit of 10 ug/L. These results indicate that total contaminant
loading had no measurable effect on the 2-butanone
evaporation efficiency or product condensate quality.
During the unspiked test runs, the methylene chloride
concentration in feed waste samples ranged from 640 to
1,700 ug/L; in brine samples it was less than the detection
limit of 50 ug/L; in product condensate samples it was less
than the detection limit of 5 ug/L during the first and third
unspiked test runs. However, during the second unspiked
test run, the concentration of methylene chloride in product
condensate ranged from 5 to 8 ug/L. During the spiked test
runs, methylene chloride concentrations in feed waste
samples ranged from 88,000 to 110,000 ug/L; in brine
samples it ranged from 110 to 200 ug/L. The results suggest
that total contaminant loading, which increased during the
spiked test runs, had a slight but measurable effect on
methylene chloride evaporation efficiency. However, the
concentration of methylene chloride in product condensate
samples was less than the detection limit of 5 ug/L,
12
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indicating that total contaminant loading had no measurable
effect on product condensate quality.
During the unspiked test runs, the PCE concentration
in feed waste samples was less than the detection limit of
500 ug/L; in brine samples it was below the detection limit
of 50 ug/L; in product condensate samples it was less than
the detection limit of 5 ug/L. During the spiked test runs,
the PCE concentration in feed waste samples ranged from
47,000 to 60,000 ug/L; in brine samples it ranged from less
than the detection limit of 50 to 69 ug/L. The results
suggest that total contaminant loading, which increased
during the spiked test runs, had a slight but measurable
effect on PCE evaporation efficiency. However, the
concentration of PCE in product condensate samples was
less than the detection limit of 5 ug/L, indicating that total
contaminant loading had no measurable effect on product
condensate quality.
During the unspiked test runs, the toluene concentration
in feed waste samples was less than the detection limit of
500 ug/L; in brine samples it was less than the detection
limit of 50 ug/L; and in product condensate samples it was
less than the detection limit of 5 ug/L. During the spiked
test runs, the toluene concentration in feed waste samples
ranged from 46,000 to 69,000 ug/L; in brine samples it was
less than the detection limit of 50 ug/L; and in the product
condensate, it was less than the detection limit of 5 ug/L.
The results suggest that total contaminant loading had no
measurable effect on the toluene evaporation efficiency or
on product condensate quality.
During other case studies conducted by CWM (see
Appendix C), landfill leachate spiked with 100 mg/L of
each of the following VOCs was treated in the
PO*WW*ER™ pilot plant: acetone, carbon disulfide,
chlorobenzene, methanol, methyl ethyl ketone, methylene
chloride, toluene, and trichloroethene. The results show
that all of the spiking VOCs were effectively evaporated
from the brine and successfully oxidized in the catalytic
oxidizer. Oxidation efficiencies greater than 99 percent
were achieved.
In another case study conducted by CWM, landfill
leachate spiked with methanol ranging from 500 to
5,000 mg/L was treated in the PO*WW*ER™ pilot plant.
Methanol was effectively evaporated and oxidized. An
overall removal efficiency of 98 percent was achieved.
3.2.2 SVOC Removal
The PO*WW*ER™ system removes some SVOCs
from the feed waste during evaporation. The evaporated
SVOCs are subsequently oxidized in the catalytic oxidizer.
SVOCs with relatively high boiling points do not totally
vaporize but remain in the brine. The product condensate
contains nondetectable amounts of SVOCs. During the
SITE demonstration, SVOC oxidation efficiencies were
not determined (see Section 3.8 for details).
Benzoic acid and phenol were identified as critical
SVOCsforthePO*WW*ER™systemSITEdemonstration.
During the spiked tests, feed waste was spiked with 10 mg/L
of phenol to test the effect of contaminant loading on
SVOC treatment efficiency.
During the unspiked test runs, the benzoic acid
concentration in feed waste samples ranged from 6,300 to
24,000 ug/L; in brine samples it ranged from 600,000 to
1,600,000 ug/L; and in product condensate samples it was
less than the detection limit, which ranged from 25 to 130
ug/L. During the spiked test runs, the benzoic acid
concentration in feed waste samples ranged from 13,000 to
24,000 ug/L; in brine samples concentrations ranged from
620,000 to 930,000 ug/L; and in product condensate samples
it was less than the detection limit, which was 130 ug/L for
most samples analyzed. The results indicate that during the
unspiked and spiked test runs, benzoic acid concentrated
primarily in the brine.
During the unspiked test runs, the phenol concentration
in feed waste samples ranged from 5,300 to 11,000 ug/L;
in brine samples it was less than the detection limit of
200,000 ug/L; and in product condensate samples it was
less than the detection limit, which ranged from 10 to 50
ug/L. During the spiked test runs, the phenol concentration
in feed waste samples ranged from 12,000 to 17,000 ug/L;
in brine samples it was less than the detection limit of
200,000 ug/L; and in product condensate samples it was
less than the detection limit of 50 ug/L. The results indicate
that phenol apparently vaporizes, at least partially, and is
presumably oxidized in the catalytic oxidizer.
Although benzoic acid and phenol are both acidic
compounds, they have very different physical-chemical
properties. Given these properties, phenol is more likely
than benzoic acid to be removed from the brine. Phenol has
a vapor pressure over 30 times greater than that of benzoic
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acid. Also, under the test conditions, phenol was likely
present in the brine primarily in unionized form while
benzoic acid was likely present in ionized form.
Results from other case studies also indicate that
certain SVOCs vaporize and are successfully oxidized (see
Appendix C). However, SVOCs with high boiling points
will generally concentrate in the brine.
3,2.3 Ammonia and Cyanide Removal
Ammonia and cyanide evaporation efficiency in the
PO*WW*ER™ system depends on the feed waste pH and
the types of metals present. Under certain conditions, the
PO*WW*ER™ system vaporizes ammonia and cyanide in
the evaporator and effectively oxidizes both in the catalytic
oxidizer. During the SITE demonstration, ammonia and
cyanide oxidation efficiencies were not determined (see
Section 3.8 for details). Ammonia forms very strong
complexes with cadmium, cobalt, copper, silver, mercury,
nickel, and zinc. Cyanide forms complexes with cadmium,
copper, silver, mercury, iron, nickel, and zinc. All the
above-mentioned metals were present in feed waste samples
taken during unspiked and spiked test runs. The metal
complexes of ammonia and cyanide need to be destroyed
before cyanide can be evaporated and oxidized. Free
ammonia volatilizes effectively atpH values greater than 9,
while free cyanide volatilizes effectively at pH values less
than 9.
During the unspiked test runs, the ammonia
concentration in feed waste samples ranged from 150 to
160 mg/L; in brine samples it ranged from 5.4 to 23 mg/L;
and in product condensate samples it was less than the
detection limit of 0.1 mg/L. During the spiked test runs, the
ammonia concentration in feed waste samples ranged from
140 to 160 mg/L; in brine samples it ranged from 7.4 to
7.8 mg/L. The results indicate that during the unspiked and
spiked test runs, ammonia was not completely removed
from the brine, possibly because the feed waste pH ranged
from 8.5 to 9.1, close to the lower optimum pH range for
ammonia volatilization, or because ammonia complexed
with metals, which were present in the feed waste. The
concentration of ammonia in product condensate was less
than the detection limit of 0.1 mg/L for all samples analyzed,
indicating that total contaminant loading, which increased
during the spiked test runs, had no measurable effect on
product condensate quality.
Duringthe unspiked testruns, the cyanide concentration
in feed waste samples ranged from 25 to 34 mg/L; in brine
samples it ranged from 77 to 150 mg/L; and in product
condensate samples it was less than the detection limit of
0.01 mg/L. During the spiked test runs, the cyanide
concentration in feed waste samples ranged from 24 to
36 mg/L; in brine samples it ranged from 17 to 77 mg/L.
The results indicate that during the unspiked and spiked test
runs, cyanide was not completely removed from the brine,
possibly because the feed waste pH ranged from 8.5 to 9.1,
which is close to the upper optimum pH range for cyanide
volatilization, or because cyanide complexed with metals,
which were present in the feed waste. The concentration of
cyanide in product condensate was less than the detection
limit of 0.01 mg/L for all samples analyzed, indicating that
total contaminant loading had no measurable effect on
product condensate quality.
During one case study conducted by CWM, waste water
contaminated with nitrogen-containing organic compounds
and cyanide was treated in the PO*WW*ER™ pilot plant
(see Appendix C). The pH of the feed waste ranged from 4
to 4.42. Cyanide removal efficiencies ranging from 96.9 to
99.99 percent were achieved. Cyanide oxidation efficiencies
ranged from 93.5 to 99.96 percent. Ammonia removal
efficiencies ranging from 91.6 to greater than 99.6 percent
were achieved. Ammonia oxidation efficiencies ranged
from 83.8 to greater than 99.6 percent.
In another case study conducted by CWM, well water
spiked with cyanide at 139 mg/L was treated (see
Appendix C). The well water was acidified to cause the
release of hydrogen cyanide (HCN) gas. Cyanide was
removed from the brine to below the detection limit.
Cyanide in the product condensate also was below the
detection limit.
Results from another case study conducted by CWM
(see Appendix C) with landfill leachate spiked with
ammonia ranging from 75 to 2,880 mg/L indicate that
ammonia was effectively evaporated when the feed waste
pH ranged from 9 to 11.
In another case study, landfill leachate spiked with
1,000 mg/L ammonia was treated in the PO*WW*ER™
system (see Appendix C). At pH 11, ammonia evaporation
efficiency was significantly higher than at a pH ranging
from 7 to 8.
3.2.4 Noncondensible Gas Emissions
During the SITE demonstration, continuous emissions
monitoring (CEM) of the noncondensible vent gas was
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conducted. CO, SO2, and NOx are critical analytes and are
discussed below. The average CO concentrations ranged
from 9.58 to 37.3 parts per million by volume (ppmv),
resulting in emissions ranging from l.lxlO'3 to
3.92x 10'3 pounds per hour (Ib/hr). The 60-minute maximum
CO concentrations ranged from 11.1 to 40.8 ppmv, resulting
in emissions ranging from 1.27xlQ-3 to 4.28xlQ-3 Ib/hr. The
average SO2 concentrations were less than 2 ppmv, resulting
in emissions of less than 5.5xlCH Ib/hr. The 60-minute
maximum SO2 concentrations ranged from less than 2 to
3.49 ppmv, resulting in emissions ranging from less than
S.SxlO'4 to 8.4xlO-4 Ib/hr. The average NOx concentrations
ranged from 233 to 292 ppmv, resulting in emissions
ranging from 3.46xlO'2 to 5.03xlO'2 Ib/hr. The 60-minute
maximum NOX concentrations ranged from 241 to
309 ppmv, resulting in emissions ranging from 3.59x10~2 to
5.34xlO'2 Ib/hr. The noncondensible vent gas emissions for
these parameters met the proposed regulatory requirements
for the LCTC site.
During the SITE demonstration, noncondensible vent
gas samples were collected and analyzed for VOCs, S VOCs,
and HC1. The following VOCs were detected at trace
levels: chloromethane; bromomethane; methylene chloride;
acetone; carbon disulfide; 2-butanone; 1,1,1-
trichloroethane; benzene; PCE; toluene; chlorobenzene;
andethylbenzene. Acetone, 2-butanone, methylene chloride,
PCE, and toluene are critical analytes consistently present
in the feed waste. The critical VOC present in the
noncondensible vent gas at the highest concentration was
PCE. During the first and third unspiked test runs, the
concentration of PCE was less than the detection limits of
2.47 and 2.44 ppmv, respectively. During the second
unspiked run, PCE was present at 3.93 ppmv. During the
spiked test runs, the concentration of PCE ranged from 173
to 285 ppmv. The highest PCE concentration occurred
during the first spiked test run, which also had the highest
NOx, SO2, CO, and total nonmethane hydrocarbon
(TNMHC) concentrations. All other VOCs were present at
concentrations less than 50 micrograms per dry standard
cubic meter (ug/dscm) and usually below 10 ug/dscm.
HC1 and some SVOCs were also detected in
noncondensible vent gas samples. HC1 was detected only
during the second and third unspiked test runs at
concentrations of 48.6 and 247 ug/dscm, respectively.
The following SVOCs were also present in the
noncondensible gas emissions at trace levels: phenol,
benzoic acid, bis-(2-ethylhexyl) phthalate, and di-n-
octylphthalate. During the unspiked test runs, SVOCs were
present at the following concentrations: phenol from less
than 1.4 to 1.6 ug/dscm, benzoic acid from less than 6.8 to
6.8 ug/dscm, bis-(2-ethylhexyl) phthalate at less than
1.4 ug/dscm, and di-n-octylphthalate from less than 1.4 to
3.9 ug/dscm. During the spiked test runs, phenol
concentrations ranged from less than 1.4 to 1.7 ug/dscm,
benzoic acid concentrations ranged from less than 6.7 to
31.8 ug/dscm, bis-(2-ethylhexyl) phthalate concentrations
ranged from less than 1.3 to 31.4 ug/dscm, and di-n-
octylphthalate concentrations ranged from less than 1.4 to
9 ug/dscm.
During the SITE demonstration, TNMHC concentration
was monitored by the CEM system. During the unspiked
test runs, the average and maximum TNMHC was less than
the detection limit of 2 ppmv, resulting in emissions of less
than 3.7x10-" Ib/hr. During the spiked test runs, the average
TNMHC was also less than the detection limit of 2 ppmv,
resulting in emissions of less than 3.7xlO'4 Ib/hr. However,
during the spiked test runs, the maximum TNMHC
concentration ranged from 2.53 to 3.59 ppmv, resulting in
emissions ranging from 3.8xlO~4 to 6.7xlO'4 Ib/hr.
Noncondensible gas emissions results from the SITE
demonstration indicate that increases in total contaminant
loading result in slight increases in contaminant
concentrations in the vent gas. However, the noncondensible
vent gas emissions met the proposed regulatory requirements
for the LCTC site.
3.2.5 Acute Toxicity
TheabilityofthePO*WW*ER™technologytoproduce
nontoxic product condensate was evaluated by collecting
grab samples of leachate feed and product condensate and
testing those samples for acute toxicity. The tests were
performed off site with the freshwater species Ceriodaphnia
dubia (a cladocera) and Pimephales promelas (fathead
minnow), and the marine species Mvsidopsis bahia (mysid
shrimp) and Cvprinodon variegatus (sheepshead minnow).
Acute toxicity was measured by counting the number of
organisms surviving after 48 hours of exposure to leachate
feed, product condensate, and control water. The survival
data were used to compute a median lethal concentration
(LC50). The LC50 represents a sample concentration,
which is expressed as a percentage that is lethal to 50
percent of the test organisms.
Acute toxicity was measured using two sample
conditions. Condition 1 involved adjusting leachate feed
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and product condensate to equivalent pH, temperature, and
hardness or salinity levels to meet demonstration objectives,
and as allowed in EPA acute toxicity testing procedures.
The adjusted levels were optimal for survival of the test
species (EPA, 1991) and sources of toxicity other than
metals and organics were absent. Condition 2 involved
adjusting product condensate pH and temperature to the
same levels used in Condition 1, but without hardness
adjustment. Salinity was not adjusted for Condition 2
because only freshwater species were tested.
Acute toxicity results show that the PO*WW*ER™
technology reduced sources of acute toxicity in leachate
feed. Condition 1 leachate feed samples were highly toxic,
with LC50 values consistently less than 10 percent, while
product condensate samples were consistently nontoxic,
with no statistically significant difference in acute toxicity
between 100 percent product condensate and the control
(LC50 was less than 100 percent). Ceriodaphnia dubia was
the most sensitive of the four species to leachate feed.
Sample conditions such as pH, temperature, and
hardness can influence the toxicity test (EPA, 1991). Field
measurements taken during the SITE demonstration at the
LCTC site show that product condensate discharged from
the PO* W\V*ER™ technology had an average temperature
of about 125 °F and a pH of between 3.83 and 4.27. Acute
toxicity may occur in unacclimated species from elevated
temperatures and low pH. Also, the PO*WW*ER™
technology produces a product condensate with a hardness,
as measured in the laboratory, of less than 1 mg/L as
calcium carbonate. This lack of hardness increased acute
toxicity. Condition 2results indicate thatproduct condensate
without hardness adjustment was acutely toxic to both
freshwater species.
3.3 Compliance With Regulatory Requirements
This subsection discusses specific environmental
regulations pertinent to the operation of the PO* WW*ER™
technology, including the transport, treatment, storage, and
disposal of wastes generated during the operation of the
PO*WW*ER™ system. The regulations that apply to a
particular remediation activity depend on the type of
remediation site and the type of waste being treated. These
regulations include the Comprehensive Environmental
Response, Compensation, and Liability Act (CERCLA);
RCRA; the Clean Water Act (CWA); the Safe Drinking
Water Act (SDWA); the Clean Air Act (CAA); the Toxic
Substances Control Act (TSCA); various radioactive waste
regulations; mixed waste regulations; and the Occupational
Safety and Health Act (OSHA).
3.3.1 CERCLA
CERCLA, as amended by SARA of 1986, provides for
federal authority to respond to releases of hazardous
substances, pollutants, or contaminants to air, water, and
land (Federal Register, 1990a). Section 121 (Cleanup
Standards) of SARA requires that selected remedies be
protective of human health and the environment and be
cost-effective. SARA states a preference for remedies that
are highly reliable, provide long-term protection, and employ
treatment that permanently and significantly reduces the
volume, toxicity, or mobility of hazardous substances,
pollutants, or contaminants. Section 121 also requires that
remedies selected at Superfund sites comply with federal
and state applicable or relevant and appropriate requirements
(ARAR). Six conditions exist under which ARARs for a
remedial action may be waived: (1) the action is an interim
measure and the ARAR will be met at completion;
(2) compliance with the ARAR would pose a greater risk to
human health and the environment than noncompliance;
(3) it is technically impracticable to meet the ARAR;
(4) the standard of performance of an ARAR can be met by
an equivalent method; (5) a state standard has not been
consistently applied elsewhere; and (6) ARAR compliance
wouldnotprovideabalance between the protection achieved
at a particular site and demands on the Superfund for other
sites. These waiver options apply only to Superfund actions
taken on site, and justification for the waiver must be
clearly demonstrated (EPA, 1988).
Generally, contaminated water and noncondensible
gas emissions treatment using the PO*WW*ER™
technology will take place on site, but treated water (product
condensate) reuse or discharge and brine disposal may take
place either on site or off site. On- and off-site actions must
meet the substantive requirements (for example, emission
standards) of all ARARs. Off-site actions must also meet
permitting and any other administrative requirements of
environmental regulations.
5.3.2 RCRA
RCRA, as amended by the Hazardous and Solid Waste
Amendments of 1984, regulates management and disposal
of municipal and industrial solid waste. The EPA and
RCRA-authorized states (listed in 40 Code of Federal
Regulations [CFR] Part 272) implement and enforce RCRA
and RCRA-equivalent state regulations.
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RCRAregulations define hazardous wastes and regulate
their transport, treatment, storage, and disposal. Wastes
defined as hazardous under RCRA include characteristic
and listed wastes. Criteria for identifying characteristic
hazardous wastes are included in 40 CFR Part 261,
Subpart C. Listed wastes from nonspecific and specific
industrial sources, off-specification products, spill cleanups,
and other industrial sources are itemized in 40 CFR Part 261,
Subpart D.
The PO*WW*ER™ technology has been used to treat
industrial wastewaters and landfill leachate contaminated
with a variety of organic and inorganic contaminants.
Contaminated water to be treated by the PO*WW*ER™
technology will probably be hazardous or sufficiently
similar to hazardous waste so that RCRA requirements will
apply. If contaminated water to be treated is determined to
be a hazardous waste, the PO*WW*ER™ technology will
need to meet 40 CFR Part 265 standards for tank storage
(Subpart J) because the technology includes tank storage
of contaminated and treated water. Also, RCRA treatment
requirements must be met.
Brine and product condensate generated during
treatment must be stored and disposed of properly. If
contaminated water treated by the PO*WW*ER™
technology is a listed waste, treatment residues (brine and
product condensate) will be considered listed wastes unless
RCRA delisting requirements are met. If treatment residues
are not listed wastes, they should be tested to determine if
they are RCRA characteristic hazardous wastes. The brine
should also be tested using EPA Method 9095 (paint filter
liquids test) to determine if it contains free liquids. During
the SITE demonstration brine contained free liquids.
However, brine characteristics may vary for different
applications depending on feed waste characteristics.
Wastes containing no free liquids are excluded from various
leak detection and secondary containment requirements
for disposal. If the brine is not hazardous and does not
contain free liquids, it can be disposed of at a nonhazardous
waste landfill. If the brine or product condensate is
hazardous, the RCRA standards discussed below apply.
In 40 CFR Part 262, standards for generators of
hazardous waste are presented. These requirements include
obtaining an EPA identification number, meeting waste
accumulation standards, labeling wastes, and maintaining
appropriate records. Part 262 allows generators to store
wastes up to 90 days without a permit and without having
interim status as a treatment, storage, or disposal facility. If
treatment residues are stored on site for 90 days or more,
40 CFR Part 265 requirements apply.
Any facility designated for permanent disposal of
hazardous wastes must be in compliance with RCRA.
Disposal facilities must fulfill permitting, storage,
maintenance, and closure requirements presented in 40 CFR
Parts 264 through 270. In addition, any authorized state
RCRA requirements must be fulfilled. If treatment residues
are disposed of off site, 40 CFR Part 263 transportation
standards apply.
For both CERCLA actions and RCRA corrective
actions, the brine waste generated by the PO*WW*ER™
technology will be subject to federal Land Disposal
Restrictions (LDR) if it is hazardous and land disposed
(EPA, 1989a). Several LDR compliance alternatives exist
for disposing of brine waste if it is hazardous: (1) comply
with the LDR in effect; (2) comply with the LDRs by
choosing one of the LDR compliance alternatives (for
example, treatability variance, no migration petition); or
(3) invoke an ARAR waiver (this option applies only to on-
site CERCLA disposal).
In 40 CFR Part 264, Subparts F (promulgated) and S
(proposed), requirements for corrective action at RCRA-
regulated facilities are presented. These subparts generally
apply to remediation at Superfund sites. Subparts F and S
include requirements for initiating and conducting RCRA
corrective actions, remediating ground water, and ensuring
that corrective actions comply with other environmental
regulations. Subpart S also details conditions under which
particular RCRA requirements may be waived for temporary
treatment units operating at corrective action sites (Federal
Register, 1990b).
During the SITE demonstration, the PO*WW*ER™
system at the LCTC site treated a listed hazardous waste—
F039, landfill leachate. Therefore, the product condensate
and waste brine were also considered hazardous wastes.
However, if the leachate was not a listed waste, the product
condensate and brine would need to be tested for hazardous
waste characteristics.
Based on the SITE demonstration test results, the
product condensate contained no detectable levels of VOCs
and SVOCs and only trace levels of metals. If the product
condensate was not a listed waste, it could have been
disposed of as nonhazardous waste. The brine, however,
exhibited the hazardous characteristic of toxicity and has
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the potential to exhibit the characteristic of reactivity
becauseof its cyanidecontent(seeSection3.6.2).Hazardous
contaminants in the feed waste that do not evaporate or
oxidize in the PO*WW*ER™ system concentrate in the
brine; therefore, this treatment residual will likely always
be a hazardous waste.
3.3.3 CWA
The National Pollutant Discharge Elimination System
(NPDES) permitting program established under the CWA
issues, monitors, and enforces permits for direct discharges
to surface water bodies. Discharges to off-site receiving
waters or to publicly owned treatment works (POTW) must
comply with applicable federal, state, and local
administrative and substantive requirements. Effluent limits
are specified in the NPDES permit issued for direct
discharges to off-site receiving waters. NPDES permits
protect aquatic life by imposing chemical-specific limits
and whole effluent toxicity (WET) limits. WET is defined
in 40 CFR Part 122.2. EPA-approved test methods for
measuring acute and chronic WET are referenced in 40 CFR
Part 136. No NPDES permits are required for on- or off-site
discharges to POTWs, but all substantive requirements
(such as discharge limitations) should be identified and
achieved. Discharges to POTWs are generally regulated
through local sewer use ordinances.
Based on the SITE demonstration test results, the
product condensate could probably be discharged to either
a POTW without further treatment or to a nearby surface
water body after additional treatment. Additional treatment
would probably include increasing the pH from about 4,
increasing the hardness from less than 1 mg/L, and
decreasing the temperature from about 125 °F. Final pH,
hardness, and temperature levels are site-specific and will
need to be determined for each discharge location.
3.3.4 SDWA
The SDWA as amended in 1986 includes the following
programs: (1) drinking water standards; (2) underground
injection control (UIC); and (3) sole-source aquifer and
well-head protection.
SDWA drinking water primary (health-based) and
secondary (aesthetic) maximum contaminantlevels (MCLs)
are generally appropriate cleanup standards for water that
is or may be used as a source of drinking water. In some
cases, alternate concentration limits (ACL) are appropriate
(for example, in cases where multiple contaminants are
present). Decision makers should refer to CERCLA and
RCRA standards for guidance in establishing ACLs. The
SITE demonstration test results show that the product
condensate has the potential to meet MCLs and ACLs.
Water discharge through injection wells is regulated
under the UIC program. This program categorizes injection
wells as Classes I through V, depending on their construction
and use. Reinjection of treated water (product condensate)
involves Class IV (reinjection) or Class V (recharge) wells
and should meet the appropriate requirements for well
construction, operation, and closure.
The sole-source aquifer protection" and well-head
protection programs are designed to protect specific drinking
water supply sources. If such a source is to be remediated,
appropriate regulatory agency officials should be notified,
and any potential problems should be identified before
treatment begins.
3.3.5 CAA
Pursuant to the CAA, EPA has set national ambient air
quality and pollutant emissions standards. CAA
requirements generally apply to the PO*WW*ER™
technology noncondensible gas emissions. Noncondensible
gas emissions should be monitored to ensure that they
comply with CAA standards, especially for CO and NOx.
During the SITE demonstration, the noncondensible gas
emissions met proposed permit levels for CO, NOx, and
SO2attheLCTC site. The respective average and maximum
permitted discharge rates for CO, NOx, and SO2 are 0.15
and 1.5; 0.25 and 2.5, and 0.25 and 2.5 Ib/hr.
RCRA air standards generally must be met for CERCLA
response actions and RCRA corrective actions. Forthcoming
RCRA regulations (40 CFR Part 269) will address air
emissions from hazardous waste treatment, storage, or
disposal facilities. When promulgated, these requirements
will include air emission standards for equipment leaks and
process vents. These requirements will cover any fugitive
air emissions from the PO*WW*ER™ technology. Also,
states' programs to regulate toxic air pollutants, when
established, will be the most significant regulations affecting
environmental remediation activities.
3.3.6 TSCA
Testing, premanufacture notification, and
recordkeeping requirements for toxic substances are
regulated under TSCA. TSCA also includes storage
requirements for polychlorinated biphenyl (PCB) (see
40 CFR Part 761.65).
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Because the PO*WW*ER™ technology has the
potential to handle wastewaters or leachates containing
PCBs, PCB storage, treatment, and disposal requirements
will apply if PCB-contaminated wastes are treated. The
EPA document entitled "CERCLA Compliance with Other
Laws Manual, Part II: Clean Air Act and Other
Environmental Statutes and State Requirements" discusses
TSCA as it pertains to Superfund actions (EPA, 1989b).
For ground-water remediation at Superfund sites and RCRA
corrective action sites, the treatment standard is generally
the SDWA MCL of 0.05 ug/L for PCBs. RCRA LDRs for
PCBs may also apply, depending on the liquid waste PCB
concentration (see 40 CFR Part 268).
3.3.7 Radioactive Waste Regulations
The PO*WW*ER™ technology has the ability to treat
water contaminated with radioactive materials. Decisions
concerning appropriate requirements for sites contaminated
with radioactive waste should be based on the following
factors: (1) type of radioactive constituents present and
how they contaminate the site; (2) regulatory agency the
site is subject to; and (3) most protective or appropriate
regulations. The primary agencies that regulate the cleanup
of radioactively contaminated sites are EPA, the Nuclear
Regulatory Commission (NRC), the Department of Energy
(DOE), and the states. In addition, nongovernmental
agencies may issue advisories or guidance, which should
also be considered in developing a protective remedy.
The SDWA has established MCLs for radionuclides in
community water as aconcentration limit for alpha-emitting
radionuclides and as an annual dose limit for the ingestion
of beta and gamma-emitting radionuclides. These standards
are appropriate in setting cleanup standards for radioactively
contaminated water. Discharge of treated water (product
condensate) from radioactively contaminated sites could
besubjectto40 CFRPart 440,Subpart C, which establishes
radionuclide concentration limits for liquid effluent from
facilities that extract and process uranium, radium, and
vanadium ores. The PO*WW*ER™ technology has the
potential to treat water to well within radioactivity limits
established by these regulations. However, treated water
should be tested to ensure that such limits are met.
Any fugitive radioactive air emissions resulting from
the PO*WW*ER™ technology must comply with
radionuclide emissions standards promulgated under the
CAA (codified in 40 CFR Part 61).
The Environmental Radiation Protection Standards
(40 CFR Part 190) promulgated under the authority of the
Atomic Energy Act (AEA) set standards for radiation doses
to the general public caused by normal operations within
the uranium fuel cycle. These requirements should be
considered at sites where uranium fuel waste is being
treated or disposed of. Standards regulating the stabilization,
control, and disposal of uranium and thorium mill tailings
are included in 40 CFR Part 192. These regulations set
cleanup, control, and release standards for radioactive
materials.
NRC regulations cover the possession and use of
source, by-product, and special nuclear materials by NRC
licensees. These regulations apply to sites where radioactive
contamination exists. Ten CFR Parts 20,30,40,61, and 70
cover protection of workers and the public from radiation,
discharges of radionuclides to air and water, and waste
treatment and disposal requirements for radioactive waste.
The brine and product condensate generated by the
PO* WW*ER™ technology during treatment of radioactive
water may be regulated under these regulations if they
contain residual radioactivity.
DOE requirements are included in a series of internal
DOE orders that have the same force as regulations at DOE
facilities. These DOE directives should be considered
when developing protective remedies at CERCLA sites or
RCRA corrective action sites, although they apply directly
only to DOE sites. DOE orders address exposure limits for
the public, concentrations of residual radioactivity in soil
and water, and management of radioactive wastes (DOE,
1988).
3.3.8 Mixed Waste Regulations
Use of the PO*WW*ER™ technology at sites with
radioactive contamination may involve the treatment or
generation of mixed waste. Mixed waste contains both
radioactive and hazardous components as defined by AEA
and RCRA and is subject to the requirements of both acts.
When the application of both regulations results in a
situation inconsistent with the AEA (for example, an
increased likelihood of radioactive exposure), AEA
requirements supersede RCRA requirements.
EPA's Office of Solid Waste and Emergency Response
(OSWER), in conjunction with the NRC, issued several
directives to assist in the identification, treatment, and
disposal of low-level radioactive mixed waste. Various
OSWER directives include guidance on defining,
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identifying, and disposing of commercial mixed low-level
radioactive and hazardous wastes (EPA, 1987). If the
PO*WW*ER™ technology is used to treat low-level mixed
wastes, these directives should be considered. If high-level
mixed waste or transuranic mixed waste is treated, DOE
internal orders should be considered when developing a
protective remedy (DOE, 1988).
3.3.9 OSHA
CERCLA response actions and RCRA corrective
actions must be performed in accordance with OSHA
requirements detailed in 29 CFR Parts 1900 through 1926,
especially Part 1910.120, which provides for the health
and safety of workers at hazardous waste sites. On-site
construction activities at Superfund or RCRA corrective
action sites must be performed in accordance with Part 1926
of OSHA (Safety and Health Regulations for Construction).
For example, construction of electric utility hookups for
the PO*WW*ER™ technology will need to comply with
Part 1926,Subpart K(Electrical).Productchemicals, such
as sodium hydroxide, that will likely be used for pre- or
post-treatment with the PO*WW*ER™ technology will
need to comply with Part 1926, Subparts D (Occupational
Health and Environmental Controls) and H (Materials
Handling, Storage, and Disposal). Also, state requirements
that are more stringent than OSHA requirements will need
to be met.
3.4 PO*WW*ER™ System Implementation
PO*WW*ER™ system implementation includes site
preparation, operation and maintenance (O&M), reliability,
and personnel requirements. These aspects of
implementation are discussed below. Because
PO*WW*ER™ system is to be marketed on a turnkey
basis, the system will be set up by the technology licenser,
ARI Technologies, Inc. (ART). The owner is required to
provide utilities.
CWM, the technology developer, has built two pilot-
and one full-scale PO*WW*ER™ plants. One
PO*WW*ER™ pilot plant, with a processing capacity of
0.5 gallon per minute (gpm), was built in February 1988 at
the LCTC site in Lake Charles, Louisiana. The plant has
been used for demonstration purposes. The SITE
demonstration was conducted at the LCTC site pilot plant.
Another PO*WW*ER™ pilot plant with a processing
capacity of 1.5 gallons per hour (gph) was built in December
1991 in Clemson, South Carolina. This PO*WW*ER™
pilot plant has also been used for demonstration purposes.
A full-scale PO*WW*ER™ plant was built at Yising Yi
Island in Hong Kong. This full-scale plant has a processing
capacity of 50 gpm and started operating in December
1992.
According to CWM, the PO*WW*ER™-based system
can be supplied as a single unit with modular construction
for a processing capacity of up to 50 gpm for each module.
Larger plants can either be supplied as multiple modular
units, each with a processing capacity of up to 50 gpm, or
designed for a given capacity as a single, integrated plant to
be field fabricated and installed.
3.4.1 Site Preparation
The 50-gpm PO*WW*ER™ system occupies
approximately 4,000 square feet. Full-scale PO*WW*ER™
treatment systems will be designed to meet site-specific
waste volume requirements and will therefore vary in size.
Area requirements are not directly proportional to the
PO*WW*ER™ system capacity. Equipment configuration
is flexible, but adequate height allowances must be
considered for the evaporator, which is about 50 feet tall.
The PO*WW*ER™ system equipment should be placed
on a level concrete pad, and equipment containing liquids
should be located within a secondary containment.
At the LCTC site, the 0.5-gpm PO*WW*ER™ pilot
plant was set up in a concrete bermed area. A trailer near the
PO*WW*ER™ system was used as a command center with
office space and computer access.
Site access requirements for the PO*WW*ER™
equipment are minimal. The site must be accessible to
trailer trucks delivering PO*WW*ER™ equipment and
any other vehicles needed to prepare the site. Site access
can be restricted by a fence.
3.4.2 Operation and Maintenance Requirements
O&M requirements for the PO* WW*ER™ unit include
general utility services and services and supplies. These
requirements are discussed below.
Utilities
Operation of the PO*WW*ER™ system requires the
following utilities:
- Electrical Power—The 50-gpm PO*WW*ER™
system requires a 440-volt, three-phase electrical
service and uses 445 kilowatt hours (kWh).
Additional 220-volt service is required for the
control room.
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• Fuel—The 50-gpm PO*WW*ER™ system also
requires approximately 22,000 standard cubic feet
per hour (scfh) of natural gas for the burner that
heats the catalytic oxidizer. Propane can also be
used as an alternate fuel.
• Process Water—Water is needed for boiler and
cooling tower make-up. Water can be supplied by
an existing on-site water distribution system. If
suitable, product condensate can be used for make-
up water. Also, an air-cooled condenser can be
used instead of a water-cooled system.
Utilities required for the PO*WW*ER™ technology
demonstration are in place and operational at the LCTC
site. If electricity and water are not readily available,
provisions for obtaining a generator should be made to
provide electricity and generate steam, and a tank for water
storage. Outdoor lighting for 24-hour operation of the plant
is available at the LCTC site and is required for other sites.
The control room requires electricity for lighting and
computer operation.
Services and Supplies
A number of readily obtainable services and supplies
are required to operate the PO*WW*ER™ system. Major
services needed for remedial activities may include (1) a
ground-water or leachate collection or storage system, and
(2) laboratory analyses and CEM to monitor the system's
performance. The PO*WW*ER™ system requires a
wastewater feed system.
Supplies required for operation of the PO*WW*ER™
system at Superfund and RCRA corrective action sites
include (1) several consumable materials, (2) steel drums
for waste brine disposal (waste brine may be collected
directly into a tanker truck instead of steel drums), and
(3) sample containers. Most of these services and supplies
were already available at the LCTC site during the SITE
demonstration. Consumable materials include antifoaming
agent, sodium hydroxide or sulfuric acid for pH adjustment,
and oxidizer catalyst.
SupportfacilitiesneededforthePO*WW*ER™system
demonstration include an office trailer, sanitary facilities,
and temporary enclosures, such as tents, to cover monitoring
equipment. Telephone service is also required to contact
emergency services and to provide normal communications.
3.4.3 Reliability
Generally, the PO*WW*ER™ system operated reliably
during the SITE demonstration. During startup, the
PO*WW*ER™ system at the LCTC site required about 9
days to reach steady-state operation because the solids
content in the feed waste was lower than expected. After
startup, a few minor operational problems were observed.
This section summarizes operational observations made
during the SITE demonstration at the LCTC site.
During the SITE demonstration, a 1-hour areawide
electrical power outage caused the temperature in the
evaporator to drop, which resulted in the system deviating
from steady-state conditions. The unit required 5 hours of
continuous operation to return to steady state operation.
Also, the evaporator recirculation pump shaft had to be
manually turned to prevent the brine from solidifying in the
lines.
Clogged sample lines limited sampling of the brine
until a new sampling location was made available during
the PO*WW*ER™ system demonstration. Brine sample
lines were easily clogged because of their small internal
diameter (0.25 inch) and minimal line flushing after
sampling. One set of brine samples could not be collected
because the brine sample line became completely clogged.
Clogging may not be a problem for a full-scale
PO*WW*ER™ system because the brine transfer lines
will be larger.
These are minor operational problems that do not
affect the system's reliability but should be considered in
the design of a full-scale PO*WW*ER™ system.
3.4.4 Personnel Requirements
According to the developer, operation of the
PO*WW*ER™ system requires two persons per shift for
2 weeks during startup, and one person per shift during
normal operations. During the SITE demonstration, one
operator and one technician were on site at all times. The
operator manually recorded hourly temperature, tank level,
and evaporator level readings. The technician was available
in case of an emergency and to make minor modifications
to the system. Personnel requirements are expected to be
low at full-scale PO*WW*ER™ system installations
because full-scale systems will be equipped with computer-
interfaced automatic monitoring and recording devices and
safety shutdown controls.
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3.5 Short-Term Impact
The potential short-term impact of PO*WW*ER™
system application involves worker safety and potential
community exposures. Personnel operating the
PO*WW*ER™ system and performing remedial activities
are required to have health and safety training. With proper
operation and monitoring of the PO*WW*ER™ system,
community exposure should be minimal. Worker safety
and potential community exposure are discussed below.
3.5J Worker Safety
Personnel operating the PO*WW*ER™ system at a
Superfund or RCRA corrective action site are subject to
OSHA regulations. Specific health and safety issues will
vary depending on physical site hazards and the type of
contamination present at a site. Therefore, a site-specific
health and safety plan should be prepared.
General site hazards during the operation of a
PO*WW*ER™ system include the following:
(1) occupational noise exposure; (2) potential slip, trip, or
fall hazards; (3) potential for contact with mechanical
equipment(forexample, motors) and electrical equipment;
and (4) potential burn hazards (forexample, during brine or
product condensate sampling or in the event of a line
rupture). Potential exposure to contaminants involves
inhaling, absorbing, ingesting, and dermal contact with
contaminants of concern. During the SITE demonstration,
contaminants of concern included PCE, vinyl chloride,
phenol, and methyl ethyl ketone (2-butanone). Samplers
were required to wear modified Level C personal protective
equipment and were monitored for heat stress.
3.5.2 Potential Community Exposure
Potential community exposure to health hazards
associated with the operation of PO* WW*ER™ technology
include exposure to (1) noncondensible vent gas emissions,
(2) potential spills resulting from waste brine or product
condensate handling, and (3) noise from the operation of
the PO*WW*ERTM system. A full-scale PO*WW*ER™
system that is operating properly and regularly monitored
and maintained should pose a minimal potential for
community exposure.
3.6 Long-Term Effectiveness
The PO* WW*ER™ system evaporates and effectively
oxidizes volatile organic and inorganic contaminants in the
catalytic oxidizer. Therefore, the PO*WW*ER™ system
treats various aqueous wastes permanently. However, brine,
which is a treatment residual, requires proper off-site
treatment and disposal. Long-term effectiveness of the
PO*WW*ER™ system was assessed based on the
permanence of the treatment and the handling of process
residuals. These factors are discussed below.
3.6.1 Permanence of Treatment
The PO*WW*ER™ system evaporates and
permanently removes contaminants from aqueous wastes.
During each 9-hour demonstration test run, the
PO* WW*ER™ system produced approximately 92 gallons
of product condensate. Product condensate from each test
run was temporarily stored on site before being disposed of.
The product condensate contained nondetectable amounts
of VOCs, SVOCs, ammonia, and cyanide. The
PO*WW*ER™ system removed sources of toxicity in the
feed waste, such as metals, VOCs, SVOCs, ammonia, and
cyanide. However, pH, hardness or salinity, and temperature
of the product condensate were outside the optimum range
for survival of acute toxicity test organisms. Therefore, the
above-mentioned parameters may need to be adjusted to
produce a product condensate that does not adversely
affect aquatic life, if the product condensate is to be
discharged to a surface water.
The pH of the product condensate ranged from 3.83 to
4.27. The acidic pH of the product condensate possibly
resulted from the hydrolysis of NOx produced in the catalytic
oxidizer. This hypothesis is discussed further in Appendix B.
3.6.2 Residuals Handling
The only residual generated from the PO*WW*ER™
process is brine. The long-term effectiveness of the
PO* WW*ER™ system ultimately depends on the treatment
and disposal of brine. During the SITE demonstration,
brine from the PO*WW*ER™ system was wasted once
each 9-hour test period. The amount of brine wasted may
vary depending on the TS concentration in the feed waste.
Also, the contaminant characteristics of the brine are a
function of the contaminant concentrations in the feed
waste. Ultimate treatment and disposal of the brine depends
on the types and concentrations of contaminants present.
The brine produced during the SITE demonstration exhibited
one hazardous waste characteristic—toxicity—and
potentially could exhibit the hazardous characteristic of
reactivity. Both of these characteristics are discussed below:
Toxicity
Based on the results of the toxicity characteristic
leaching procedure (TCLP) test for metals, brine, which is
an F039-derived hazardous waste, also exhibits the
22
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characteristic of a D004 hazardous waste because it contains
TCLP arsenic at concentrations ranging from 34,400 to
103,000 |ag/L. These concentrations are greater than the
regulatory level of 5,000 ng/L.
Brine stabilization for subsequent disposal was not
evaluated during the SITE demonstration. However, case
study results evaluated by CWM show that after brine was
stabilized, all extraction procedure (EP) toxicity levels for
metals met their respective regulatory levels.
Reactivity
Brine produced during the SITE demonstration
contained cyanide at concentrations ranging from 17 to
150 mg/L. If brine is exposed to acidic pH conditions, toxic
hydrogen cyanide gas may be generated.
3.7 Factors Influencing Performance
Factors that may affect the performance of the
PO*WW*ER™ system in meeting evaluation criteria
include waste characteristics and operating parameters.
Each of these factors is discussed below.
3.7.1 Waste Characteristics Influencing
Performance
Waste characteristics influencing the PO*WW*ER™
system's performance include: (1) feed waste pH, (2) ionic
strength, (3) contaminant loading, (4) nature of
contaminants in the feed waste, (5) catalytic poisons, and
(6) foaming. Each of these characteristics is discussed
below:
Feed Waste pH
Feed waste pH affects the evaporation of inorganic
contaminants because it determines their chemical
speciation. Feed waste pH is more important when more
than one volatile inorganic contaminant is present and
when each volatile inorganic contaminant volatilizes at a
different pH range.
For example, in solution, HCN exists either as HCN or
cyanide (CN~~) species depending on the solution pH. HCN
is a volatile inorganic acid that predominates at pH values
less than 9. Case study results show that cyanide was
effectively stripped from the brine by acidifying the brine
to cause the release of HCN.
Ammonia (NH3) in solution exists either as NH3 or as
an ammonium ion (NH4+). Ammonia is a volatile compound
that predominates at pH values greater than 9. Case study
results show that less ammonia was evaporated from the
brine atpHs of 7 to 8 than atpH 11.
Ammonia and cyanide also form complexes with metals
present in aqueous wastes. Aqueous waste pH can also
affect the stability of ammonia and cyanide metal complexes,
which ultimately determines the ammonia and cyanide
removal efficiency.
Aqueous waste pH may also determine the corrosivity
characteristics of the waste. According to CWM case
studies, when corrosive material is to be treated, the
PO*WW*ER™ system may need to be constructed of
corrosion resistant material.
Ionic Strength
The ionic strength of an aqueous waste is a measure of
the concentration and the charge of ionic species present.
High ionic strength of an aqueous waste can cause a
phenomenon known as "salting-out effect." Because of
this phenomenon, increasing ionic strength can cause a
decrease in the solubility of molecular species such as
VOCs and SVOCs, thus increasing their evaporation
efficiency (Snoeyink and Jenkins, 1980). According to
CWM, during bench-scale studies, sodium chloride was
added to aqueous wastes to increase ionic strength and the
evaporation efficiency of organic contaminants present.
Contaminant Loading
Total contaminant loading may affect the performance
of the PO*WW*ER™ system. For some applications, it
may determine the PO*WW*ER™ system's applicability.
Contaminant loading determines the amount, rate, and
characteristics of the brine produced. Brine is removed
from the evaporator when it reaches a specific temperature
corresponding to a specific BPR. BPR is the difference
between the boiling point of a solution and the boiling point
of water at the same pressure. BPR is associated with a
specific brine concentration. During the SITE
demonstration, BPR was not determined (see Section 3.8
for details). The evaporator BPR is an important operating
parameter because it determines contaminant removal
efficiencies.
Total contaminant loading may also affect the
concentration levels of contaminants in the brine and may
result in slight increases in contaminant concentrations in
the noncondensible vent gas. SITE demonstration results
show that an increase in total contaminant loading may
23
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result in slight increases in contaminant concentrations in
the noncondensible vent gas and in reduced VOC
evaporation efficiency. Also, SITE demonstration and case
study results show that the PO* WW*ER™ system can treat
wastes with high total organic and inorganic contaminant
loading without any measurable effect on product
condensate quality.
Nature of Contaminants in the Feed Waste
SITE demonstration and other case study results show
that volatile organic and inorganic contaminants are
effectively evaporated from the brine and successfully
oxidized in the catalytic oxidizer. However, nonvolatile
contaminants, such as certain SVOCs, metals, and other
inorganic contaminants, remained in the brine.
Higher molecular weight hydrocarbons are more easily
oxidized than those with lower molecular weights. Catalytic
reactivity also varies with molecular structure, increasing
in the following order: aromatic hydrocarbons, branched
paraffins, normal paraffins, olefinic hydrocarbons,
acetylenic hydrocarbons (Wark and Warner, 1981).
Catalytic Poisons
Deposition of particulates on the surface of a typical
catalyst bed decreases the available surface area for catalytic
action. This decrease lowers the effectiveness of the catalyst
and its operating life. The normal operating life of a catalyst
without particulate deposition problems may be from 3 to
5 years. One other problem associated with catalytic
oxidation is poisoning of the bed by specific contaminants
in the waste gas. Materials such as iron, lead, silicon, and
phosphorous shorten the lives of many catalysts. Sulfur
compounds may also suppress the effectiveness of some
catalysts (Wark and Warner, 1981).
Thecatalystused in thePO*WW*ER™ system oxidizer
is the main innovative feature of the system. The catalyst is
a proprietary nonprecious metal oxide catalyst in a specific
support medium. According to CWM, the catalyst is not as
expensive or limited in versatility as a precious metal
catalyst and was designed to withstand problems common
to precious metal catalysts such as fouling, particulate
deposition, activity suppression and poisoning. However,
because of the nature of the catalyst, periodic make-up is
required.
Foaming
Depending on the nature of the feed waste, foaming
may occur in the vapor body. If foaming is not controlled,
foam can pass through the mesh pad, leave deposits in the
oxidizer, plug the catalyst tray, and contaminate the product
condensate. An antifoaming agent can be added to the feed
waste to prevent vapor body foaming. In addition, the vapor
body is equipped with a foam alarm that is activated if the
foam reaches a certain level in the vessel. If the alarm is
activated, antifoaming agent can be injected directly over
the foam in the vapor body until foaming subsides.
3.7.2 Operating Parameters Influencing
Performance
Operating parameters that may influence the
PO*WW*ER™ system's performance include (l)feed
waste flow rate, (2) ratio of propane (or other fuel) flow
rate to air flow rate, (3) excess air, (4) catalyst bed depth,
and (5) heat transfer coefficients. Each of these parameters
is discussed below.
Feed Waste Flow Rate
The feed waste flow rate determines the mass loadings
on the individual components of the PO* WW*ER™ system.
Mass loading determines the treatment time required and
the treatment efficiency that can be achieved.
Ratio of Propane (or Other Fuel) Flow Rate to Air Flow
Rate
This parameter affects the oxidizer temperature, which
in turn affects the oxidation efficiency and the formation of
oxidation byproducts. Case study results also show that
increased treatment temperature results in increased
oxidation efficiency.
Literature data indicate that the oxidation temperatures
for the following solvents range from 500 to 850 °F: toluene,
methyl ethyl ketone (2-butanone), xylene, and alcohols.
The oxidation temperature required for exhaust gas from
chemical processes ranges from 400 to 750 °F. Typical
examples of contaminants present in the exhaust gas from
chemical processes include CO, ethylene, ethylene oxide,
and propylene (Wark and Warner, 1981). Most catalysts
have an upper limit in their operating temperature range,
which for many is around 1,500°F. During the SITE
demonstration, propane was used as fuel for the oxidizer
burner.
Excess Air
The percent of excess air added to the oxidizer affects
oxidation efficiency and the oxidation products formed.
The rate of oxidation of a hydrocarbon is proportional to
24
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the concentration of that hydrocarbon in the gas stream if
at least 2 percent oxygen by volume is present in excess of
that required for complete oxidation (Wark and Warner,
1981). At an oxygen level greater than 30 percent of the
stoichiometric requirement, a removal efficiency of greater
than 99 percent was achieved. If hydrocarbons are only
partially oxidized, a considerable amount of CO may be
formed.
Catalyst Bed Depth
The catalyst bed depth may affect oxidation efficiency
because it determines the contact time between the catalyst
and the vapor stream. The oxidation efficiency of several
organic and inorganic compounds is afunction of residence
time. Current practice indicates that 85 to 95 percent
conversion of pollutants typically requires 2.0 cubic feet
(ft3) of catalyst for each 106 standard cubic feet per minute
(scfm) of gas (Wark and Warner, 1981).
Heat Transfer Coefficients
The physical-chemical characteristics of the brine may
have a fouling effect on the heat transfer surfaces. Periodic
system cleaning may be required to maintain high heat
transfer coefficients (see Appendix C). During the SITE
demonstration, heat transfer coefficients were not
determined (see Section 3.8 for details).
3.8 Evaluation Limitations
Two major limitations that restricted evaluation of the
PO*WW*ER™ system's performance were testing
limitations and confidential information limitations. These
limitations were imposed by CWM, mostly for protection
of proprietary know-how. Each of these limitations is
discussed below.
3.8.1 Testing Limitations
Testing limitations include sampling and monitoring
location limitations and spiking compound and spiking
concentration limitations. Both of these limitations are
discussed below.
Sampling and Monitoring Location Limitations
During the SITE demonstration, CWM allowed only
four peripheral locations on the PO*WW*ER™ system to
be sampled and monitored. However, these locations did
not include several locations within the PO*WW*ER™
pilot plant process, such as before and after the catalytic
oxidizer. Also, the monitoring parameters recorded during
the demonstration were only those approved by CWM.
These parameters did not include several key parameters
such as BPR, oxidizer temperature, and heat transfer
coefficients. According to CWM, by analyzing samples
taken within the PO*WW*ER™ pilot plant process,
monitoring additional locations, and recording values of
key parameters within the system, proprietary information
about the PO*WW*ER™ system may be disclosed to the
public.
Spiking Compound and Spiking Concentration
Limitations
CWM limited the spiking compounds and
concentrations used during the SITE demonstration.
According to CWM, spiking with additional proposed
compounds (for example, aromatics such as benzene) or at
concentrations different from those permitted by CWM
during the SITE demonstration would not be allowed
because of health and safety concerns to individuals at the
LCTC site and the possibility of changing the residual
waste characteristics to the extent that the LCTC site would
violate its hazardous waste operating permit.
3.8.2 Confidential Information Limitations
CWM provided reports that summarize case study
results. However, several sections of the reports are
classified as confidential by CWM, and the information
was therefore deleted from these reports. Consequently,
only select information is available regarding the
PO*WW*ER™ system's performance in the case study
reports.
25
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Section 4
Economic Analysis
This section presents cost estimates for using a 50-gpm
PO*WW*ER™ system to treat landfill leachate at a
Superfund site. Cost estimates presented in this section are
based primarily on data compiled from the developer of the
technology and partly on the SITE demonstration at the
LCTC site. Costs have been placed in 12 categories
applicable to typical cleanup activities at Superfund and
RCRA sites (Evans, 1990). Costs are presented in January
1993 dollars and are considered to be order-of-magnitude
estimates with an accuracy of plus 50 percent and minus
30 percent.
Table 4-1 presents a breakdown of costs for the 12
categories. The table presents fixed costs and annual variable
costs, the total costs and net present values for a 15-year and
30-year leachate remediation project, and costs per 1,000
gallons of leachate treated. Site-specific factors affecting
costs, the basis of this economic analysis, and the 12 cost
categories are discussed in the following sections. A
summary of the economic analysis is also presented at the
end of this section.
4.1 Site-Specific Factors Affecting Costs
A number of factors affect the estimated costs of
treating landfill leachate with the PO*WW*ER™ system.
Factors affecting costs generally include physical site
conditions, geographical site location, treatment goals,
leachate characteristics, and the total volume of leachate to
be treated.
The cost data presented in this analysis were primarily
provided by the technology developer. Certain operating
conditions could not be monitored during the SITE
demonstration (see Section 3.8 for details). As a result,
many operating parameters could not be independently
verified or quantified.
4.2 Basis of Economic Analysis
The PO* WW*ER™ technology can treat several types
of aqueous wastes, including landfill leachate, contaminated
.ground water, and industrial wastewater. Landfill leachate
has been selected for this economic analysis because it
represents a waste commonly found at Superfund and
RCRA corrective action sites, and because it is a waste
whose treatment involves most of the cost categories.
This analysis assumes that the PO*WW*ER™ system
will treat landfill leachate on a continuous basis 24 hours
per day, 7 days per week, 365 days per year, and will be on-
line 90 percent of the time. Based on this assumption, a50-
gpm PO*WW*ER™ system can annually treat about
24 million gallons. Because most landfill leachate remedial
projects are characteristically long term, this analysis
compares the costs of operating the system for 15 and
30 years in Table 4-1.
Other assumptions used for this analysis include the
following:
• The site is a Superfund landfill located near a large
municipality in the Gulf Coast Region of the United
States.
• No pretreatment of the feed waste is required.
• An access road, utilities, and a sewer line need to
be extended to the PO*WW*ER™ system site.
• A1,000-square-foot storage building is needed for
supplies, laboratory equipment, office space, and
sanitary facilities.
• A natural gas, engine-driven, electric generator
will be installed as an emergency power source.
• About 200 gallons per day (gpd) of potable water
are required.
• The treatment system is constructed of suitable
material and operates automatically.
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Table 4-1. Costs Associated with the PO*WW*ER™ Technology
Cost Categories
Estimated Costs
(1993 Dollars)
Site Preparation3
Permitting and Regulatory Requirements3
Capital Equipment3
Startup'
Labor5
Consumables and Supplies0
Utilities0
Effluent Treatment and Disposal"1
Residual and Waste Shipping and Handling0
Analytical Services0
Maintenance and Modifications0
Demobilization3
Total One-Time Costs
Total Annual O&M Costs
Total Cost of 15-Year Project'^
Total Cost of 30-Year Project"'''"
Net Present Value of 15-Year Project1
Net Present Value of 30-Year Project1
Costs per 1,000 Gallons Treated (15 Years)'
Costs per 1,000 Gallons Treated (30 Years)'
$1,100,000
200,000
4,200,000"
55,000
230,000
28,000
480,000
0
2,300,000
42,000
200,000
70,000
$5,600,000
$3,300,000
$80,000,000
$240,000,000
$37,000,000
$52,000,000
$100
$73
Notes:
• One-time costs
b Capital equipment cost for a modular 50-gpm PO*WW*ER™ system,
installed and assembled on a turnkey basis, is $4 million.
c Annual O&M costs
d Not applicable
• Annual inflation rate assumed to be 5 percent
1 Capital equipment not discounted over term of project
o For a 15-year project, a 50-gpm PO*WW*ER™ system will treat a total
of 360 million gallons.
h For a 30-year project, a 50-gpm PO*WW*ER™ system will treat a total
of 720 million gallons.
1 Net present value discounted at annual rate of 10 percent
I Presented in terms of a net present value.
One technician per shift is required to monitor the
equipment, collect all required samples, and
perform equipment maintenance and minorrepairs.
Almost all of the product condensate will be
discharged to a POTW; the remainder will be used
on-site as process make-up water.
Product condensate requires pH adjustment from 4
to greater than 6.
The catalytic oxidizer operates in a fluidized bed
mode requiring the periodic addition of make-up
catalyst to compensate for attrition losses.
Treated and untreated leachate samples will be
collected once every month and analyzed off site
for VOCs, SVOCs, and metals to monitor system
performance.
Waste brine from the treatment system is considered
a hazardous waste and requires off-site stabilization
and disposal at an approved disposal facility.
Labor costs associated with major equipment
repairs or replacement are not included.
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4.3 Cost Categories
Cost data associated with the PO*WW*ER™
technology have been assigned to the following 12
categories: (1) site preparation; (2) permitting and
regulatory requirements; (3) capital equipment; (4) startup;
(5) labor; (6) consumables and supplies; (7) utilities;
(8) effluent treatment and disposal; (9) residuals and waste
shipping and handling; (10) analytical services;
(11) maintenance and modifications; and
(12) demobilization. Costs associated with each of these
categories are discussed below.
4.3.1 Site Preparation Costs
Site preparation costs include administrative,
construction, and mobilization costs. For this analysis,
administrative costs such as legal searches, access rights,
and other site planning activities are estimated to be $50,000.
Construction costs include (1) construction of aroofed
structure with concrete foundations, equipment pads, sumps,
and secondary containment curbs to house the
PO*WW*ER™ system and liquid storage tanks;
(2) construction of a storage building; (3) construction of
an access road; (4) construction of a leachate collection
system including all required pumps and piping; and
(5) extension of all necessary utility lines such as electric,
natural gas, sewer, and water lines to the treatment system
site.
This analysis assumes a 3,000-foot access road will
be constructed from a main thoroughfare to the
PO*WW*ER™ system. The road will be either asphalt
or concrete and will be 16 feet wide. The total cost for
this road will be approximately $240,000.
The PO*WW*ER™ system will be installed on
reinforced concrete foundations inside an open, roofed
structure with sumps and secondary containment curbs.
These reinforced concrete foundations will occupy
approximately 4,000 square feet. The total cost for the
foundations and structure will be about $150,000.
A 1,000-square-foot storage building will be required
for storage of supplies and laboratory equipment and for
office space and sanitary facilities. The building will be a
prefabricated metal structure and will be located next to the
PO*WW*ER™ system. The total cost for this storage
building will be approximately $80,000.
This analysis assumes a leachate collection system will
be installed to collect and convey leachate to the
PO*WW*ER™ system. The leachate collection system
will consist of a leachate collection trench with perforated
piping and a leachate sump equipped with two pumps and
all required piping, valves, and controls to transfer the
leachate to the PO*WW*ER™ system. The total cost of
installing the leachate collection system is approximately
$150,000.
Electrical power, natural gas, sewer, and water lines
will be extended to the treatment system. It is assumed that
these lines will be installed alongside the access road.
Installation of overhead electrical power costs about $25,000
per 1,000 feetof line for atotalcostof $75,000; installation
of required transformers is estimated to be $50,000.
Installation of natural gas pipeline costs about $20,000 per
500 feet for a total cost of $ 120,000. Potable water lines to
be connected to the storage building are estimated to cost
about $15 per linear foot for a total cost of $45,000. An 8-
inch-diameter sewer line for discharging product condensate
and sanitary water is estimated to cost $40 per linear foot
for a total cost of approximately $ 120,000. The total cost of
extendingutilities to thePO*WW*ER™systemis $410,000.
Mobilization involves • transporting the entire
PO*WW*ER™ treatment system to the site. ARI
Technologies, Inc. (ARI), the technology licenser, will
deliver the system from the Chicago area. For this analysis,
the site is assumed to be located in the Gulf Coast Region.
The total estimated mobilization cost is about $50,000.
Total site preparation costs, rounded to two significant
figures, are estimated to be $1,100,000.
4.3.2 Permitting and Regulatory Requirements
Costs
Permitting and regulatory costs vary depending on
whether treatment is performed at a Superfund site or a
RCRA corrective action site and how treated effluent and
solid wastes are disposed of. Superfund sites also require
remedial actions to be consistent with ARARs including
environmental laws, ordinances, regulations, and statutes
for federal, state, and local standards and criteria. In general,
ARARs must be determined on a site-specific basis. RCRA
corrective action sites require additional monitoring records
and sampling protocols that can increase the permitting and
regulatory costs by an additional 5 percent.
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Permitting and regulatory costs are assumed to be
about 5 percent of the total capital equipment costs for this
treatment operation, which is assumed to be part of a
Superfund remedial action. The annual discharge permit to
a POTW is included in this estimate. For this analysis, total
permitting and regulatory costs are estimated to be $200,000.
4.3.3 Capital Equipment Costs
Capital equipment costs include purchasing the
PO*WW*ERTM treatment system and emergency power
source equipment. ARI estimates that the cost for a 50-gpm
PO*WW*ER™ treatment system is about $4 million. ARI
includes the following elements in the turnkey costs of
purchasing each PO*WW*ER™ treatment system:
• Complete PO*WW*ER™ treatment system,
including a scrubber (see Section 2 for description)
• Treatability study to determine the appropriate
treatment specifications
• System design costs
• Assembly of the system including all
interconnecting piping, controls, and utilities
• All necessary tanks including the waste feed tank,
chemical feed system for pH adjustment, and
metering pumps
• On-line installation of effluent monitoring
equipment, including CEM, to measure all critical
parameters
A natural gas, engine-driven emergency generator will
be required to provide uninterrupted electric power to the
system. The cost for installing the emergency generator,
automatic transfer switch, and all required appurtenances
is estimated to be $200,000.
Total capital equipment costs are estimated to be
$4,200,000.
4.3.4 Startup Costs
Startup costs include all activities required to make the
PO*WW*ER™ system fully operational. These costs
include initial operator training and optimization and
shakedown costs. ARI will provide personnel to assist with
startup activities.
Initial operator training is needed to ensure safe and
economical operation of the treatment system. ARI provides
O&M training as part of the costs of purchasing the
treatment system. However, a 40-hour health and safety
training course is needed for each operator. Total startup
training costs, which also include developing a health and
safety program, are estimated to be $25,000.
Optimization and shakedown activities include initial
startup, trial runs, and final equipment inspection. ARI
estimates that these activities require 2 weeks to complete
and that total optimization and shakedown costs will be
approximately $30,000.
Total startup costs are estimated to be about $55,000.
4.3.5 Labor Costs
Labor costs include the following: total staff needed
for O&M of the PO*WW*ER™ system; annual health and
safety training refresher courses; and demobilization costs,
which are discussed in Section 4.3.12. The labor wage
rates provided in this analysis include fringe benefits. Once
the system is functioning, it is assumed that it will operate
continuously at the designed flow rate.
Three 8-hour shifts will be worked each day, 7 days per
week. Each shift will require one technician earning $18
per hour and one supervisor who will work during the first
shift only and earn $22 per hour. The operator will monitor
the equipment, perform routine maintenance, and perform
routine sample collection. This analysis assumes a total of
five workers rotating shifts to allow for weekends and
vacations. Total annual labor costs, rounded to two
significant figures, are estimated to be about $220,000.
Annual health and safety training refresher courses
will cost about $2,000 per person for a total annual cost of
about $10,000.
Total annual labor costs, rounded to two significant
figures, are estimated to be $230,000.
4.3.6 Consumables and Supplies Costs
Consumables and supplies costs include oxidizing
catalyst replenishment and purchase of antifoaming agents,
sodium hydroxide, personal protective equipment, and
personal protective equipment disposal drums. Costs of
these items are discussed below.
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About 2 to 4 percent of the initial catalyst bed volume
will need replenishment every month. ARI estimates about
85 pounds of catalyst are needed per month. According to
ARI, catalyst costs about $1.025 per pound. ARI will
provide the proprietary nonprecious metal catalyst. Total
annual catalyst replenishment costs are estimated to be
about $1,100.
Antifoaming agents may be needed to reduce the
amount of foam generated during treatment. About 0.5
gallon of antifoaming agent was used for every 1,000
gallons of leachate treated during the SITE demonstration.
Assuming the same usage rate, and operating 90 percent of
the time, the 50-gpm PO*WW*ER™ system will require
about 12,000 gallons of antifoaming agent annually. It is
assumed that antifoaming agent will be ordered when
needed and stored on site in a 500-gallon tank. The costs of
the tank and its feed system are provided in the cost of
purchasing the PO*WW*ER™ system (see Section 4.3.3,
Capital Equipment Costs). The antifoaming agent cost
provided by ARI is about $1.85 per gallon. Total annual
antifoaming agent costs are estimated to be $23,000.
This analysis assumes sodium hydroxide will need to
be added to the product condensate to adjust the pH from
4 to greater than 6 in order to meet POTW discharge
requirements. Approximately 65 gallons of sodium
hydroxide per year will be used. Sodium hydroxide is
commercially available in a 50-percent solution for about
$1.50 per gallon. Based on this estimate, annual sodium
hydroxide usage would cost approximately $200.
Personal protective equipment (PPE) typically consists
of nondisposable and disposable equipment. Nondisposable
equipment consists of hard hats, steel-toed boots, and full-
face air respirators. Disposable personal protective
equipment includes Saranax- or Tyvek-type coveralls, latex
inner gloves, nitrile outer gloves, and safety glasses.
Disposable personal protective equipment will be worn
during sample collection only. Annual personal protective
equipment costs are estimated to be about $3,000.
PPE is assumed to be hazardous and will need to be
disposed of in 24-gallon fiber drums. Any other potentially
hazardous wastes will also be disposed of in these drums.
One drum is assumed to be filled every 2 weeks. Drums
cost about $12 each for a total annual cost of about $300.
Disposal of the drums is discussed in Section 4.3.9,
Residuals and Waste Shipping and Handling Costs.
Total annual consumables and supplies costs are
estimated to be $28,000.
4.3.7 Utilities Costs
Total utilities costs are based on electricity, natural
gas, and water used to operate the PO*WW*ER™ system,.
its auxiliary equipment, and the storage building. It is also
assumed that the system will be operating at 90 percent of
the time. Actual costs vary depending on the site's
geographical location and local utility rates. These cost
estimates assume flat utility rates and no monthly charges.
According to ARI, the 50-gpm PO*WW*ER™ system
uses about 445 kilowatts and would use about 3.9 million
kilowatt-hours (kWh) annually. This analysis assumes that
electricity costs about $0.10 per kWh and that any auxiliary
equipment draws an additional 10 percent of the total
annual electrical power of the PO*WW*ER™ system.
Total annual electrical costs would therefore be
approximately $390,000.
According to ARI, the 50-gpm PO*WW*ER™ system
uses about 2,200 standard cubic feet per hour (scfh) of
natural gas. This analysis assumes that natural gas costs
about $0.50 per 1,000 therms. With the system operating
90 percent of the time, total annual natural gas costs would
be approximately $90,000.
Approximately 200 gpd of water will be required for
cleanup and sanitary uses. This analysis assumes that water
costs $ 1.50 per 1,000 gallons. Total annual water costs will
be about $100.
Total annual utility costs, rounded to two significant
figures, are estimated to be about $480,000.
4.3.8 Effluent Treatment and Disposal Costs
Effluent from the PO*WW*ER™ system includes
product condensate and noncondensible gases generated
during the scrubbing and condensing stage; For this analysis,
product condensate is assumed to need pH adjustment and
will be discharged to a POTW. The costs associated with
treating effluent are discussed in Section 4.3.6, Consumables
and Supplies Costs. The costs of discharging effluent to a
POTW are discussed in Sections 4.3.1, Site Preparation,
and 4.3.2, Permitting and Regulatory Requirements. It
should be noted that the Gulf Coast Region is topographically
flat and the discharge to the POTW is assumed to be by
gravity flow. If one or more pump stations are needed to
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convey the product condensate and sanitary flow to the
POTW, effluent treatment and disposal costs will be higher.
Noncondensible gases will be monitored but are
assumed to meet local and regional emissions requirements
and will be released to the atmosphere. This release is also
assumed to not require an air permit. The costs of air
monitoring equipment are included in the cost of purchasing
the PO*WW*ER™ system (see Section 4.3.3, Capital
Equipment).
4.3.9 Residuals and Waste Shipping and
Handling Costs
Waste brine and personal protective equipment drums
are the only wastes generated from operating the
PO*WW*ER™ system. These wastes are considered
ha2ardous and require disposal at a permitted facility.
Waste disposal costs include transportation, stabilization,
and landfill disposal. The cost estimates discussed below
do not include approval fees, state taxes, or state landfilling
permits.
The waste brine is required to be disposed of off site as
a hazardous waste. To minimize storage costs, this analysis
assumes that waste brine can be transferred by gravity
directly from the PO*WW*ER™ system into a 6,000-
gallon tanker truck parked on site. This analysis also
assumes that for a full-scale PO*WW*ER™ system
operating on a continuous basis, about 3 gallons of brine
would be generated for every 100 gallons of leachate
treated (approximately 3 percent of the feed volume). At
this rate, the 50-gpm flow-rate system will generate about
1 720,000 gallons of brine per year, or about 60,000 gallons
per month. This analysis further assumes that the wastes
will be shipped 100 miles to the nearest RCRA-permitted
treatment and disposal facility. Transportation costs for the
waste brine are estimated to be about $700 per 6,000-gallon
tanker. At a RCRA-permitted facility, brine can be stabilized
by solidification and disposed of at a cost of about $3 per
gallon. Total annual brine disposal costs will be about $2.2
million.
This analysis also assumes that the cost of shipping,
handling, and transporting the personal protective equipment
drums to a hazardous waste disposal facility are about
$1,000 per drum. Total annual drum disposal costs are
estimated to be $26,000.
Total annual disposal costs, rounded to two significant
figures, are estimated to be about $2,300,000.
4.3.10Analytical Services Costs
Analytical costs include laboratory analyses, data
reduction and tabulation, QA and QC, and reporting. This
analysis assumes that one sample of treated and untreated
leachate will be collected each month to be analyzed for
VOCs, SVOCs, and metals. Monthly laboratory analyses
will cost about $3,000; data reduction, tabulation, QA/QC,
and reporting are estimated to cost a total of about $500 per
month.
A treatability study will need to be performed to
determine the appropriate specifications of the
PO*WW*ER™ system. The cost of purchasing the
PO*WW*ER™ system includes the cost of the treatability
study.
Total annual analytical services costs are estimated to
be about $42,000.
4.3.11 Maintenance and Modifications Costs
ARI estimates that maintenance and modifications
costs for the PO*WW*ER™ treatment system will be low
because the system does not have many moving parts and
is not expected to be shutdown for routine maintenance.
However, the extreme heat generated by the system may
affect maintenance requirements.
This analysis assumes that annual maintenance costs
will be about 5 percent of capital equipment costs, which is
about $200,000.
4.3.12 Demobilization Costs
Site demobilization will include shutdown,
disassembly, transportation, and disposal of all equipment
to a licensed hazardous waste disposal facility. Site cleanup,
building decontamination, and site restoration costs will
also be incurred during demobilization. This analysis
assumes the storage building will remain on site. Total
demobilization is estimated to take about 1 week to complete
and will cost about $70,000, including labor.
The costs of demobilization, however, will occur at the
end of the remediation project. Therefore, based on the
annual inflation rate of 5 percent, the net future values of
this cost for a 15-year project and 30-year project are
estimated to be $ 140,000 and $300,000, respectively. These
costs are rounded to two significant figures and were used
to calculate the total costs of the 15-year and 30-year
projects presented in Table 4-1.
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4.4 Summary
This economic analysis presents the costs associated
with a 50-gpm PO*WW*ER™ system treating landfill
leachate at a Superfund landfill site. The costs associated
with this project are presented in Table 4-1.
Total estimated one-time costs are about $5.6 million.
Of this $5.6 million, $4 million are for purchasing the
PO*WW*ER™ system. Total annual O&M costs are
estimated to be about $3.3 million and reflect a 90 percent
on-line factor. Waste disposal costs account for about 70
percent of annual O&M costs.
A remediation project lasting 15 years would treat
about 360 million gallons of leachate at an estimated total
cost of $80 million. The total net present value of this
project would be about $37 million, which results in a cost
of about $100 per 1,000 gallons of leachate treated. A
remediation project lasting 30 years would treat about 720
million gallons of leachate at an estimated total cost of $240
million. The total net present value of this project would be
$52 million, which results in a cost of about $73 per 1,000
gallons of leachate treated.
As mentioned earlier, costs presented in this analysis
are order-of-magnitude estimates (plus 50 percent to minus
30 percent) and are rounded to two significant figures.
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Section 5
References
Evans, G., 1990, Estimating Innovative Technology
Costs for the SITE Program. Journal of Air and
Waste Management Association, 40:7, pages 1047
through 1051.
Federal Register, 1990a, National Oil and Hazardous
Substances Contingency Plan; Final Rule.
Volume 55, No. 46 (March).
Federal Register, 1990b, Proposed Rules for Corrective
Action for Solid Waste Management Units at
Hazardous Waste Management Facilities.
Volume 55, No. 145, July 27.
Snoeyink, V.L., and Jenkins, D., 1980, Water Chemistry.
John Wiley and Sons, New York, NY.
U.S. Department of Energy (DOE), 1988, Radioactive
Waste Management Order. DOE Order 5820.2A
(September 26).
U.S. Environmental Protection Agency (EPA), 1987,
Joint EPA and Nuclear Regulatory Commission
(NRC) Guidance on Mixed Low-Level Radioactive
and Hazardous Waste. Office of Solid Waste and
Emergency Response (OSWER) Directives 9480.00-
14 (June 29); 9432.00-2 (January 8); and 9487.00-8
(August 3).
EPA, 1988, Comprehensive Environmental Response,
Compensation, and Liability Act (CERCLA)
Compliance with Other Laws Manual (Interim Final),
OSWER, EPA/540/G-89/006.
EPA, 1989a, Superfund Federal Land Disposal
Restrictions (LDR) Guide No. 1, Overview of
Resource Conservation and Recovery Act (RCRA)
LDR, EPA Directive 9346.3-01FS.
EPA, 1989b, CERCLA Compliance with Other Laws
Manual: Part II. Clean Air Act and Other
Environmental Statutes and State Requirements
(Interim Final), OSWER Directive 9234.1-02.
EPA, 1991, Methods for Measuring the Acute Toxicity
of Effluents and Receiving Waters to Freshwater and
Marine Organisms. EPA Office of Research and
Development, Washington, DC, EPA/600/4-90/027
(September).
Wark, K., and Warner, C.F., 1981, Air Pollution: Its
Origin and Control. Second Edition, Harper & Row
Publishers, New York, NY.
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Appendix A
Developer's Claims for the PO*WW*ER™ Technology
A.1 Developer's Claims
This appendix summarizes claims made by the
developer, Chemical Waste Management, Inc. (CWM),
regarding the PO*WW*ER™ system. The information
presented herein represents the developer's point of view
and does not constitute U.S. Environmental Protection
Agency (EPA) approval or endorsement of the statements
made in this appendix.
A. 1.1 Introduction
Complex industrial and hazardous wastewaters
containing mixtures of inorganic salts, metals, volatile and
semivolatile organics, volatile inorganics, radionuclides,
and other compounds, pose a challenge to engineers of
treatment systems. These wastewaters differ greatly from
one another and change characteristics during the course of
operation. Treatment standards also change, requiring
engineers to anticipate future requirements.
The conventional treatment approach has been to
integrate a number of unit operations in a treatment train
specifically designed for a particular wastewater after
conducting elaborate treatability studies. The treatment
train requires constant monitoring and adjustment to ensure
proper operation of each unit in the train. This approach is
operation and maintenance intensive.
The PO*WW*ER™ technology treats complex
industrial and hazardous wastewaters in a single integrated
system. The technology is flexible enough to accommodate
wide variations in wastewater composition and is operator
friendly because it does not require constant monitoring
and adjustment. This patented, proprietary technology was
developed over an 8-year period and uniquely combines
evaporation with catalytic oxidation to concentrate the
nonvolatile contaminants in a residual brine stream of very
small volume. The technology also catalytically oxidizes
volatile contaminants. Most wastewater is converted into
high-quality water that can be reused or discharged and that
meets not only today's treatment standards but also
foreseeable future requirements. This technology has been
tested and well demonstrated on a number of complex
wastewaters through the operation of fully integrated pilot
plants. PO*WW*ER™ is now used commercially to treat
a variety of industrial and hazardous wastewaters.
A.1.2 Technology Description
ThePO*WW*ER™technologycombinesevaporation
with catalytic oxidation in a flexible, easy to operate
system. A PO*WW*ER™ based wastewater treatment
facility can generally be designed with a minimal upfront
treatability effort and once built, can handle significant
variations in wastewater composition. The system does not
require expensive constant monitoring and operates
unattended. Table A-l summarizes some capabilities of
the PO*WW*ER™ system.
A.1.3 Benefits
Besides being flexible, easy to operate, and uniquely
accommodating significant variations in wastewater
composition, the PO*WW*ER™ technology offers the
following specific advantages:
• Treats a wide spectrum of aqueous wastewater,
and system components are not affected by any
unexpected contaminants
• Produces high-quality water that can be used as
boiler feed water makeup, cooling tower makeup,
or high-quality process water, saving the cost of
expensive treatment in all cases
• Destroys the organic pollutants reducing overall
pollution to the environment
• Achieves high volume reduction by minimizing
the volume of waste for final disposal
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Table A-1. Capabilities of PO*WW*ER™
Specific Capabilities of PO'WW'ER™
Demonstrated Results
Comparison to
Conventional Technology
High volume reduction of waste materials
High removal efficiency for organic
pollutants
High removal efficiency for volatile
inorganics
High removal efficiency for heavy metals
Significant flexibility to handle changes in
feed composition
Minimal pretreatment required
Concentrates wastewaters from 0.5% to
65% total solids, providing a volume
reduction of 130 to 1 with no pretreatment
requirements
Routinely removes 99% of all organic
compounds; higher removals achieved
forspecif ic pollutants (forexample, 99.99%
for toluene)
Generally removes 99% of ammonia and
cyanide compounds
Heavy metals separated by evaporation
of wastewater; therefore, PO*WW*ER™
can achieve extremely high removal
efficiencies
System insensitive to changes in heavy
metal concentration and only sensitive to
changes in organic composition
Only possible pretreatment may be
neutralization and control of foaming
Reverse Osmosis: limited to 7 to 8% total
solids and requires substantial
pretreatment; volume reductions of only
15 to 1 typical.
Biological Treatment: limited to 95 to 98%
for biologically degradable compounds;
others not removed
Stripping and oxidation: limited to
equilibrium solubility at operating
temperatures
Precipitation: limited to solubility point of
metallic species
General: Most systems cannot
accommodate changes in feed
composition and providing high-quality
effluent
General: comprehensive pretreatment
may be required for sophisticated
treatment processes
• Uses no chemicals except for pH adjustment or
defoaming chemicals
• Can use waste energy to significantly improve cost
economics
• Requires a small area, enabling the location of the
technology next to processing plants, thus
improving operatingflexibility and saving valuable
real estate.
A.L4 Applications
PO*WW*ER™ technology is ideally suited for
treatment and volume reduction of complex industrial and
hazardous wastewaters containing mixtures of inorganic
salts, metals, volatile and semivolatile organics, volatile
inorganics, and radionuclides. The technology is
particularly suited to wastewater that cannot be treated by
a single conventional step and that requkes a complex
treatment train involving a number of unit operations.
A partial list of the contaminants and pollutants treatable
by the PO*WW*ER™ technology are presented in Table
A-2. The general ranges of contaminants and pollutants in
wastewaters successfully treated by PO*WW*ER™
technology applications are presented below.
Total Volatile Organics:
Total Semivolatile Organics:
Total Dissolved Solids:
Radioactive Contaminants:
100 to 10,000 parts per
million (ppm)
10 to 500 ppm
0.25% to 15%
Up to 500 ppm
Examples of wastewaters that are good candidates for
treatment by the PO*WW*ER™ technology include the
following:
• Landfill leachates
• Lagoon waters
• Contaminated ground water
• Low-level radioactive mixed wastewaters
• Industrial wastewaters from chemical,
petrochemical, steel, automobile, synthetic rubber,
wood finishing, paint, and pulp and paper plants
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Table A-2. Contaminants and Pollutants Treatable by PO*WW*ER™
Organic Inorganic
Radioactive
Halogenated volatiles
Halogenated semivolatiles
Nonhalogenated volatiles
Nonhalogenated semi-volatiles
Organic pesticides and herbicides
Solvents
Benzene, toluene, ethylbenzene, and xylenes
Organic cyanides
Nonvolatile organics
Heavy metals
Nonmetallic toxic elements
Cyanides
Ammonia
Nitrates
Salts
Plutonium
Americium
Uranium
Technetium
Thorium
Radium
Barium
A.1.5 Design Options
The basic PO*WW*ER™ system consists of a forced
circulation evaporator, an oxidizer, and an air-cooled
condenser. The system is supplied in modular design for up
to 50 gallons per minute of treatment capacity for easy
installation and commissioning. Larger systems are provided
as multiple units of modular construction or are designed for
the required capacity for field construction and installation. A
number of options are available to enhance the performance
or improve the overall cost economics of the PO* WW*ER™
system for a given application. Some of these design options
and their contributing benefits are listed in Table A-3.
Depending on wastewater characteristics, costs of utilities,
and availability of waste heat, one or more of these options
may be incorporated to provide an optimum design for the
application.
Table A-3. Design Options for the PO*WW*ER™ System
Option Contributing Effect
Multi-effect Evaporator Saves up to 50 to 70% energy
consumption compared to a single effect
evaporator
Mechanical Vapor
Recompression
Evaporator
Scrubber
Waste Heat Utilization
Saves up to 50% energy
consumption when reasonably
priced electricity is available
Removes acid gases formed in the
oxidizer when chlorinated hydrocarbons
are present in the wastewater
Improves cost economics depending
upon the level and quantity of waste
heat available
A. 1.6 Cost Economics
The typical cost of a PO*WW*ER™ system with a 50
gallon per minute (gpm) treatment capacity that is
completely assembled and installed on a turnkey basis is
$4.0 million. Similarly, a 25 gallon per minute treatment
capacity system costs $3.0 million.
Utilities required for these two system sizes are as
follows:
Electricity, Kilowatt
hours per hour
Natural Gas, standard
cubic feet per hour (scfh)
50 GPM
445
22,000
25 GPM
275
11,000
Total operating costs, which include utilities and minor
additions of antifoam and catalyst agents, are less than
$0.04 per gallon.
The above examples were estimated for a wastewater
stream of landfill leachate treated in a PO*WW*ER™
systemhaving adouble effect evaporator. Other wastewater
streams would have similar capital and operating costs.
A.2 Summary
The PO*WW*ER™ technology is an innovative, cost-
effective, and flexible technology for treating industrial
and hazardous wastewaters. The technology can treat
wastewaters with varying complexities, changing
characteristics, varying levels of contaminants, and different
quantities of total dissolved solids.
A PO*WW*ER™ system produces high-quality
effluent, destroys organic pollutants, and achieves very
high volume reduction. This technology has been well
demonstrated and is now commercially used to treat a
variety of hazardous industrial wastewaters.
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Appendix B
Site Demonstration Results
The Chemical Waste Management, Inc. (CWM),
Superfund Innovative Technology Evaluation (SITE)
demonstration was conducted in September 1992 at CWM's
LakeCharlesTreatmentCenter (LCTC) site in Lake Charles,
Louisiana. This appendix briefly describes the LCTC site
and technology demonstration testing and sampling
procedures, and summarizes the SITE demonstration
treatment results. References appear at the end of this
appendix.
B.I Site Description
CWM's LCTC site is located near the cities of Sulphur
and Lake Charles in the southwest corner of Louisiana. The
LCTC site has facilities that include a hazardous waste
landfill, a high-capacity stabilization unit, and drum
managing and decanting facilities. CWM began operating
the site's first hazardous waste disposal cell in 1980.
Although CWM constructed and operated two sanitary
landfills at the site during the early 1980s, the company's
primary focus remains hazardous waste treatment and
disposal. The LCTC is capable of handling almost any type
of liquid hazardous waste, including wastes containing
organics, cyanide, sulfide, and other inorganics.
The PO*WW*ER™ pilot-scale plant located at the
LCTC site has been operative since 1988. The
PO*WW*ER™ pilot plant is used primarily as a
demonstration unit for companies interested in testing the
PO*WW*ER™ system's applicability to specific aqueous
wastes. The PO*WW*ER™ system was originally
developed to handle leachates from CWM's hazardous
waste land disposal units, but it is currently being marketed
for a variety of aqueous treatment applications.
B.2 Technology Demonstration Testing and
Sampling Procedures
The objectives of the SITE demonstration of CWM's
PO*WW*ER™ system were to assess the system's
effectiveness in (1) removing organic and inorganic
contaminants from leachate; (2) producing a small volume
of concentrated residual waste known as brine for further
treatment or disposal; (3) producing a noncondensible gas
stream that meets proposed permit requirements for the
LCTC site, and (4) producing a condensate stream nontoxic
to aquatic organisms. This section discusses technology
testing and sampling procedures.
The technology demonstration was conducted under
one set of operating parameters, which were established by
CWM based on past operating experience with the
PO*WW*ER™ system. Table B-l summarizes thesystem's
operating parameters during the SITE demonstration. These
operating parameters were applied in two sets of test runs:
one set of three replicate test runs using unspiked LCTC
landfill leachate and one set of three replicate test runs
using LCTC landfill leachate spiked with the following
compounds: 100 milligrams per liter (mg/L) each of
methylene chloride, tetrachloroethene (PCE), and toluene;
10 mg/L of phenol; 2 mg/L cadmium; 0.2 mg/L mercury;
and 50 mg/L each of copper, nickel, and iron. Table B-2
presents a summary of the operating temperatures and flow
rates recorded during each SITE demonstration test run.
Table B-1. SITE Demonstration Test Conditions
Parameter Value
Acid or caustic addition to feed
Antifoam agent addition to feed
Feed rate
Concentration ratio
Oxidizer inlet temperature
Catalyst bed depth
Scrubbing liquor
Boiling point rise (BPR)
None
Agent EP-530 as needed
0.16 to 0.21 gallons per minute
(gpm)
31.4 to 32.3
NA
NA
NA
NA
Note:
NA — Information not available (see Section 3.8 for details).
41
-------
Table B-2. Operating Temperatures and Flow Rates of the PO*WW*ER™ Pilot System During the SITE Demonstration
Run No.
1
2
3
1
2
3
Flow Rate
(gpm)
0.18
0.21
0.19
0.19
0.16
0.17
Feed'
Temperature
•op
75
77
78
81
80
79
Product
Flow Rate
(gpm)
0.18
0.19
0.17
0.21
0.15
0.12
Condensate"
Temperature
°F
Unspiked
132
135
133
Spiked
132
116
99
Brine0
Volume
(Gallons)
5.05
4.73
3.61
5.00
4.26
5.91
Noncondensible Gas
Flow Rated
(scfm)
24.1
27.3
25.7
24.9
23.6
21.5
Temperature
°F
80
78
77
81
78
70
Average
0.18
78
0.17
125
4.76
24.52
77
Notes:
• Tha feed waste flow rate was estimated using the rate of level indicator changes. The rate of level indicator changes were converted
to volumetric rate changes by using a calibration line established during the SITE demonstration. The volume of feed waste
sampled and purged was subtracted from the volume fed into the PO*WW*ER™ pilot system. The feed waste temperatures
reported represent an average of nine hourly independent measurements.
b The product condensate flow rate was estimated using the rate of level indicator changes. The rate of level indicator changes were
converted to volumetric rate changes by using a calibration line established during the SITE demonstration. The product
oondensate was sampled after the product condensate tank; therefore, no volume corrections were required. The product
condensate temperatures reported represent an average of nine hourly independent measurements.
c Brine was wasted and sampled only once during each 9-hour test period. Therefore, the reported values represent the total volume
wasted and sampled during the 9-hour test period. Because of field difficulties, brine temperature was not measured during the
SITE demonstration.
4 scfm — standard cubic feet per minute
During the SITE demonstration, about 308 gallons of
unspiked landfill leachate and 280 gallons of spiked landfill
leachate were treated. Each demonstration test required
about 9 hours of PO*WW*ER™ system operation to
conduct sampling and monitoring operations.
Sampling began when the PO*WW*ER™ system
operatedunder steady-state conditions. During the unspiked
test runs, sampling began 9 days after the LCTC
PO*WW*ER™ pilot plant started operating. For each set
of test runs, sampling was conducted over a period of 3
days. During the spiked test runs, sampling began 48 hours
after the spiked leachate feed waste was first introduced in
the PO*WW*ER™ system. The target spiking solution
concentrations were based on a feed waste volume of
500 gallons. The actual spiking solution concentrations of
some VOCs were less than the target spiking solution
concentrations probably because of VOC losses during
mixing of feed waste with the spiking solution. During the
3-day sampling period, spiking compounds were added
daily to the feed waste tank, which contained unspiked
leachate, at least 1 hour before sampling began. This
procedure allowed the leachate and the spiking compounds
in the feed tank to mix for approximately 1 hour, ensuring
thorough mixing of the leachate and preventing stratification
of the chemicals added. Spiking solutions were added to the
feed tank daily. Spiking during the approximate 48-hour
period preceding sampling allowed the concentrations of
spiking compounds in the brine to reach approximately
steady-state concentrations.
During each test run, samples were collected from the
feed waste, product condensate, brine, and noncondensible
gas stream. Feed waste, product condensate, and brine
samples were analyzed for total suspended solids (TSS),
total dissolved solids (TDS), ammonia, cyanide, volatile
organic compounds (VOC), semivolatile organic
compounds (SVOC), oil and grease, total organic halides
(TOX), total organic carbon (TOC), metals, chloride, nitrate,
sulfate, and pH. Samples of feed waste and product
condensate were also analyzed for acute toxicity. Brine
samples were also analyzed for toxicity characteristic
leaching procedure (TCLP) metals, VOCs, and SVOCs.
Continuous emissions monitoring (CEM) of the
noncondensible gas stream included monitoring for total
nonmethane hydrocarbons (TNMHC), carbon dioxide
(CO2), carbon monoxide (CO), nitrogen oxides (NOx),
sulfur dioxide (SO2), and oxygen. Noncondensible gas
samples were also collected and analyzed for VOCs,
SVOCs, and hydrochloric acid (HC1).
42
-------
Critical analytes for the feed waste and product
condensate included VOCs, SVOCs, ammonia, cyanide,
TSS, TDS, and acute toxicity, which was a critical analyte
only for the product condensate. Critical analytes for the
brine were TSS and TDS. Critical analytes for the
noncondensible gas stream were CO, NOx, and SO .
For feed waste and product condensate, nine samples
were collected for each critical analyte during each set of
three replicate runs. For each critical analyte except VOCs
and acute toxicity testing, one composite sample was
collected every 3 hours, resulting in nine samples at the end
of each set of three replicate runs. A sample was composited
from equal portions of three successive grab samples
collected every hour. VOC samples were collected as grab
samples once every 3 hours in order to avoid losses during
compositing. Acute toxicity testing samples were collected
as grab samples once each day. Brine was wasted and
sampled only once during each 9-hour test run. The
noncondensible gas stream was monitored using a CEM
system.
For feed waste and product condensate, three samples
were collected for each noncritical analyte during each set
of three replicate test runs, one 9-hour composite sample
for each analyte. Feed waste and product condensate pH
was measured in the field every 3 hours. Brine pH was
measured in the laboratory.
During each set of three replicate runs for the
noncondensible gas stream, nine samples were collected
for VOCs using the Volatile Organic Sampling Train
(VOST) sampling method; three samples were collected
for SVOCs using the Modified Method 5 (MM5) sampling
method, and three samples were collected for HC1 using the
Boilers and Industrial Furnaces (BIF) 0051 sampling
method.
All sampling and analysis procedures met the
requirements of a U.S. Environmental Protection Agency
(EPA) Category II quality assurance project plan (QAPP)
as specified in EPA's Risk Reduction Engineering
Laboratory (RREL) document Preparation Aids for the
Development of Category II Quality Assurance Project
PJans,datedFebruaryl991,DocumentNo.EPA/600/8-91/
004.
B.3 Treatment Results
This section summarizes analytical results of the
PO*WW*ER™ system SITE demonstration and evaluates
the system's effectiveness in treating landfill leachate
contaminated with VOCs, SVOCs, ammonia, cyanide,
metals and other inorganic contaminants and oil and grease.
The following sections summarize: (1) results for critical
parameters and (2) results for noncritical parameters.
B.3.1 Summary of Results for Critical Parameters
Critical parameters for the PO*WW*ER™ system
SITE demonstration include (1) volume reduction, (2)
VOC removal, (3)SVOC removal, (4) ammonia and cyanide
removal, (5) noncondensible gas emissions, and (6) acute
toxicity. These parameters are discussed below.
Volume Reduction
The PO*WW*ER™ system reduces the volume of an
aqueous waste by evaporation and concentrates nonvolatile
contaminants in the brine. During each 9-hour testrun at the
LCTC site, the PO*WW*ER™ system processed about
98 gallons of feed waste. Brine was wasted and sampled
only once during the 9-hour test period. The total volume
of brine wasted during each 9-hour test run washout
4.8 gallons, or about 5 percent of the feed waste volume.
Figure B-l shows the volume of feed waste processed by
the PO*WW*ER™ system and the volume of brine wasted
during each unspiked and spiked test run.
The PO*WW*ER™ system's effectiveness for volume
reduction was evaluated based on the concentration ratio,
which is defined as the ratio of TS concentration in the
brine over the TS concentration in the feed waste. The TS
concentration is estimated as the sum of TSS and TDS.
Tables B-3 and B-4 summarize TSS and TDS concentrations
in feed waste, product condensate, and brine during the
unspiked and spiked test runs, respectively. The results
show that the brine TS concentration during the unspiked
and spiked test runs remained almost the same. However,
the TSS concentration in brine increased during the spiked
test runs, probably because of the precipitation of metals
used as spiking compounds. Figure B-2 shows the TS
concentration in feed waste and brine during each unspiked
and spiked test run. The TS concentration in the brine was
significantly higher than that in the feed waste. The TS
concentration in brine was primarily comprised of
nonvolatile contaminants originally present in the feed
waste. Therefore, the increase in TS concentration in the
brine was caused by the volume reduction of the feed waste.
Therefore, the TS concentration ratio is a reliable measure
of feed waste volume reduction that occurs during treatment
in the PO*WW*ER™ system.
43
-------
120
-g 90+
o
O
-------
Table B-4. Summary of TSS, TDS, and TS Concentrations in Feed Waste, Product Condensate and Brine During Spiked Test Runs
Feed Waste Product Condensate Brine3
Run No.
1
Average
2
Average
3
Average
TSS
(mg/L)
750
500
400
550
700
600
600
630
350
400
400
380
TDS
(mg/L)
16,000
15,000
16,000
16,000
17,000
16,000
16,000
16,000
16,000
17,000
17,000
17,000
(mg/L)
17,000
16,000
16,000
16,000
18,000
17,000
17,000
17,000
16,000
17,000
17,000
17,000
TSS
(mg/L)
<4°
<4
<4
<4
<4
<4
<4
<4
<4
<4
<4
<4
TDS TSb TSS
(mg/L) (mg/L) (mg/L)
<10 <14
<10 <14 4,800
<10 <14
<10 <14 NAd
<10 <14
<10 <14 5,500
<10 <14
<10 <14 NA
<10 <14
<10 <14 7,500
16 <20
<12e <16 NA
TDS
(mg/L)
560,000
NA
540,000
NA
500,000
NA
TS"
(mg/L)
560,000
NA
550,000
NA
510,000
NA
Notes:
a Brine was wasted and sampled once per test run. Therefore, the reported results represent analysis of one sample.
b This value represents the sum of the respective TSS and TDS values.
c < = Not detected at detection limit shown
d NA = Not applicable
e This value represents the average of concentrations measured above and below the detection limit.
600,000/
f
§ 400,000
1
I
| 200,000-
0
3 4
Run No.
^!:;>"s
$&&:
Feed Waste
mm
Brine
Note: Runs 1 through 3 were conducted with unspiked landfill leachate, and Runs 4 through 6 were
conducted with spiked landfill leachate.
Figure B-2. TS concentration of feed waste and brine during the unspiked and spiked test runs.
45
-------
The concentration ratio of chloride and metals in the
brine and feed waste was also estimated. Table B-5
summarizes the concentration ratios estimated based on
TS, chloride, and metals. The concentration ratio based on
TS was estimated to be about 31 to 1 and 32 to 1 during the
unspiked and spiked test runs, respectively. The chloride
concentration ratio was 33 to 1 and 31 to 1 during the
unspiked and spiked test runs, respectively. The metals
concentration ratio was 33 to 1 and 30 to 1, respectively.
The results show thatTS, chloride, and metals concentration
ratios are almost identical. A statistical test was conducted
usingtheStudent'st-testdistribution to compare theaverage
concentration ratios of TS, chloride, and metals (Kleinbaum
and Kupper, 1978). The statistical test shows that with
99 percent confidence, the average ratios are not
significantly different. Therefore, the estimate of the
concentration ratio is reliable and is considered to represent
areliable measure of feed waste volume reduction achieved
during treatment in the PO*WW*ER™ system. The
concentration ratios achieved during the unspiked test runs
are very similar to those achieved during the spiked test
runs. This similarity is expected because during the spiked
test runs, the spiking compounds added in relatively large
amounts were VOCs, which evaporate and do not contribute
to TS concentration in the brine.
Table B-5. Concentration Ratios During Unspiked and Spiked
Test Runs
Unspiked Test Runs
Run No.
1
2
3
Average
Standard Deviation
Run No.
1
2
3
Average
Standard Deviation
TS
32
31
31
31
0.65
Spiked Test
TS
35
32
30
32
2.1
Chloride
32
35
32
33
1.6
Runs
Chloride
33
28
33
31
2.0
Metals
31
35
34
33
1.8
Metals
30
29
31
30
1.0
VOC Removal
Acetone, 2-butanone, methylene chloride, PCE, toluene,
and vinyl chloride were identified as critical VOCs for the
PO*WW*ER™ system SITE demonstration. During the
spiked test runs, feed waste was spiked with 100 mg/L of
each of the following: methylene chloride, PCE, and toluene.
The purpose of spiking the feed waste was to test the effect
of contaminant loading on VOC treatment efficiency.
Vinyl chloride was not detected during unspiked and
spiked test runs in feed waste, product condensate, or brine.
Thedetectionlimitforthe feed waste was 1,000 micrograms
per liter (ug/L) during the unspiked test runs and ranged
from5,000to 10,000 ug/L; for the brine it was less than 100
ug/L during both the unspiked and spiked test runs.
Therefore, vinyl chloride is not discussed further. Table B-6
summarizes analytical results of critical VOCs during the
unspiked and spiked test runs.
During the unspiked test runs, acetone concentration in
feed waste samples ranged from 8,200 to 12,000 ug/L; in
brine samples it was less than the detection limit of 100 ug/L
during the first and second unspiked test runs and 140 ug/L
during the third unspiked test run; and in product condensate
samples it was less than the detection limit of 10 ug/L.
During the spiked test runs, acetone concentration in feed
waste samples ranged from 13,000 to 18,000 ug/L; in brine
samples, it ranged from 180 to 220 ug/L. The results
indicate that during the spiked test runs, acetone was not
completely removed from the brine. Because acetone was
not one of the spiking compounds, the results suggest that
total contaminant loading, which increased during the
spiked test runs, had a measurable effect on the acetone
evaporation efficiency. However, the concentration of
acetone in product condensate was less than the detection
limit of 10 ug/L, indicating that total contaminant loading
had no measurable effect on product condensate quality.
During the unspiked test runs, 2-butanone concentration
in feed waste samples ranged from 1,500 to 2,200 ug/L; in
brine samples it was less than the detection limit of 100 ug/L;
and in product condensate samples it was less than the
detection limit of 10 ug/L. During the spiked test runs, 2-
butanone concentration in feed waste samples was less
than 10,000 ug/L; in brine samples it was less than the
detection limit of 100 ug/L; and in product condensate
samples it was less than the detection limit of 10 ug/L.
These results indicate that total contaminant loading had no
measurable effect on 2-butanone evaporation efficiency or
product condensate quality.
During the unspiked test runs, methylene chloride
concentration in feed waste samples ranged from 640 to
1,700 ug/L; in brine samples it was less than the detection
limit of 50 ug/L; in product condensate samples it was less
than the detection limit of 5 ug/L during the first and third
unspiked tests. However, during the second unspiked test
run, methylene chloride concentration ranged from 5 to"
8 ug/L. During the spiked test runs, methylene chloride
46
-------
Table B-6. Critical VOC Concentrations During Unspikecl and Spiked Test Runs
Unspiked Test Runs
Run No.
Feed Waste
Product Condensate Brine3
Feed Waste
Product Condensate
Brine3
Acetone (\ig/L)
1
Average
2
Average
3
Average
11000Mb
11000M
12000 M
11000M
8300 M
8800 M
9100 M
8700 M
8200 M
9300 M
9700 M
9100M
<10°
<10
<10
<10
4 (10)d
<10
5(10)
<6"
<10
<10
<10
<10
<100
NA1
<100
NA
140
NA
13000 M
13000 M
13000 M
13000 M
14000 M
13000 M
13000 M
13000 M
17000 M
18000 M
15000 M
17000 M
<10M
<10M
<10M
<10M
<10M
<10M
<10M
<10M
<10M
<10M
<10M
<10M
220 M
NA
180 M
NA
180 M
NA
2-Butanone (M9/L)
1
Average
2
Average
3
Average
1
Average
2
Average
3
Average
1
Average
2
Average
1800
2200
2200
2100
1500
1500
1500
1500
1600
1800
1900
1800
1300
1100
890
1100
1700
1100
640
1100
710
640
730
690
<500
170 (500)
<500
<390"
<500
<500
<500
<500
<10
<10
<10
<10
<1 0
<1 0
<1 0
<1 0
<10
<10
<10
<10
<5
<5Ce
<5
<5
8
6
5C
6
<5
<5C
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<100
NA
<100
NA
<100
NA
Methylene Chloride
<50
NA
<50
NA
<50
NA
PCE (ug/L)
<50
NA
<50
NA
47
<10000
<10000
<10000
<10000
2900 (5000)
2700 (5000)
<5000
<3500"
<10000
<10000
3100(5000)
<770Q9
(M9/L)
110000 C
110000 C
100000 C
110000 C
93000 C
93000 C
88000 C
91000 C
95000 C
100000 C
96000 C
97000 C
50000 M
54000 M
55000 M
53000 M
47000 M
47000 M
52000 M
49000 M
<10
<10
<10
<10
<10
<10
<10
<10
<10
<10
<10
<10
<5
<5
<5
<5
<5C
<5
<5
<5
<5C
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<100M
NA
<100M
NA
<100M
NA
190
NA
110
NA
200 C
NA
69 M
NA
46 (50)M
NA
-------
Table B-6. Critical VOC Concentrations During Unspiked and Spiked Test
Unspiked Test Runs
Run No.
3
Average
1
Average
2
Average
3
Average
Feed Waste
<500
<500
<500
<500
370 (500)
420 (500)
370 (500)
390 (500)
370 (500)
350 (500)
320 (500)
350 (500)
410 (500)
440 (500)
350 (500)
400 (500)
Product Condensate Brine3
<5
<5
<5
<5
1(5)
<5
1(5)
<2o
<5
<5
<5
<5
<5
<5
<5
<5
<50
NA
Toluene (pg/L)
<50
NA
<50
NA
<50
NA
Runs (Continued)
Feed Waste
55000 M
60000 M
49000 M
55000 M
68000
69000
62000
66000
55000
50000
52000
52000
55000
57000
46000
53000
Spiked Test Runs
Product Condensate
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
Brine3
34 (50)M
NA
49 (50)
NA
49 (50)
NA
37(50)
NA
Notes:
Brine was wasted and sampled once per test run. Therefore, the reported results represent analysis of one sample.
M Indicates that the analytes concentration is estimated because MS/MSD precision or accuracy criteria were not met.
< = Analyte not detected at the detection limit shown
Analyte detected at an estimated concentration below the detection limit shown in parentheses
C indicates that analyte concentration is estimated because calibration criteria were not met.
NA = Not applicable
This value represents the average of concentrations estimated below the detection limit and at the detection limit, as well.
concentrations in feed waste samples ranged from 88,000
to 110,000 ug/L, and in brine samples it ranged from 110
to 200 ug/L. The results suggest that contaminant loading,
which increased during the spiked test runs, had a slight but
measurable effect on methylene chloride evaporation
efficiency. However, methylene chloride concentration in
product condensate was less than the detection limit of
5 ug/L, indicating that total contaminant loading had no
measurable effect on product condensate quality.
During the unspiked test runs, PCE concentration in
feed waste samples were less than the detection limit of
500 ug/L; in brine samples it was less than the detection
limit of 50 ug/L; and in product condensate samples it was
less than the detection limit of 5 ug/L. During the spiked
test runs, PCE concentration in feed waste samples ranged
from 47,000 to 60,000 ug/L, and in brine samples it ranged
from less than the detection limit of 50 to 69 ug/L. The
results suggest that contaminant loading, which increased
during the spiked test runs, had a slight but measurable
effect on PCE evaporation efficiency. However, the
concentration of PCE in product condensate was less than
the detection limit of 5 ug/L, indicating that total
contaminant loading had no measurable effect on product
condensate quality.
During the unspiked test runs, toluene concentration in
feed waste samples was less than the detection limit of
500 ug/L; in brine samples it was less than the detection
limit of 50 ug/L; and in product condensate samples it was
less than the detection limit of 5 ug/L. During the spiked
test runs, toluene concentration in feed waste samples
ranged from 46,000 to 69,000 ug/L; in brine samples it was
less than the detection limit of 50 ug/L; and in product
condensate samples it was less than the detection limit of
5 ug/L. The results suggest that contaminant loading had
no measurable effect on toluene evaporation efficiency or
product condensate quality.
48
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SVOC Removal
Benzole acid and phenol were identified as critical
SVOCsforthePO*WW*ER™systemSriEdemonstration.
During the spiked tests feed waste was spiked with 10 rng/L
of phenol to test the effect of contaminant loading on the
SVOC treatment efficiency. Table B-7 summarizes
analytical results of critical SVOCs during unspiked and
spiked test runs.
During the unspiked test runs, benzoic acid
concentration in feed waste samples ranged from 6,300 to
24,000 ug/L; in brine samples it ranged from 600,000 to
1,600,000 ug/L; in product condensate samples it was less
than the detection limit, which ranged from 25 to 130 ug/L.
During the spiked test runs, the benzoic acid concentration
in feed waste samples ranged from 13,000 to 24,000 ug/L;
in brine samples it ranged from 620,000 to 930,000 ug/L;
and in product condensate samples it was less than the
detection limit, which was 130 ug/L for most samples
analyzed. The results indicate that during the unspiked and
spiked test runs, benzoic acid remained primarily in the
brine.
During the unspiked test runs, phenol concentration in
feed waste samples ranged from 5,300 to 11,000 ug/L; in
brine samples it was less than the detection limit of
Table B-7. Critical SVOC Concentrations During Unspiked and Spiked Test Runs
Unspiked Test Runs
Run No.
Feed Waste Product Condensate Brine3
Spiked Test Runs
Feed Waste Product Condensate Brine3
Average
2
Average
3
Average
17000 Mb
15000 M
15000 M
16000 M
16000 M
18000 M
16000 M
17000 M
6300 M
24000 M
7100 M
12000 M
<25C
<25
<25
<25
<130
<130
<130
<130
<25
<25
<25
<25
Benzoic Acid (ug/L)
600000 Hd
NAe
690000
NA
1600000
NA
Phenol (ug/L)
24000
23000
21000
23000
13000
13000
15000
14000
20000
15000
16000
17000
<130
<130
<130
<130
<130
<130
<25
<95f
<130
<25
<130
<95f
620000 H
NA
800000 H
NA
930000 H
NA
1
Average
2
Average
3
Average
8900 M
8800 M
9600 M
9100 M
8100 M
11000 M
11000 M
10000 M
5300 M
7300 M
5300 M
6000 M
<10
<10 <200000 H
<10
<10 NA
<50
<50 <200000
<50
<50 NA
<10
<10 <200000
<10
<10 NA
17000 M
17000 M
17000 M
17000 M
14000 M
13000 M
12000 M
13000 M
12000 M
13000 M
14000 M
13000 M
<50
<50
<50
<50
<50
<50
<10
<37f
<50
<10
<50
<37f
<200000 H
NA
<200000 H
NA
<200000 H
NA
Notes:
3 Brine was wasted and sampled once per test run. Therefore, the reported results represent analysis of one sample
b M indicates analyte concentration was estimated because MS/MSD accuracy or precision criteria were not met.
0 < = Analyte not detected at detection limit shown
d H indicates that analyte concentration is estimated because holding time was exceeded.
NA = Not applicable
' This value represents the average of three detection limits, where at least one limit differs from the other two.
49
-------
200,000 ug/L; in product condensate samples it was less
than the detection limit, which ranged from 10 to 50 ug/L.
During the spiked test runs, the phenol concentration in
feed waste samples ranged from 12,000 to 17,000 ug/L; in
brine samples it was less than the detection limit of
200,000 ug/L; and in product condensate samples it was
less than the detection limit of 50 ug/L. The results suggest
that phenol vaporizes, at least partially, and is presumably
oxidized in the catalytic oxidizer. Although-benzole acid
and phenol are both acidic compounds, they have very
different physical-chemical properties. Given these
properties, phenol is more likely than benzoic acid to be
removed from the brine. Phenol has a vapor pressure over
30 times greater than benzoic acid. Also, under the test
conditions, phenol was likely present in the brine primarily
in unionized form while benzoic acid was likely present in
ionized form.
Phenol has a boiling point of 358 °F, which is
significantly higher than the steam temperature used for
heating in the evaporator heat exchanger. However, the
evaporation of semivolatile contaminants in the evaporator
can take place because of the increase in boiling point,
known as the BPR, the stripping effect of steam, and the
solution ionic strength. The BPR is the difference between
the boiling point of asolution and the boiling point of water
at the same pressure. The BPR occurs because of increased
concentration of solids in the evaporator. During the SITE
demonstration, the BPR was not recorded because of
testing limitations imposed by CWM.
Another reason that could have caused the evaporation
of phenol is the effect of ionic strength. Because the
concentration of ionic species increases in the brine because
of the evaporation of water, ionic strength also increases.
High ionic strength results in a decrease in the solubility of
molecular species such as phenol. This phenomenon is
known as the "salting-out effect" and may cause the
evaporation of some SVOCs.
Ammonia and Cyanide Removal
Ammonia and cyanide were identified as critical
inorganic contaminants during the SITE demonstration.
The evaporation efficiency of ammonia and cyanide in the
PO*WW*ER™ system depends on feed waste pH and the
types of metals present. Under certain conditions, the
PO* WW*ER™ system vaporizes ammonia and cyanide in
the evaporator and oxidizes both in the catalytic oxidizer.
Ammonia forms complexes with cadmium, cobalt, copper,
silver, mercury, nickel, and zinc. Cyanide forms complexes
with cadmium, copper, silver, mercury, iron, nickel, and
zinc. All the above-mentioned metals were present in feed
waste samples during unspiked and spiked test runs. Metal
complexes of ammonia and cyanide need to be destroyed
before ammonia and cyanide can be evaporated and
oxidized. Free ammonia volatilizes effectively at pH values
greater than 9. Free cyanide volatilizes effectively at pH
values less than 9. Table B-8 summarizes analytical results
of ammonia and cyanide during unspiked and spiked test
runs.
During the unspiked test runs, ammonia concentration
in feed waste samples ranged from 150 to 160 mg/L; in
brine samples itranged from 5.4 to 23 mg/L; and in product
condensate samples it was less than the detection limit of
0.1 mg/L. During the spiked test runs, ammonia
concentration in feed waste samples ranged from 140 to
160 mg/L; in brine samples it ranged from 7.4 to 7.8 mg/L;
and in product condensate samples it was less than the
detection limit of 0.1 mg/L. The results indicate that during
the unspiked and spiked test runs, ammonia was not
completely removed from the brine, possibly because the
feed waste pH ranged from 8.5 to 9.1, close to the lower
optimum pH range for ammonia volatilization, or because
ammonia complexed with metals, which were present in
the feed waste.
During the unspiked test runs, cyanide concentration in
feed waste samples ranged from 25 to 34 mg/L; in brine
samples it ranged from 77 to 150 mg/L; and in product
condensate samples it was less than the detection limit of
0.01 mg/L. During the spiked test runs, cyanide
concentration in the feed waste ranged from 24 to 36 mg/L;
in brine samples it ranged from 17 to 77 mg/L; and in
product condensate samples it was less than the detection
limit of 0.01 mg/L. The results indicate that during the
spiked test runs, cyanide was not completely removed from
the brine, possibly because the feed waste pH ranged from
8.5 to 9.1, which is near the upper optimum pH range for
cyanide volatilization, or because cyanide complexed with
metals, which were present in the feed waste.
Figure B-3 shows evaporation efficiencies of ammonia
and cyanide during the unspiked and spiked test runs. The
percent (%) evaporation efficiency is defined by the
following equation:
%Evap.Eff. =
W,
feed waste
-W,
brine
W,
x 100
feed waste
(B-l)
50
-------
Table B-8. Critical Inorganic Contaminants During Unspiked and Spiked Test Runs
Unspiked Test Runs
Spiked Test Runs
Run No.
1
Average
2
Average
3
Average
1
Average
2
Average
3
Average
Feed Waste
150
150
160
150
150
150
150
150
160
160
150
160
32
31
25
29
32
34
34
33
29
31
. 31
30
Product Condensate
<0.10b
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Brine3
NH3(mg/L)
5.4
NAd
23 H
NA
11
NA
CN-(mg/L)
77
NA
150
NA
140
NA
Feed Waste
160 H
150 H
160 H
160 H
140 H
150 H
150 H
150 H
140
140
140
140
30
36
33
33
32
31
33
32
24
24
24
24
Product Condensate
<0.10H
<0.10H
<0.10 H
<0.10H
<0.10H
<0.10 H
<0.10H
<0.10 H
<0.10
<0.10
<0.10
<0.10
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Brine"
7.8 H°
NA
7.5 H
NA
7.4
NA
36
NA
17
NA
77
NA
Notes:
a Brine was wasted and sampled once per test run. Therefore, the reported results represent analysis of one sample.
b < = Analyte not detected at detection limit shown
c H indicates that analyte concentration was estimated because holding time was exceeded.
d NA = Not applicable
where
Wfeed was[e = mass of ammonia or cyanide in feed
waste
W
brine
= mass of ammonia or cyanide in brine
The ammonia evaporation efficiencies ranged from
99.4 to 99.8 percent during the unspiked test runs and from
99.7 to 99.8 percent during the spiked test runs. The cyanide
evaporation efficiencies ranged from 81.0 to 86.0 percent
during the unspiked test runs and from 79.1 to 97.4 percent
during the spiked test runs. Apparently, ammonia showed
a higher evaporation efficiency because the pH of the feed
waste, which ranged from 8.5 to 9.1, and the pH of brine,
which was greaterthan 10, encourage ammonia evaporation.
Cyanide evaporation is more effective in the acidic pH
range. Another reason that may have contributed to the
lower cyanide evaporation efficiency is its tendency to
form much stronger complexes with metals, particularly
iron. These complexes are very hard to destroy in order to
release the cyanide. Some metal cyanide complex
destruction can be achieved under acidic conditions, but
iron-cyanide complexes are hard to destroy even under
acidic conditions (Butler, 1964). During the SITE
demonstration, the pH of the brine was greater than 10,
which is advantageous to the volatilization of ammonia but
not cyanide.
51
-------
10CH
I
I
fi
•4—*
g
D-i
3 4
Run No.
Cyanide
;V";
Ammonia
Note: Runs 1 through 3 were conducted with unspiked landfill leachate, and Runs 4 through 6 were
conducted with spiked landfill leachate.
Figure B-3. Cyanide and ammonia evaporation efficiencies during unspiked and spiked test runs.
Noncondensible Gas Emissions
During the SITE demonstration, CEM of the
noncondensible vent gas was conducted. Table B-9
summarizes the CEM results. The CO, SO2, and NOx
concentrations are discussed below. The average CO
concentrations ranged from 9.58 to 37.3 parts per million
by volume (ppmv), resulting in emissions ranging from
1.1 x 10'3 to 3.92x 1O'3 pounds per hour (Ib/hr); the 60-minute
maximum CO concentrations ranged from 11.1 to
40.8 ppmv, resulting in emissions ranging from 1.27xlO~3
to 4.28x10"3 Ib/hr. The average SO2 concentrations were
less than 2 ppmv, resulting in emissions of less than 5.5x10"4
Ib/hr, The 60-minute maximum SO2 concentrations ranged
from less than 2 to 3.49 ppmv, resulting in emissions
ranging from less than 5.5xlO'4 to 8.4xlO'4 Ib/hr. The
average NOX concentrations ranged from 233 to 292 ppmv,
resulting in emissions ranging from 3.46xlQ-2 to 5.03xlO'2
' Ib/hr. The 60-minute maximum NOx concentrations ranged
from 241 to 309 ppmv, resulting in emissions ranging from
3.59x10'2 to 5.34xlO"2 Ib/hr. The noncondensible vent gas
emissions for these parameters met the proposed regulatory
requirements for the LCTC site.
During the SITE demonstration, noncondensible vent
gas samples were collected and analyzed for VOCs, S VOCs,
and HC1. The following VOCs were detected at trace
levels: chloromethane; bromomethane; methylene chloride;
acetone; carbon disulfide; 2-butanone; 1,1,1-
trichloroethane; benzene; PCE; toluene; chlorobenzene;
and ethylbenzene. Acetone, 2-butanone, methylene chloride,
PCE, and toluene are critical analytes consistently present
in the feed waste. The critical VOC present at the highest
concentration in the noncondensible vent gas was PCE.
During the first and third unspiked test runs, the
concentration of PCE was less than the detection limits of
2.47 and 2.44 ppmv, respectively. During the second
unspiked run, PCE was present at 3.93 ppmv. During the
spiked test runs, the concentration of PCE ranged from 173
to 285 ppmv. The highest PCE concentration occurred
during the first spiked test run, which had the highest NOx,
SO2, CO, and TNMHC concentrations. All other VOCs
were present at concentrations less than 50 micrograms per
dry standard cubic meter (ug/dscm) and usually below
10 ug/dscm.
52
-------
Table B-9. Noncondensible Gas Average and Maximum Concentrations and Mass Emissions Rates
Contaminant
Unspiked Test Runs
Spiked Test Runs
Average3 CO (ppmv)
Average CO (Ib/hr)
60-minute RAb Maximum CO (ppmv)
60-minute RA Maximum CO (Ib/hr)
Average SO2 (ppmv)
Average SO2 (Ib/hr)
60-minute RA Maximum SO2 (ppmv)
60-minute RA Maximum SO2 (Ib/hr)
Average NOxd (ppmv)
Average NOxd (!b/hr)
60-minute RA Maximum NOxd (ppmv)
60-minute RA Maximum NOxd (Ib/hr)
Average TNMHC (ppmv)
Average TNMHC (Ib/hr)
60-minute RA Maximum TNMHC (ppmv)
60-minute RA Maximum TNMHC (Ib/hr)
1
21.4
0.00217
22.5
0.00228
°<2
<0.00049
2.40
0.00056
242
0.0404
253
0.0421
<2
<0.00033
<2
<0.00033
2
9.58
0.00110
11.1
0.00127
<2
<0.00055
<2
<0.00055
260
0.0491
275
0.0519
<2
<0.00037
<2
<0.00037
3
13.9
0.00151
15.4
0.00166
<2
<0.00052
<2
<0.00052
243
0.0432
254
0.0452
<2
<0.00035
<2
<0.00035
1
37.3
0.00392
40.8
0.00428
<2
<0.00051
3.49
0.00084
292
0.0503
309
0.0534
<2
<0.00037
3.95
0.00067
2
24.6
0.00244
26.5
0.00263
<2
<0.00048
2.87
0.00065
255
0.0417
280
0.0458
<2
<0.00032
3.54
0.00057
3
18.7
0.00169
19.8
0.00179
<2
<0.00043
<2
<0.00043
233
0.0346
241
0.0359
<2
<0.00029
2.53
0.00038
Notes:
a Average pollutant concentrations are calculated as the time-weighted average of each sampling period.
b Maximum pollutant concentrations are calculated as the maximum 60-minute rolling average (RA) concentration observed during
each sampling period.
c < = Analyte not detected at the detection limit shown.
d As a corrective action, a conservative correction factor of about 10 percent increase was applied to all NO CEM readings.
HC1 and some SVOCs were also detected. HC1 was
detected only during the second and third unspiked test
runs. During the second unspiked test run, the concentration
of HC1 was 48.5 ug/dscm. The HC1 concentration during
the third unspiked test run was 247 ug/dscm.
The following SVOCs were also present in the
noncondensible gas emissions at trace levels: phenol,
benzoic acid, naphthalene, bis-(2-ethylhexyl) phthalate,
and di-n-octylphthalate. During the unspiked test runs,
SVOCs were present in the noncondensible gas emissions
at the following concentrations: phenol from less than 1.4
to 1.6 ug/dscm, benzoic acid from less than 6.8 to
6.8 ug/dscm, bis-(2-ethylhexyl) phthalate at less than
1.4 ug/dscm, and di-n-octylphthalate from less than 1.4 to
3.9 ug/dscm. During the spiked test runs, phenol
concentrations ranged from less than 1.3 to 1.7 ug/dscm;
benzoic acid concentrations ranged from less than 6.7 to
31.8 ug/dscm, bis-(2-ethylhexyl) phthalate concentrations
ranged from less than 1.3 to 31.4 ug/dscm, and di-n-
octylphthalate concentrations ranged from less than 1.4 to
9 ug/dscm.
During the SITE demonstration, the TNMHC
concentration was also monitored by the CEM system.
During the unspiked test runs, the average and maximum
TNMHC concentration was less than the detection limit of
2 ppmv, resulting in emissions of less than 3.7xl(r4 Ib/hr.
During the spiked test runs the average THMHC
concentration was also less than the detection limit of 2
ppmv, resulting in emissions of less than 3.7xlO'4 Ib/hr.
However, during the spiked testruns, the maximum TNMHC
concentration ranged from 2.53 to 3.95 ppmv, resulting in
emissions ranging from 3.8xlO4 to 6.7xlCr4 Ib/hr.
The SITE demonstration noncondensible gas emissions
results indicate that increased contaminant loading during
the spiked test runs results in relatively small increases in
contaminant concentrations in the noncondensible vent
gas.
Toxicity Test Results
The acute toxicity of leachate feed waste and product
condensate was measured during each of the six test runs by
conducting forty-eight-hour, static nonrenewal acute
toxicity tests. Acute toxicity tests were conducted using
53
-------
respectively. No other samples were available for brine pH
measurement because of the small amount of brine wasted.
The pH of the product condensateranged from 3.83 to 4.27
during the unspiked test runs and from 4.02 to 4.22 during
the spiked test runs. The acidic pH of product condensate
could be attributed to the presence of HC1, CO2, and nitric
acid (HNO3). HC1 and CO2 are usually formed during the
catalytic oxidation of chlorinated organic compounds. HNO3
is formed from the hydrolysis of nitrogen dioxide (NO2).
Both potential factors are discussed below.
Analytical results showed that chloride concentration
in the product condensate was less than the detection limit
of 1 mg/L during both the unspiked and spiked test runs.
HC1 was detected in the noncondensible vent gas only
during the second and third unspiked runs at concentrations
of48.6 ug/dscmand247 ug/dscm, respectively. Therefore,
during the other SITE demonstration runs, HC1 that may
have formed in the catalytic oxidizer was effectively
removed in the caustic scrubber.
Also, CO2 is not likely present in the product condensate
in significant amounts because of the wet caustic scrubber
used before the condenser. Because of the elevated
temperature of the product condensate (about 125 °F) and
its low pH (about 4), any residual CO2 is expected to escape
through the noncondensible gas vent.
Analytical results show that nitrate was consistently
present in product condensate at concentrations ranging
from 0.23 to 0.37 mg/L during the unspiked test runs and
from 0.44 to 0.68 mg/L during the spiked test runs. Because
nitrate concentration in the feed waste was less than the
detection limit (see Nitrate), nitrate apparently originated
from the catalytic oxidation process. This possibility is
further discussed below.
Nitrate could have resulted from the hydrolysis of NO2.
Three sources of nitrogen may contribute to the formation
of NO2 during the oxidation reactions that take place in
PO*WW*ER™ catalytic oxidizer: (1) ammonia (NH3),
(2) air, which is an inevitable source in fuel-air reactions
and contains molecular nitrogen (N2) and oxygen (O2) in a
molar ratio of roughly 3.75 to l,and(3) cyanide (CN). The
bond energy of N=N in molecular nitrogen is much greater
than that of a C-N bond (Wark and Warner, 1981).
The potential formation pathways of NO2 from the
above-mentioned nitrogen sources are presented below.
However, the intermediate reaction steps are outside the
scope of this discussion and are not presented.
According to the discussion presented in Section B .3.1,
most of the ammonia present in the feed waste was
effectively evaporated and presumably oxidized in the
catalytic oxidizer. Ammonia oxidizes in air according to
the following reaction (Cotton and Wilkinson, 1976):
4NH3 + 3O2
2N2 + 6H2O
(B-2)
In the presence of a catalyst, some ammonia oxidizes
according to the following reaction:
4NH3 + 5O2 <-> 4NO + 6H2O
(B-3)
This reaction leads to the synthesis of nitrogen monoxide
(NO), which reacts with excess O2 to produce NO2, and the
mixed oxides that can be absorbed in water to form HNO
3
2ND + O <-> 2NO
3N02 + H2O <-» 2HN03 + NO
(B-4)
(B-5)
The formation of NO2 fromNO is rate limited. However,
the equilibrium rate constant for the oxidation of NO to
NO2 increases dramatically when the temperature decreases
in the presence of excess oxygen. Therefore, it is very likely
that the oxidation of NO to NO2 occurs instantly in the
condenser in the presence of O2.
HNO3 also results from NO2 produced from the
oxidation of nitrogen present in the air used as oxidation
fuel according to the reactions below (Wark and Warner,
1981):
N2 + O2 <-> 2NO
NO
(B-6)
(B-7)
Some of the cyanide originally present in feed waste is
evaporated and is oxidized in the catalytic oxidizer to form
CO2 and N2. In the presence of excess air, N2 oxidizes to
form NO2 according to equations B-6 and B-7. NO2 in turn
hydrolyzes in water to form HNO3 according to Equation B-
5.
The results show that NH3, N2, and CN are sources of
nitrogen, which oxidize in the catalytic oxidizer to form
58
-------
NO2, which in turn hydrolyzes in water to produce HNO3.
HNO3 is a strong acid that dissociates completely in water
according to the following reaction:
HNO3
(B-8)
Figure B-5 presents the product condensate pH values
predicted for the scenario discussed above for the formation
of HNO3. Figure B-5 also presents the median measured
pH values of the product condensate. The predicted and
measured pH values are similar and also follow the same
trend, which supports this scenario.
In order to produce product condensate with neutral
pH, an NO2 absorption step is required before the
condensation step. NO2 can be absorbed by water, hydroydde,
and carbonate solutions; sulfuric acid; organic solutions;
and molten alkali carbonates and hydroxides (Wark and
Warner, 1981).
Oil and Grease, TOX, and TOC
During the unspiked test runs, oil and grease
concentration in feed waste samples ranged from 550 to
730 mg/L and in brine samples from 330 to 1,400 mg/L,
resulting in an average concentration ratio of 1.5 to 1.
During the spiked test runs, oil and grease concentration
in feed waste samples ranged from 430 to 540 mg/L and in
brine samples from 1,800 to 2,200 mg/L, resulting in an
average concentration ratio of 4.2 to 1.
Because the TS concentration ratio is about 32 to 1, the
results indicate that some of the material contributing to oil
and grease is also removed during treatment of landfill
leachate in the PO* WW*ER™ system. During the unspiked
test runs, oil and grease removal efficiency ranged from 88
to 98 percent. During the spiked test runs, oil and grease
removal efficiency ranged from 76 to 78 percent.
During unspiked test runs, TOX concentration in feed
waste samples ranged from 144 to 155 mg/L; in brine
samples it ranged from 2,780 to 5,650 mg/L; and in product
condensate samples from 0.049 to 0.077 mg/L. Therefore,
TOX primarily concentrates in the brine, with an average
concentration ratio of 28 to 1. During the spiked test runs,
TOX concentration in feed waste samples ranged from 142
3 4
Run No.
•"
Predicted pH
Median pH Measured
Note: Runs 1 through 3 were conducted with unspiked landfill leachate, and
Runs 4 through 6 were conducted with spiked landfill leachate.
Figure B-5. Product condensate pH predicted and median pH measured during unspiked and spiked test runs.
59
-------
to 170 mg/L; in brine samples it ranged from 4,640 to
5,270 mg/L; and in product condensate samples it ranged
from 0.050 to 0.059 mg/L. Therefore, TOX primarily
concentrates in the brine, with an average concentration
ratio of 32 to 1.
The TOC concentration in the feed waste was
determined reliably only during the second unspiked test
run and during the first spiked test run. Therefore, only
these results are discussed.
During the unspiked test run, TOC in the feed waste
sample was 33,600 mg/L; in the brine sample it was
41,300 mg/L; and in the product condensate sample it was
less than 0.5 mg/L. The TOC evaporation efficiency was
about 94 percent.
During the spiked test run, TOC in the feed waste
sample was 34,500 mg/L; in the brine sample it was
51,800 mg/L; and in the product condensate sample it was
2.98 mg/L. The TOC evaporation efficiency was about 93
percent. The TOC evaporation efficiency did not change
significantly during the spiked test runs, which is when the
total contaminant loading increased.
TCLP VOCs and SVOCs
During the unspiked test runs, TCLP VOCs in brine
were less than the detection limits, which were less than
100 ug/L for most compounds. During the spiked test runs,
the TCLP VOCs were as follows: (1) acetone ranged from
140 to 180 ug/L, (2) methylene chloride ranged from 84 to
140 ug/L, (3) PCE ranged from 27 to 68 ug/L, and
(4) toluene ranged from 25 to 51 ug/L.
During the unspiked test runs, the only TCLP SVOC
detected in brine above the detection limit was benzoic
acid, which ranged from 110,000 to 340,000 ug/L. During
the spiked test runs, TCLP SVOCs were as follows: benzoic
acid ranged from 350,000 to 470,000 ug/L and bis-(2-
ethylhexyl) phthalate ranged from 6,200 to less than
10,000 ug/L.
The results show that total contaminant loading, which
increased during the spiked test runs, resulted in increased
concentrations of TCLP VOCs. Both TCLP VOCs and
SVOCs met RCRA TCLP standards.
B.4 References
Butler, J.N., 1964, Ionic Equilibrium a Mathematical
Approach. Addison-Wesley Publishing Company,
Inc., Boston, MA.
Cotton, F. A., and Wilkinson, G., 1976, Basic Inorganic
Chemistry. Wiley International Edition, John Wiley
& Sons, Inc., New York, NY.
Kleinbaum, D.G., and Kupper, L.L., Applied
Regression, 1978, Analysis and Other Multivariable
Methods. Duxbury Press, Boston, MA.
U.S. Environmental Protection Agency (EPA), 199la,
Technical Support Document for Water Quality
Based Toxics Control. EPA Office of Water,
Washington, D.C., EPA/505/2-90-001 (March).
EPA, 1991b, Methods for Measuring the Acute Toxicity
of Effluent and Receiving Waters to Freshwater and
Marine Organisms. EPA Office of Research and
Development, Washington, D.C., EPA/600/4-90/027
(September).
Wark, K., and Warner, C. F., 1981, Air Pollution: Its
Origin and Control. Second Edition, Harper & Row,
Publishers, New York, MY.
60
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Appendix C
Case Study Results
During the development of the PO*WW*ER™
technology, Chemical Waste Management, Inc. (CWM),
performed several test runs on various wastewaters. The
test runs were conducted at the PO*WW*ER™ pilot-scale
(pilot) plant located at the Lake Charles Treatment Center
(LCTC) site. The key performance parameters investigated
in these test runs were (1) concentration ratio, (2) boiling
point rise in the evaporator, (3) heat transfer coefficient,
(4) oxidation efficiency, and (5) product condensate quality.
The results of these test runs are summarized below as
individual case studies. However, results of the boiling
point rise in the evaporator and heat transfer coefficients
are not reported because CWM considers the information
proprietary.
In one case study, landfill leachate was treated in the
PO*WW*ER™ pilot plant. The landfill leachate contained
total organic carbon (TOC) at concentrations ranging from
980 to 4,000 milligrams per liter (mg/L) and total dissolved
solids (TDS) at 2 percent. The landfill leachate pH ranged
from 9 to 11. The results show that a concentration ratio of
40 to 1 was achieved. The brine contained 63 percent total
solids (TS) and TOC concentrations ranging from 15,000
to 42,000 mg/L. The pH of the product condensate ranged
from 6 to 9.
In a second case study, landfill leachate was also
treated in the PO*WW*ER™ pilot plant. The landfill
leachate contained TOC ranging from 730 to 3,100 mg/L
and TDS at 2 percent. The pH of the landfill leachate
ranged from 6.7 to 11.9. A concentration ratio of 40 to 1 was
achieved in the evaporator. The brine contained 49.5 percent
TS. All metals in the product condensate were at
concentrations below National Pollutant Discharge
Elimination System (NPDES) storm water discharge limits.
In a third case study, landfill leachate spiked with
ammonia was treated in the PO*WW*ER™ pilot plant.
The landfill leachate contained TOC ranging from 850 to
2,850 mg/L; ammonia ranging from 75 to 2,880 mg/L; and
TDS at 1.3 percent. The landfill leachate pH ranged from
9 to 11. A concentration ratio of 40 to 1 was achieved. The
brine contained 50 to 70 percent TS and 4 to 8.5 percent
TOC. The ammonia was effectively removed from the
brine. In the product condensate, both metals and organics
were removed to below NPDES storm water discharge
limits without further treatment.
In a fourth case study, landfill leachate spiked with
methanol was treated. The landfill leachate contained TOC
at 540 to 2,300 mg/L; methanol at 500 to 5,000 mg/L; and
TDS at 1.3 percent. The pH of the landfill leachate ranged
from 2.2 to 9.4. A concentration ratio of 40 to 1 was
achieved. The brine contained 46 to 52 percent TS. Methanol
was effectively evaporated and successfully oxidized. A
removal efficiency of 98 percent was achieved. Ammonia
concentration in the brine was less than the detection limit
of 5 mg/L.
In a fifth case study, landfill leachate spiked with
100 mg/L of each of the following chemicals was treated:
acetone, carbon disulfide, chlorobenzene, methanol, methyl
ethyl ketone, methylene chloride, nitrobenzene, toluene,
and trichloroethylene. TDS concentration was 1.3 percent
and pH ranged from 7.5 to 11.2. The results show that a
concentration ratio of 38 to 1 was achieved in the evaporator.
The brine contained 49 percent TS. All spiking chemicals
were effectively stripped from the brine. Only the nonvolatile
organics originally present in the landfill leachate remained.
Oxidation efficiencies of greater than 99 percent were
achieved for all spiking organics.
In a sixth case study, landfill leachate was spiked with
ammonia and methanol at concentrations of 0.1 percent
ammonia and 3 percent methanol, respectively. At pH 11,
the ammoniaevaporation efficiency was significantly higher
than at a pH ranging from 7 to 8. The methanol was
removed from the brine.
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In a seventh case study, lagoon water was treated in the
PO*WW*ER™ pilot plant. The lagoon water contained
TOC ranging from 280 to 1,500 mg/LandTDS at less than
1 percent. The lagoon pH was adjusted to 12. A
concentration ratio of 50 to 1 was achieved. The brine
contained 51 percent TS. The concentration of TOC in the
product condensate without oxidation ranged from 80 to
145 mg/L. The oxidation efficiency ranged from 90 to
97 percent.
In an eighth case study, fuels decant water was treated.
The fuels decant water contained 2 percent TOC and had
pH of 8. A concentration of 42 to 1 was achieved in the
evaporator. The TOC removal efficiency was greater than
99 percent.
In a ninth case study, well water spiked with cyanide at
139 mg/L was treated. The well water was acidified to
cause the release of hydrogen cyanide (HCN) gas. Cyanide
was evaporated from the brine to below detection limits.
The cyanide level in the product condensate was also below
detection limits.
In a tenth case study, oil emulsion wastewater was
treated in abench-scale system. The oil emulsion wastewater
contained 4,750 mg/L of TOC and 130 mg/L of ammonia;
had a pH of 8.8; and contained 14,000 mg/L TS. The TS
concentration ratio achieved was 35 to 1. The oxidized
product condensate contained 1.5 mg/L TOC, 0.1 mg/L
ammonia, and 55 mg/L chloride and had a pH of 3.1.
In an eleventh case study, wastewater contaminated
with nitrogen-containing organic compounds and cyanide
was treated in the PO*WW*ER™ pilot plant. The feed
waste pH was not adjusted. Antifoaming agent (EP-530)
was added on an as-needed basis. The feed waste processing
rate was 0.2 gallons per minute (gpm). The scrubber
operated with water alone. The feed waste had apH ranging
from 4 to 4.42; ammonia-nitrogen (NH3-N) ranging from
13,000 to 15,400 mg/L; sulfate ranging from 45,000 to
58,200 mg/L; TOC ranging from 20,500 to 36,300 mg/L;
cyanide ranging from 205 to 1,613 mg/L; and nitrogen-
containing organics content from 50 to 11,000 mg/L. The
brine had a pH of 4.31; 68,500 mg/1 NH3-N; sulfate at
306,300 mg/L; TOC at 84,000 mg/L; cyanide at 124 mg/L;
and nitrogen-containing organics ranging from 77 to
456 mg/L. The TS concentration hi the feed ranged from
8.57 to 10.1 percent. The TS in the brine ranged from 28 to
80 percent. The cyanide concentration in the product
condensate ranged from 0.2 to 51 mg/L, representing
removal efficiencies ranging from 96.9 to 99.99 percent.
Oxidation efficiencies ranged from 93.5 to 99.96 percent.
NH -N in product condensate ranged from less than 5 to
210 mg/L, representing removal efficiencies ranging from
91.6 to greater than 99.6 percent. Oxidation efficiencies
ranged from 83.8 to greater than 99.6 percent.
During the eleventh case study, the evaporator heat
exchanger heat transfer coefficients were also determined.
Under certain conditions, the physical-chemical
characteristics of the brine may have a fouling effect on the
heat transfer surfaces. As the TS concentration in the brine
increases, the solids in thetooiling brine provide a significant
scouring action and thus clean the evaporator surface.
Periodic system cleaning may be required to maintain high
heat transfer coefficients.
Based on the case studies discussed above, CWM
concludes thatproductcondensatefromthePO*WW*ER™
system meets stringent discharge standards and chronic
toxicity testing. The product condensate may be reused as
cooling tower make-up water, boiler make-up water, or
process feed water. In addition, CWM states that the
PO*WW*ER™ product condensate quality is as follows:
(1) TDS less than 25 mg/L, (2) TOC less than 10 mg/L,
(3) suspended solids less than 1 mg/L, and (4) hardness
less than 1 mg/L. According to CWM, the product
condensate quality that can be achieved by the
PO*WW*ER™ system exceeds requirements for typical
boiler make-up water and typical cooling tower make-up
water.
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