United States Environmental Protection Agency Municipal Environmental Research, Laboratory Cincinnati OH 45268 Research and Development EPA-600/S2-82-020 May 1982 Project Summary Biological Processes in the Treatment of Municipal Water Supplies R. G. Rice, C. M. Robson, G. W. Miller, J. C. Clark, and W. Kuhn Studies were conducted of a Euro- pean water treatment technique that appears to produce high quality drink- ing water without the synthesis of hal- ogenated organic materials during the water treatment process. This biologi- cal treatment technique involves the sequential application of chemical oxidation (usually by means of ozone), rapid media filtration, optional reaera- tion, and granular activated carbon (GAC) adsorption. The use of this biologically enhanced, granular activated carbon (BEGAC) technology was studied in several European water treatment plants to determine its advantages and disadvantages for use in the Uni- ted States. Seven European water works were visited where chemical preoxidation is followed by rapid media filtration and GAC adsorption. The process is still under develop- ment in these European water works, but results to date are positive. They indicate that in those water works using GAC adsorption of dissolved organic materials, incorporation of chemical preoxidation with small amounts of ozone (1 to 2 mg/L) can result in extending the life of GAC adsorbers by factors of 4 to 6 before reactivation is required. The process can be used for the biological removal of ammonia from raw water supplies and has replaced breakpoint chlorina- tion in several European plants. Such replacement eliminates the prechlori- nation step, which in turn eliminates the formation of significant quantities of halogenated organics. Results to date indicate that after biological equilibrium is attained in GAC adsorbers, 25 to 35 percent of the influent dissolved organic carbon is removed from solution biologically. This Project Summary was devel- oped by EPA's Municipal Environ- mental Research Laboratory, Cincinnati, OH, to announce key find- ings of the research project that is fully documented in a separate report of the same title (see Project Report ordering information at back). Introduction This project resulted from the current need to learn as much as possible about methods for controlling organic con- taminants in drinking water. The pres- ent project is an outgrowth of an earlier study on the state of the art of ozone and chlorine dioxide technologies in munici- pal water treatment (Public Technology, Inc. 1976. An Assessment of Ozone and Chlorine Dioxide Technologies for Treatment of Municipal Water Supp- lies. EPA-600/2-78-147. U.S. Environ- mental Protection Agency, Cincinnati, Ohio). During the course of this 4-week, onsite survey of European water treat- ment facilities, the site team observed the use of a biological treatment tech- nique in France, the Federal Republic of Germany, and Switzerland that is not ------- currently practiced in the United States. This technique involves the deliberate promotion of aerobic biological growths on filter media (sand, anthracite) and GAC media (columns or beds) for pur- poses of nitrification and of removing organic chemicals. The aerobic biologi- cal activity appears to be enhanced by an oxidation step applied before the activated carbon treatment. Such preoxidation steps frequently involve the addition of ozone. Evidence obtained from numerous European pilot-plant studies and from several full-scale operating plants in Europe supported the claim that a prop- erly designed and operated combina- tion of ozone and GAC unit processes enhances the removal of some types of organic chemicals and can reduce the frequency of regeneration of the acti- vated carbon media, depending on the reactivation criteria. The latter charac- teristic is vital, since one of the primary concerns of public water supply sys- tems regarding the use of GAC (in addi- tion to the high capital cost) is the relatively high cost associated with fre- quent reactivation. Furthermore, this biological process replaces breakpoint chlorination and eliminates the genera- tion of chlorinated organic materials during the early stages of the water treatment processes. Some experiences with the BEGAC process were described briefly in the earlier report (EPA-600/2-78-147), but additional details were required to establish this method as a viable means of enhancing treatment effectiveness and reducing operating costs. This study was therefore undertaken to acquire information on the following specific subject areas: Determining design criteria used for BEGAC systems in Europe; Determining mechanisms by which BEGAC systems operate; Determining microbiological as- pects of BEGAC systems; Gathering field operational and cost data on BEGAC systems; Quantification of technical and cost benefits of BEGAC systems; Determining changes in U.S. treat- ment plant designs required for retrofitting BEGAC systems into existing plants. Site Visits After consulting with leading Euro- pean water treatment authorities dur- ing early 1978, the site visit team conducted visits to selected European facilities during June 1978. The prim- ary questions to be answered were: 1. Is BEGAC effective for removal of organic chemicals, and if so, under what conditions? 2. Is BEGAC an effective replace- ment process for ammonia remo- val by breakpoint chlorination, and if so, under what conditions? 3. How and why does the BEGAC process achieve its effectiveness? 4. Is a preoxidation step necessary? If so, must the preoxidant always be ozone? 5. Can the added capital and operat- ing costs of an ozonation or other preoxidant system be offset by the increase in operating time before the GAC must be regenerated? 6. Is BEGAC bacteriologically safe to use for drinking water treatment? 7. What pretreatment and post- treatment steps are made neces- sary when BEGAC is incorporated into a drinking water treatment system? 8. Does biological regeneration of the GAC truly occur, and if so, to what extent? Not all of these questions were an- swered, since the BEGAC process still is being studied and developed by Euro- pean water treatment specialists. But answers to some of these questions were obtained by conducting a review of the published literature and a 3-week site visitation of the following facilities: 1. Operational drinking water treat- ment plants using granular acti- vated carbon facilities designed to promote biological growth, 2. Research institutes and universi- ties conducting studies on the BEGAC process, and 3. Activated carbon and ozone sys- tems manufacturers in Western Europe during June 1978. The scope of this report could not be confined to ozone/GAC treatment sys- tems alone, however. Early in the study, it became apparent that Europeans use many biological processes in the treat- ment of drinking water and that BEGAC appeared to be a more advanced treat- ment system based on earlier operating experiences with other biological pro- cesses. The scope of this final report was thus extended to include discus- sion of other European biological drink- ing water treatment methods. But because of the complex problems of removing organic chemicals, our pri- mary emphasis during the study phase remained on ozone and GAC systems. Seven European drinking water treat- ment plants were visited that currently use ozone/GAC processing. Tabfe 1 summarizes pertinent parameters deal- ing with the status of BEGAC process- ing at each plant. In most of these plants, criteria for reactivating the GAC have not yet been specified. Literature Search and Review Many papers were obtained from per- sons and institutions visited during the June 1978 survey. In addition, two technical conferences contributed timely, pertinent papers. One confer- ence (Oxidation Techniques in Water Treatment) was held in Karlsruhe, Fed- eral Republic of Germany during Sep- tember 1978, and the other (Adsorption From the Aqueous Phase) was part of the 176th Annual Meeting of the Amer- ican Chemical Society held in Miami Beach, Florida, also in September 1978. A search of the published literature yielded many applicable papers. Results of this literature review are interwoven throughout the report. Results 1. The primary responsibility of a drinking water producer is to provide drinking water safe from harmful pathogenic microorganisms. To this end, water supply utilities of the United States have sought to preclude the growth of all types of microorganisms within the water treatment system. But in other countries, some water utilities intentionally incorporate biological pro- cesses into their water treatment sys- tems to reduce the levels of dissolved organics and still maintain the microbi- ologically safe quality of the finished waters 2. The treatment of drinking water by the application of biological processes is not new. Biological activity is one of the processes in the slow sand filter, which was a key treatment step of early water treatment facilities, but which is generally considered obsolete in con- temporary U.S. practice. But biological treatment in many forms is an impor- tant process in many European drinking water treatment systems. Examples of biological treatment of drinking water include the following. River sand bank filtration Surface storage (reservoirs) Gravity clarification Coarse media biological reactors Fluidized bed nitrification Biologically active filter media ------- Table 1. Water Treatment Plants Visited That Use Ozone/GAC Treatment Plant la Chapelle Morsang-sur- Seine Kralingen Dohne Holthausen & Flehe Hardhof (Lengg & Moos) Location Rouen, France Villabe, France Rotter- dam, The Nether- lands Miilheim, FRG Dussel- dorf. FRG Zurich, Switzer- land Type of Date Ozone Primary Purpose Date GAC Plant Installed of Ozone Installed Municipally owned. privately operated Privately owned & operated Municipal waterworks Municipal waterworks Municipal waterworks Municipal waterworks 1977 Preozonation for Mn + organics oxidation; post- GAC ozonation for disinfection 1970 Organics oxida- tion + disinfec- tion 1977 Disinfection + organics oxida- tion April Preozonation for 1977 flocculation aid; secondary ozona- tion for disinfec- tion 1954 Fe & Mn oxidation + organics oxida- tion 1975 Disinfection/, viruses, organics oxidation 1977 ca. 1975 1977 Nov. 1977 mid- 1960's 1975 Frequency of Reactivation BEG AC operating since Jan. 1977 without reacti- vation BE GAC pilot unit in operation since 1977. Ran 1 yr w/o reactivation GAC had not operated long enough to have developed bio- logical activity BEG AC system operating since Nov. 1977 with- out reactiva- tion 5 to 6 months every 2 to 3 years GAC Reactivation Criteria Not yet defined Not yet defined Breakthrough of THM's Not yet established. Old process (which included breakpoint chlorination): break- through of roc/. When TOC1 adsorption front reaches lower GAC quadrants When COD levels in GAC effluents increase Biologically enhanced granular activated carbon (BEGAC) Ground passage of treated water 3. The incorporation of biological treatment steps into water treatment processes offers the following prospec- tive benefits in water treatment: Reduction in the level of dissolved organic materials Lower oxidant (chlorine, chlorine dioxide, or ozone) demand Reduced operational costs Reduced levels of bacterial re- growths in distribution systems 4. BEGAC can be defined as the sequential unit processes (Figure 1) consisting of: a. Oxygenation by aeration, oxygen injection, or chemical oxidation b. Sand, anthracite, or multi-media filtration c. Optional reoxygenationorreaera- tion and d. GAC adsorption This combination of three pro- cesses (chemical oxidation, adsorption, and biochemical oxi- dation) can remove ammonia and some (but not all) soluble organic substances from drinking water. 5. Dissolved organic materials in drink- ing water can be classified as follows: 1. Biodegradable, adsorbable by GAC 2. Biodegradable, nonadsorbable by GAC 3. Nonbiodegradable, adsorbable by GAC 4. Nonbiodegradable, nonadsor- bable by GAC Although these categories are simpli- fied for the purpose of discussing treat- ment of dilute water streams, they provide a framework for postulating mechanisms by which BEGAC probably functions. 6. Both the filtration media and GAC provide supports for the biomass, which uses soluble organics and ammonia as substrates. The application of strong oxidants such as ozone to a raw water stream being treated can change the chemical nature of the dissolved organic materials. Strong oxidants can convert some (but rarely all) nonbiode- gradable materials into biodegradable materials. Biochemical decomposition of organic nutrients adsorbed by the high surface area in GAC has been claimed to restore a portion of the sites to again become available for adsorp- tion. Thus one objective of preoxidation is to couple adsorption with biological degradation. 7. The porous structure of GAC pre- sents an ideal medium for proliferation of attached biological growth (fixed film biological growth). Both biomass and substrate are retained by the GACthe biomass on the outer surface, and adsorbed organics in the micropores. 8. Bacteria are too large to fit into the micropores; thus they become at- tached to GAC media only on the outer surfaces and in the larger macropores near the outer surface that are suffi- ciently large to house them. As a result, only 1 to 2 percent of the total surface area available for adsorption of dis- solved organics is used by the bacteria. This amount of bacterial growth is not sufficient to interfere with normal adsorption processes unless it becomes too dense and physically blocks the pas- sages from the outer surfaces into the micropores. 9. Bacterial growths build up rapidly in GAC media. Those species that con- sume mainly carbonaceous organic materials appear to attain their maxi- mum concentrations within 24 to 48 hr after virgin or reactivated GAC is placed in service. Nitrogen-converting bacteria take longer to build up to their equili- brium concentrations (30 to 90 days), ------- Water or Wastewater Aeration, Oxygenation or Oxidation Inert Medium Filtration Aeration or Oxygenation GAC Contactor Post-Treatment Figure 1. Block diagram of the Bio- logic a I Activated Carbon Process. but low levels of ammonia are con- verted to nitrate within a few days after fresh or reactivated GAC is placed into service. 10. Operational water treatment plants using BEGAC processes demon- strate that regeneration cycles of GAC adsorbers can be extended if a large proportion of the soluble organics entering the GAC system are biode- gradable and if essential conditions (like minimum dissolved oxygen levels) are maintained. No single BEGAC system design is as yet universally accepted. So even though data exist from a number of plants, the design engineer will still have to establish design criteria for BEGAC processing in pilot plant stud- ies. Clearly, however, designs can be developed under certain conditions to take advantage of extended GAC opera- tional life by enhanced biological activ- ity on both the filter media and the GAC. 11. Extension of the operational life of GAC adsorbers depends on the crite- ria set for reactivation. In European drinking water treatment plants using chemical preoxidation followed by GAC adsorption, these reactivation criteria have not yet been standaidized from plant to plant. In those plants that have been in operation the longest using ozone followed by GAC (the three Dus- setdorf plants), GAC is reactivated when the chlorinated organics adsorp- tion front (measured as dissolved organic chlorine) reaches the lower quadrant of the GAC. Other European plants monitor levels of dissolved organic carbon, permanganate demand, UV absorption, turbidity, and taste and odor m the GAC effluents. If any of these levels increase suddenly and significantly, the GAC may be reactivated. 12. Several microbiological studies have demonstrated that the predomi- nant microorganisms in the GAC media and in the water leaving the BEGAC system are typical soil and water bacte- ria. Pathogenic bacteria entering a properly designed and operated BEGAC system have been shown to be unable to compete with the predominant microorganisms present, and therefore the pathogenic species die off. Further study is required to confirm the pres- ence or absence of harmful endotoxins. Only low dosages of post-disinfectant have been shown to be necessary to achieve the prerequisite levels of bacte- riological quality of the treated water being discharged to the water distribu- tion system. 13. Decisions to install GAC should not be based solely on the benefits to be gained from BEGAC. Rather, the deci- sion to use GAC to remove specific organic materials should be made first. Once the decision to install GAC has been made, careful consideration should be given to extending the opera- tional life and improving the overall organic removal process performance of the GAC by enhancing biological activity in this medium. 14. Reactivation criteria for BEGAC should be the same as those for GAC, and they should be based on the partic- ular dissolved organic materials pres- ent in the raw water. 15. BEGAC processing will not pro- vide any significant advantages over GAC adsorption when the dissolved organics to be removed are nonbiode- gradable and cannot be made biode- gradable even by chemical oxidation with ozone. Exemplary materials of this type include many of the halogenated organic compounds produced prechlor- ination of raw waters. 16. BEGAC systems have replaced breakpoint chlorination processes in several new and old European drinking water treatment plants. This process change has provided the advantage of avoiding production of halogenated organic materials during the early stages of the treatment process. Once halogenated organics have been syn- thesized, they can be removed by GAC adsorption, but only with short bed or column lifetimes. In addition, replace- ment of prechlorination with BEGAC systems has also produced higher qual- ity finished water with respect to dis- solved organics, ammonia, turbidity levels, and post-disinfectant (chlorine, chlorine dioxide, or ozone) demands. 17. In European water treatment plants, chemical preoxidation with ozone applied before sand, anthracite, or dual-media filtration units followed by GAC adsorption has resulted in extending the times between back- washing in each medium by a factor of about 2. Nevertheless, authorities at the Dohne plant in Mulheim have found it necessary to backwash biologically operating filters and GAC adsorbers at no greater intervals than 3 days to ensure the absence of nematodes. 18. One older European plant (the Dohne plant in Mulheim, Federal Republic of Germany) replaced break- point chlorination with BEGAC in 1977 at no increase in annual operating costs, including allowances for annual- ized capital costs. 19. When retrofitting BEGAC sys- tems into existing drinking water treat- ment plants as post-adsorbers (after sand or other media filtration), provision should be made to incorporate air scouring into the backwash cycles of both the filtration and GAC media. 20. Biodegradable organic" materials generally are polar and less tightly held by GAC upon adsorption. Nonbiode- gradable organics tend to be nonpolar (for example, many of the halogenated organic compounds produced upon prechlorination). Some of these nonpo- lar, nonbiodegradable organic mate- rials can be adsorbed to a higherdegree and held more tightly by GAC. Because of these differences, some halogenated organic compounds are able to displace less strongly adsorbed polar organic materials from GAC surfaces by the process of desorption. As a result, even 4 ------- though a BEGAC adsorber may be oper- ating at biological equilibrium and may appear to be saturated with respect to adsorption of biodegradable organic materials, it may still be capable of adsorbing nonpolar, nonbiodegradable organics that are present. In such instances, reactivation could be delayed until the nonpolar, nonbiodegradable materials begin to break through the GAC medium. 21. A screening test can be con- ducted to determine whether BEGAC adsorption will benefit a specific raw water supply. This test shows the amount of biodegradation that can occur in the raw water supply. A sample of the raw water is ozonized with low utilized ozone dosages (1 to 10 mg/L), and the amount of biodegradable mate- rial present is compared with that of the nonozonized raw water. If oxidation of the organic materials with ozone does not increase the rate of biodegradation, then it can be concluded that BEGAC wi 11 not show a ny adva ntages over GAC for that water supply. On the other hand, if the rate of biodegradation is increased by low-level ozonation, bio- logical enhancement of GAC should provide performance advantages. The extent of such improvements must be determined for each raw water supply to assess whether these process improvements can justify the increased costs for chemical preoxidation, preox- ygenation, or preaeration. 22. Ozonation costs have been esti- mated for a hypothetical 50-mgd drink- ing water treatment plant that has installed GAC columns with empty bed contact times of 9 min and reactivation times of once every 2 months. If preoxi- dation with 2 mg/L of applied ozone dosage will extend the GAC reactivation time to 6 months, the costs associated with installing the required ozonation equipment are balanced by the savings resulting from GAC reactivation. Further extension of the GAC reactiva- tion time (to 2 and 3 years, as currently occurs in some European drinking water treatment plants using BAC pro- cesses) will provide additional savings in operating costs. Recommendations 1. Various biological water treat- ment processes should be investigated as to their applicability for the treatment of drinking water. Investigations should include the use of GAC as well as other adsorptive or inert media. Such studies should be conducted on systems that do not use initial breakpoint chlorination and, ideally, on systems with no prechlorination. 2. The nonpathogenic nature of bac- teria should be confirmed in biologically active GAC media and in the effluents from such media. 3. The endotoxins produced by these microorganisms should be identified, and their toxicological significance should be determined. 4. Studies should be conducted to confirm the nature of the operative mechanisms occurring with BEGAC (i.e., adsorption/desorption versus apparent biological regeneration). 5. More detailed operating informa- tion should be obtained at selected European plants, including the Rouen plant in France, the Dohne, Dusseldorf, and Schierstein plants in the Federal Republic of Germany, and the Kralingen plant in Rotterdam, the Netherlands. Such information would include char- acteristics of influent and BEGAC media effluents about TOC, COD, DOC, UV absorption, TOC1, ammonia, etc. The specific parameters used at each operating plant should be determined to ascertain when the GAC must be reactivated. 6. Determinations should be made of the operational costs and treatment consequences of doing away with prechlorination in drinking water treat- ment plants (for example, modification of filter bottoms to allowforairscouring and the necessity for more frequent backwashing). Prototype U.S. plants should be operated in both modes (chlorination versus preoxidation by other means) over a 1 -year cycle (minimum). 7. A variety of raw water sources should be screened to determine the applicability of biological treatment pro- cesses. Raw waters should be catego- rized according to the biodegradability of their organic components before and after preoxidation. 8. European water treatment operat- ing practices should be evaluated with- out regard to the use of GAC with preoxidation. 9. Biological processes for nitrifica- tion of ammonia should be demon- strated as possible replacements for breakpoint chlorination. 10. The use of oxidants other than ozone should be studied for the preoxi- dation step. Candidate oxidants other than ozone include H20z, KMn04, UV (plus air or oxygen), C102 (free of excess chlorine), and NHzC1 (free of excess chlorine). 11. Studies should be made of fac- tors affecting bacterial breakthrough in BEGAC adsorbers. (Such break- throughs have been reported in stud- ies conducted at the Schierstein, Federal Republic of Germany drinking water treatment plant after 3 years of use.) Bacterial monitoring should pos- sibly be considered for BEGAC systems. The full report was submitted in ful- fillment of Grant No. R-804385-01 by Public Technology, Incorporated, under the sponsorship of the U.S. Environ- mental Protection Agency. ------- R. G. Rice is with Jacobs Engineering Group, Washington, DC 20006; C. M. Robson is with Purdue University. Lafayette, IN 47907; G. W. Miller is with Public Technology, Inc., Washington, DC 20036; J. C. Clark is with Temple, Barker & Sloan, Wellesley Hills, MA 02181; and W. Kuhn is with the Universit'at Karlsruhe, Karlsruhe, Fed, Rep. Germany. J. Keith Carswell is the EPA Project Officer (see below). The complete report, entitled "Biological Processes in the Treatment of Municipal Water Supplies,"(Order No. PB 82-199 704; Cost: $31.50, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Municipal Environmental Research Laboratory U.S. Environmental Protection Agency Cincinnati. OH 45268 1982-559-092/3410 ------- United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 Postage and Fees Paid Environmental Protection Agency EPA 335 Official Business Penalty for Private Use $300 RETURN POSTAGE GUARANTEED PS 0000329 U S ENVIR PRUTECTION AGENCY KEGIQN 5 LIBRARY 250 S DEARBORN STREET CHICAGO IL 60604 ------- |