Technology Overview Report

TO-96-06

G W R TA C

SERIES

O

Ultraviolet/Oxidation Treatment

Prepared By:

Robert J. Trach
Ground-Water Remediation Technologies Analysis Center

November 1996

Prepared For: Ground-Water Remediation Technologies Analysis Center
615 William Pitt Way • Pittsburgh, PA 15238 • (412) 826-5511 • (800) 373-1973 Homepage: http://www.gwrtac.org • E-mail: gwrtac@netac.org

the listing of any technology. Environmental Protection Agency’s (EPA) Technology Innovation Office (TIO). GWRTAC is operated by the National Environmental Technology Applications Center (NETAC) in association with the University of Pittsburgh’s Environmental Engineering Program through a Cooperative Agreement with the U. They contain information gathered from a range of currently available sources. and personal communication with involved parties. No attempts are made to independently confirm or peer review the resources used. periodicals. i O Series: TO-96-06 Ultraviolet/Oxidation Treatment . or usefulness of the information. corporation. or fitness for a particular purpose. warranties as to the merchantability. NETAC. Established in 1995.FOREWORD About GWRTAC The Ground-Water Remediation Technologies Analysis Center (GWRTAC) is a national environmental technology transfer center that provides information on the use of innovative technologies to cleanup contaminated groundwater. Internet searches. company. accuracy. of facility in this report does not constitute endorsement. or recommendation by GWRTAC. GWRTAC wishes to acknowledge the support and encouragement received for the completion of this report from the EPA TIO. reports. warranty for completeness. express or implied. About “O” Series Reports This report is one of the GWRTAC “O” Series of reports developed by GWRTAC to provide a general overview and introduction to a groundwater-related remediation technology. including without limitation. including project documents. These overview reports are intended to provide a basic orientation to the technology. approval. Disclaimer GWRTAC makes no warranties. NETAC is an operating unit of the Center for Hazardous Materials Research and focuses on accelerating the development and commercial use of new environmental technologies.S. person. Moreover. or the EPA.

explosives such as TNT. mixed organic/radioactive waste and other organic compounds. depending on the flowrate under consideration. According to the information reviewed. halogenated solvents.e. pesticides.1-dichloroethane. no toxic by-products are generated in the reaction). Also. limited data relating to results of its use. A key advantage cited for UV/oxidation treatment technology is that it is a destruction process (i.ABSTRACT This technology summary report is an overview of information collected by GWRTAC on ultraviolet (UV)/oxidation treatment processes for the treatment of contaminated groundwater. Coli have reportedly been significantly reduced using UV/oxidation. and related references compiled during preparation of this report. UV/Oxidation has most often been used for contaminant concentrations in groundwater below 500 mg/L. are typically reduced by 96 percent. 1. organisms such as Salmonella and E. Also provided are a list of references cited. and HMX. UV/oxidation is a destruction process that oxidizes organic and explosive constituents in contaminated groundwater by the addition of strong oxidizers and irradiation with ultraviolet light. This document was prepared for distribution by the Groundwater Remediation Technology Analysis Center (GWRTAC). as opposed to air stripping or carbon adsorption. water and salts A wide variety of organic and explosive contaminants are susceptible to destruction by UV/oxidation. or in combination with patented treatment reactor design (in some cases). others. ozone (O3) and/or hydrogen peroxide (H2O2 ). vinyl chloride. GWRTAC is being operated by the National Environmental Technologies Application Center (NETAC). ethylbenzene. UV/oxidation processes can be configured in batch or continuous flow operations. toluene. Freon 113. for which contaminants are extracted and concentrated in a separate phase. including petroleum hydrocarbons. RDX. dioxins. The oxidation reactions are achieved through the synergistic action of high intensity UV light alone. Information provided includes an introduction to general principles and techniques associated with this technology. phenol. benzene. and xylenes (BTEX). The UV/oxidation process generates highly reactive hydroxyl radicals (OH•) that react with and destroy most organic chemical compounds. ii O Series: TO-96-06 Ultraviolet/Oxidation Treatment . such as. cyanide. advantages and limitations of use of this technology. If complete mineralization is achieved in the reaction. polychlorinated biphenyls. pentachlorophenol. the final products of the process are carbon dioxide. methyl tertiary butyl ether. Organics such as benzene can be treated to nondetectable levels. creosote. under a Cooperative Agreement with the EPA’s Technology Innovation Office (TIO). a general discussion of the applicability to groundwater remediation. glycols.

0 INTRODUCTION APPLICABILITY METHODOLOGY TECHNOLOGY PERFORMANCE 4.3 5.TABLE OF CONTENTS Section 1.0 7.0 3.0 CAVOX® (Magnum Water Technology) ULTROX ( A Division of ZIMPRO Environmental.0 4.0 8.0 6. Inc) Page 1 2 3 4 4 4 5 6 7 8 9 10 TECHNOLOGY ADVANTAGES TECHNOLOGY LIMITATIONS UV/OXIDATION GENERAL TREATMENT COST INFORMATION REFERENCES CITED RELATED REFERENCES iii O Series: TO-96-06 Ultraviolet/Oxidation Treatment . Inc) PEROX PURE ( Vulcan Peroxidation Systems.2 4.0 9.1 4.0 2.

4. which are highly reactive.1. subtraction reactions of a combination of both. the reaction by-products are carbon dioxide. Through direct photolysis. and are second only to fluorine in relative oxidation potential. 5). In most UV/oxidation processes. The hydroxyl radicals then attack the organic molecules resulting in the destruction of the parent organic compound. the hydroxyl radical reaction pathway can be one of addition reactions. high intensity UV radiation is combined with H2O2 to oxidize organic contaminants to carbon dioxide and water.0 INTRODUCTION UV/oxidation processes combine the use of ultraviolet light (UV) and chemical oxidants such as ozone (O3) and hydrogen peroxide (H2O2) to destroy organic contaminants in groundwater. With sufficient oxidation and exposure to UV energy. leading to the mineralized end products (3. water. Depending of the chemical structure of the organic molecules. 1 O Series: TO-96-06 Ultraviolet/Oxidation Treatment . The reaction is aided by the direct photolysis of the organic molecule by the UV light which can break or activate certain atomic bonds making the molecule more susceptible to oxidation. and the appropriate inorganic salt. the UV light reacts with the H2O2 to generate hydroxyl radicals (OH•).

aldehydes. glycols. phenols. TOC and most other forms of organic carbon. ethers.2.0 APPLICABILITY In general. PCB’s. BOD. pesticides. 2 O Series: TO-96-06 Ultraviolet/Oxidation Treatment . UV/oxidation is applicable at sites where groundwater is contaminated with volatile organic compounds (VOC’s). alcohols. ketones. aromatics. phthalates. PAH’s. ordnance compounds. COD. semi-VOC’s. dioxins.

bench-scale or pilot testing is required to evaluate necessary design requirements and system sizing. Proper equipment design is of paramount importance in achieving optimum UV/oxidation treatment performance for any application (3). and. and background COD levels. • • • • • Without the above design features.based automation features.0 METHODOLOGY Successful implementation of a UV/oxidation process depends on a number of factors. a configuration for minimum space requirements while maintaining serviceability and ease of upgrade for future expansion.3.or PLC. alkalinity. an oxidant dosing system which allows for multiple point dosing and continuous adjustment of the oxidant dosage. contaminant type and concentration. even at low flow rates. These factors include equipment design. Properly designed full-scale UV/oxidation equipment should at a minimum maintain the following engineering design features: • • meet all applicable manufacturing codes and OSHA safety requirements. can be effectively managed with proper pretreatment and/or utilization of proprietary catalytic additives. and oxidant type and dosage. water quality parameters. include a properly designed UV reactor which maximizes the utilization of available UV light energy and provides sufficient turbulent mixing. PC. Potential adverse effects from water quality parameters such as suspended solids. an effective and low maintenance automatic quartz tube and reactor chamber wall cleaner. iron. 3 O Series: TO-96-06 Ultraviolet/Oxidation Treatment . full-scale equipment can become operationally cumbersome and cost prohibitive (3). UV lamp/power turn-down capability while maintaining constant UV density. In most cases.

Pentachlorophenol. NETAC. Presented below are selected examples of UV/oxidation systems. It has been reported that UV/oxidation has been in full-scale groundwater treatment application for more than 12 years. without limitation or liability. ozone and UV radiation to destroy toxic organic compounds in groundwater. CHMR. No quartz tube scaling was observed (2. with over 30 systems installed.0 TECHNOLOGY PERFORMANCE Note: The following information is provided for informational purposes only. accuracy. 4. The process is designed to remove organic contaminants from groundwater without releasing volatile organic compounds into the atmosphere.1 CAVOX® (Magnum Water Technology) The CAVOX® process uses a synergistic combination of hydrodynamic cavitation and ultraviolet (UV) radiation (and where necessary. and the University of Pittsburgh) neither endorses nor in any way recommends the companies discussed below. ethylbenzene. This technology was accepted into the SITE Demonstration Program in the summer of 1992. TCA. 6). A field-scale demonstration was completed in March 1989 at the Lorentz Barrel and Drum Company site in San Jose. for the completeness. UV/oxidation processes are in operation in more than 150 full-scale remedial applications. depending on the waste stream (2. UV lamp output can be varied from 360 watts to over 20. Tests at a Superfund site treated leachate containing 15 different contaminants. the process successfully treated cyanide contamination. Off-gas from the treatment system passes through an ozone destruction Decompozon unit. The technology is fully commercial. 4. The process has also remediated a former gasoline station site over a 2-year period. since these conditions tend to lower the UV reactors’ efficiencies. the addition of hydrogen peroxide and metal catalysts) to oxidize contaminants in groundwater. Neither the cavitation chamber nor the UV lamp or hydrogen peroxide reaction generates toxic by-products or air emissions. Inc.9 percent for tricholorethene. Currently.4.2 ULTROX (A Division of ZIMPRO Environmental. A majority of these applications are for groundwater contaminated with petroleum products or with a variety of industrial solvent-related organics such as TCE. No effort has been made. GWRTAC (EPA TIO. The CAVOX® process achieved removal efficiencies of greater then 99. In other tests. or usefulness on the information provided. 4 O Series: TO-96-06 Ultraviolet/Oxidation Treatment . 6). GWRTAC makes no warranties. benzene.) The ULTROX process uses hydrogen peroxide. to verify the accuracy of the information provided.000 watts. and xylenes. expressed or otherwise. nor will be made. toluene. was reduced by 96 percent in one test series. California. The CAVOX® process cannot handle free product or highly turbid waste streams. which reduces ozone levels before air venting (8). or to assess the validity of any claims about the companies. DCE. their performance and cost information for sites utilizing UV/oxidation treatment technology (3). one of the major contaminants. and was demonstrated for four weeks in March 1993 at Edwards Air Force Base Site 16 in California. and vinyl chloride.

and dichloroethane to below analytical detection limits.) The PEROX PURE process uses UV radiation with hydrogen peroxide to destroy organic compounds in contaminated groundwater. A treatment system was demonstrated in September 1992 at the Lawrence Livermore National Laboratory (LLNL) Site 300 Superfund site in California. pesticides.3 PEROX PURE (Vulcan Peroxidation Systems. and other organic compounds at concentrations ranging from a few thousand milligrams per liter to one microgram per liter or lower. phenolics. The quartz tube wipers effectively cleaned the tubes and eliminated the interference caused by tube scaling (3. the PEROX PURE technology complied with California action levels and federal drinking water maximum contaminant levels at the 95 percent confidence level. polychlorinated biphenyls. tetrachloroethane. the treatment system can combine with air stripping. In some cases. 4. Canada. or biological treatment to optimize treatment results (9). with efficiencies greater than 99. VOC’s present in the air within the treatment system were not detected after passing through the Decompozon unit.9 percent. steam stripping. chloroform. Total organic carbon removal was low. Documented demonstration results are as follows: Contaminated groundwater treated by the system met regulatory standards at the appropriate parameter levels. The PEROX PURE technology treats groundwater contaminated with chlorinated solvents. This technology has been successfully applied to over 80 sites throughout the United States. The Decompozon unit reduced ozone to less than 0.Flow rates ranging from 5 gallons per minute to 1. Inc. For each organic contaminant. The PEROX PURE technology was accepted into the SITE Demonstration Program in April 1991. The demonstration test results showed that in most cases. 5 O Series: TO-96-06 Ultraviolet/Oxidation Treatment . fuel hydrocarbons. implying partial oxidation of organics without complete conversion to carbon dioxide and water (8).1 ppm. and Europe. the PEROX PURE technology reduced trichloroethane. 9).050 gpm are in use at various industries and site remediations.

UV radiation enhanced ozone treatment with hydrogen peroxide additions have been used in the successful treatment of particularly refractive substances such as ferricyanides and other chemical compounds (1. combustion by-products or contaminated absorbent for further disposal (1). • 6 O Series: TO-96-06 Ultraviolet/Oxidation Treatment .0 TECHNOLOGY ADVANTAGES Advantages offered by UV/oxidation processes in the treatment of contaminated groundwater include the following: • UV/O3/H2O2 treatment processes do not add to the pollutant load to the groundwater treatment system.). for example. This is in contrast to many of the existing end-of-pipe pollution abatement systems presently in use which merely transfer the waste from one medium to another leaving. 3.5.

• • • • • • • 7 O Series: TO-96-06 Ultraviolet/Oxidation Treatment . The aqueous stream to be treated by UV/oxidation should be relatively free of heavy metal ions (less than 10 mg/l) and insoluble oil or grease to minimize the potential for fouling of the UV quartz sleeves. Handling and storage of oxidizers require special material handling and safety precautions. Pretreatment of the aqueous stream may be required to minimize ongoing cleaning and maintenance of UV reactor and quartz sleeves.6. Excessive dosages of chemical additives may also act as a scavenger. The aqueous stream being treated must provide for good transmission of UV light. Possible air emission problems with ozone (O3) as the oxidant have been encountered in some UV/oxidation systems (7.0 TECHNOLOGY LIMITATIONS Limitations associated with UV/Oxidation processes involve the following: • In UV/oxidation using H2O2. Free radical scavengers can inhibit contaminant destruction efficiency. Costs may be higher than competing technologies because of energy requirements at some installations. 8). High alkalinity and carbonates in the groundwater may also cause fouling of both the reactor vessels and the UV quartz sleeves. the process is only efficient at rather low wavelengths (below 200 nm). High turbidity and high suspended solids concentration in the groundwater causes interferences.

Groundwater treatment system flowrate. • Magnum Water Technology estimates the cost of using the CAVOX® process to be half the cost of other advanced UV/oxidation systems. a comparison of various treatment strategies for groundwater contamination with TCE and other trace VOC’s (total VOC concentration = 7. Types and concentration of contaminants (as they effect oxidizer selection.0 mg/L) found that the capital costs of air stripping with vapor phase granular activated carbon were less than the Ultrox Process. 8 O Series: TO-96-06 Ultraviolet/Oxidation Treatment .40 to $5. and treatment time).10 and $10. UV light intensity. but the operation and maintenance costs of the Ultrox system were one-third to one-half of the alternatives (8).7.000 gallons treated (in 1994 dollars). oxidizer dosage. Because the process equipment has only one moving part.0 UV/OXIDATION GENERAL TREATMENT COST INFORMATION UV/oxidation treatment costs are generally between $0. Langelier’s Index of Scaling is shifted negative by the CAVOX® process (6).000 gallons. Requirements for pretreatment and/or posttreatment (7). such as activated carbon. The costs range from $0. it was found that this process was much less costly than alternatives.00 per 1. Direct operating and maintenance costs of the ULTROX Process are reported by the manufacturer for a number of applications. maintenance costs are minimal.00 per 1. The CAVOX® process does not exhibit the quartz scaling common with other UV equipment. In general. and substantially less expensive than carbon adsorption. Factors that influence the cost to implement UV/oxidation include: • • • Degree of contaminant destruction required. In one application.

Inc.gnet. available at: http://ci. (26 October 1994).edu/env/ site/democomp/ultrox.nttc. and Mattock. 9.8. Photochemical Oxidation: A Solution For the Mixed Waste Dilemma. K. Surface Water. Thorton. Technology Description of Perox Pure Chemical Oxidation Technology. David A.S. CAVOX® Process..inel.nttc. ULTROX.txt (30 October 1996). MAGNUM WATER TECHNOLOGY. Vulcan Peroxidation Systems. and Cheuvront. Demonstration Bulletin (EPA/540/MR93/524) published in May 1994.Demonstration Program.. in Chemistry and Industry Magazine.. 3. 1994 SITE Technology Profile . Halsted Press: A Division John Wiley & Sons. U. Ultraviolet Radiation and Oxidation.htm (21 October 1996). M.. W. and Leachate. 6. 1993 Annual Status Report.edu/env/site/democomp/magnwate. A Division of Zimpro Environmental.. Environmental Protection Agency. 9 O Series: TO-96-06 Ultraviolet/Oxidation Treatment . 2.nttc.gov/resources/research/ llrw/1995Conference/track2/pmt-05. 4. (1994). Ultraviolet (UV) Oxidation.0 REFERENCES CITED 1.org/gnet/ tech/techdb/site/democomp/magnwate.S. 1987.009\compgde. J. Technology Description of the ULTROX Process. also available at: http://www. Environmental Protection Agency.edu/env/site/democomp/vulcan. Prellberg. EX situ Physical/ Chemical Treatment For Groundwater. W.. 5. available at: http://www. Inc. Technology Description of the CAV-OX Process. 8. Completed Projects.449.txt (30 October 1996). available at: http://www. Magnum Water Technology.html (21 October 1996).txt (30 October 1996). available at http://www. Eilbeck. L.html (21 October 1996). 7. available at: MK01\RPT:02281012. Chemical Processes in Wastewater Treatment.. G. Rajeshwar.mond.org/9612/961216. U.. Photochemical Strategies For Abating Environmental Pollution. (27 October 1994). available at: http://www. J.

J.. 1992. 2. Odencrantz. U. ADVAN-OX Systems.llnl. G. R... King...mecom/ rem3. and Duggan. February 14-17.. Metzger.Emerging Technology Program.. G. Anaerobic Fluidized Bed Reactor. Vol.Completed Project. 26 No. ENVIRONMENTAL SCIENCE & TECHNOLOGY. 6.. 9. Kieber. Engbert. E. C. available at: http://www. Tobocman.. November 1994 .gnet. E. Above Ground Treatment of Contaminants—Off-gas Membrane Separation. available at: http://www. E. Metcalf & Eddy. SITE Technology Profile . Hernandez. MATRIX PHOTOCATALYTIC. Technology For the Nineties. R.... Vol. M. 1995.9. R. J. Environmental Protection Agency. 1996. 26. F.S. J. 27. 177-184. 4. and Pico. W. R. 2... pp. B. 10 O Series: TO-96-06 Ultraviolet/Oxidation Treatment . Zepp. available at: http://www. S. 1993.edu/VOC_Arid/VOCA_chap4.erd.. Glaze.. G.htm (21 October 1996). C. ENVIRONMENTAL SCIENCE & TECHNOLOGY. No. J. Faust. and Ferry.. S. H.4-Dinitrotoluene.1html (21 October 1996). pp. Lawrence Livermore National Laboratory. Economic Comparison of UV/ Oxidation. and Hoye. and Granular Activated Carbon for theTreatment of Propellant Production Wastewater Containing 2. Indirect Photoreduction of Aqueous Chromium (VI).0 RELATED REFERENCES 1. Bahowick. D. R. Fifth International Symposium and Principles and Practices Workshop at Vanderbilt University. Maloney. Kenneke. T.. 5. 3. R. L.gov/library/spec/122286. pp. Photocatylic Water Treatment.html (21 October 1996). available at: http:/www. 1992. ENVIRONMENTAL SCIENCE & TECHNOLOGY. Adaptive Remediaton Using Portable Treatment Units. S. INC.. 2. Kita. No. 307-312. Blake. Chlorinated Byproducts from the TiO2-Mediated Photodegradation of Trichloroethylene and Tetrachloroethylene in Water.. W. 7. Sinha. W.. Chemical Oxidation. G.htm (30 October 1996).org/gnet/tech/techdb/site/ emrgcomp/matrix1. 313-319.. Heiz.nttc. Hydroxyl Radical formation in Aqueous Reactions (pH 3-8) of Iron (II) with Hydrogen Peroxide: The Photo-Fenton Reaction. Vol. 1. and Holgné. Folsom. J. Advanced Oxidation... 8. L.

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