United States Environmental Protection Agency Municipal Environmental Researc Laboratory Cincinnati OH 45268 / Research and Development EPA-600/S2-82-046 August 1982 Project Summary Pilot Scale Evaluation of Biological Activated Carbon for the Removal of THM Precursors William H. Glaze, James L. Wallace, Kenneth L. Oickson, Douglas P. Wilcox, K. R. Johansson, Eichin Chang, Arthur W. Busch, Bobby G. Scalf, Roger K. Noack, and David P. Smith, Jr. This project evaluates a method for the removal of trihalomethane (THM) pre- cursors from surface water sources. The site of the project. Cross Lake in Shreve- port, Louisiana, represents sources in the southern United States with high concentrations of THM precursors. In one phase of the project, a pilot plant was operated for 80 weeks to test the combination of ozone and granular acti- vated carbon (GAC) for THM precursor removal. An important objective of the pilot study was to investigate the possi- bility of microbiological degradation of precursors In the GAC columns and the effect of preozonation on this process. The combination of ozone and GAC is sometimes referred to as biological activated carbon (BAG). Analysis of the pilot plant data shows microbiological activity to be a significant contributor to the removal process for total organic carbon (TOO and trihalo- methane formation potential (THMFP) in GAC columns under the conditions tested. In the initial stages, the removal mechanism appears to be primarily adsorption. But, after 50 x 103 bed volumes of water have been processed, only microbiological removal remains. During the Interim period, both adsorp- tion and microblal processes appear to contribute to TOC and THMFP removal. Comparison of costs associated with the addition of GAC and BAG to traditional water treatment plants of 100-, 10-, and 1 -mgd capacities shows that, for the conditions of this study, the addition of ozone was not cost effective in extend- ing the time between reactivations of the GAC. In a second phase of the project, studies were conducted at Shreveport's Amiss treatment plant complex to define the extent of their THM problem. Results there showed high concentrations of THM's. Alternatives for lowering the concentrations to less than 0.10 mg/L Include addition of GAC and conversion to chloramination. In either case, some type of oxidant will be required for man- ganese control. This Project Summary was developed by EPA's Municipal Environmental Re- search Laboratory, Cincinnati, OH, to announce key findings of the research project that Is fuHy documented In a sep- arate report of the same title (see Project Report ordering information at back). Introduction Following the passage of the Safe Drinking Water Act by the U.S. Congress in 1974, the U.S. Environmental Protec- tion Agency (EPA) proceeded to act under the authority of this legislation to promulgate National Interim Primary Drinking Water Standards. These stan- dards set maximum contaminant limits for several inorganic elements and com- ------- pounds, organic pesticides, radioactivity levels, and microbiological parameters. Furthermore, they were applied to essen- tially all water supplies serving popula- tions in the United States. Recently, these standards were amended to include the establishment of maximum contami- nant levels for four organic substances known as the trihalomethanes (THM's). Trihalomethanes are known to be formed by the disinfection process that uses chlorine, the most disinfectant used in water treatment in the United States. The reaction of chlorine with naturally occurring organic compounds, called THM precursors, is well known to result in the formation of a variety of chlori- nated organic compounds, including the THM's. Four THM's are now regulated by the requirements of the Safe Drinking Water Act—chloroform, bromodichloro- methane, dibromochloromethane, and bromoform. As of November 29, 1981, the combined levels of these four THM's were not permitted to exceed 0.10 mg/L in water supplies serving populations greater than 75,000. This limit will apply to all water systems serving populations of 10,000 to 75,000 as of November 29, 1983. Trihalomethane limits are expected to be extended to cover essen- tially all U.S. water supplies in the future. Methods for controlling THM levels include modification of the disinfection process (including substitution of an alternative disinfectant), removal of THM's once formed by advanced treat- ment processes including adsorption and aeration, and removal of THM pre- cursors before the use of chlorine as a disinfectant. Among the treatment methods avail- able for the removal of THM precursors, GAC adsorption has emerged as the most promising alternative. Various studies have shown that GAC can re- move natural organic compounds from groundwaters and surface waters with great efficiency. The principal disadvan- tage of the use of GAC is the need to replace or reactivate it periodically to renew its adsorption capabilities. The relatively high cost of this process has discouraged its wide application as a water treatment process. A recent dis- covery suggests the possibility of ex- tending the lifetime of GAC columns for water treatment. This discovery involves the recognition that microbiological pro- cesses occur on GAC much as they do in trickling filters used for wastewater treatment. The fact that bacterial colo- nies proliferate on GAC has been known for some time, but only recently has it been appreciated that this presence may be used beneficially to remove organic substances from the influent water. Naturally occurring organic compounds in water supplies (sometimes referred to as aquatic humus) are relatively refrac- tory materials, and their biological degra- dation is usually a relatively slow process. Thus in the application of microbiological processes to GAC, various workers have proposed to increase the biodegrada- bility of these substances by the applica- tion of an oxidation pretreatment process. Ozone has been the most favored oxidant for these purposes. The combination of ozone followed by GAC for the removal of organic substances in water has been termed the biological activated carbon (BAC) process. Proponents of this pro- cess contend that BAC can extend the life of granular activated carbon columns almost indefinitely, provided microbio- logical colonies can be maintained. Treat- ment efficiencies during such extended lifetimes ordinarily do not equal those of fresh carbon, but the proponents of the BAC process contend that longer empty bed contact times in the carbon can be used to obtain desirable treatment effi- ciencies. According to this view, the increased capital costs associated with longer GAC contact times and the addi- tion of an oxidant are more than offset by the avoidance of GAC reactivation or replacement costs. Most of the data on which these con- clusions are based have evolved from the application of ozone and GAC adsorp- tion in European waterworks. Few cases have been studied in which the perfor- mance criteria match those required by U.S. drinking water regulations; that is to say, the operational criteria used in Europe to evaluate the BAC process do not correspond to the minimization of the THM's. For this reason, EPA is spon- soring several pilotscale investigations to evaluate GAC adsorption for the direct removal of THM's or THM precursors. This report describes the results of one such investigation. The study was conducted in the southern part of the United States in Shreveport, Louisiana. The test water is taken from Cross Lake, the principal water supply for the city of Shreveport. Cross Lake contains relatively high levels of THM precursors, but it is relatively uncontaminated by anthropo- genic sources. A pilot study was carried out to evaluate GAC adsorption with and without preozonation as a means for re- moving these high levels of precursors. A variety of chemical and microbiological parameters were measured in the pilot plant and in associated laboratory exper- iments to obtain more information on the physical, chemical, and biological pro- cesses that occur in GAC filters. Parallel to this effort, studies were taking place in the Thomas L. Amiss treatment plant of the city of Shreveport to help municipal authorities develop approaches for mini- mizing trihalomethanes in the city water supply. Conclusions The pilot-scale portion of this study has shown that GAC columns may be operated for extended lifetimes by opti- mizing the physical and microbiological processes that occur in these columns. With the trihalomethane formation po- tential (THMFP) as the principal analytical criterion, water from a southern U.S. reservoir has been treated effectively for a period of 1 year using a combination of alum flocculation, multi-media filtration and 24 min of contact with Filtrasorb- 400* GAC. During this period the THMFP of the product water was less than the 0.10 mg/L maximum contaminant level except on two occasions. Engineering and cost analyses have been conducted for the addition of GAC adsorption with a 24 min contact time to an existing plant using the same reservoir as the water source. The analysis shows that costs of this additional treatment are not unreasonable. For 1-, 10-, and 100-mgd plants, additional costs per 1000 gal were computed to be $0.33, $0.20, and $0.13, respectively. The addition of ozone before GAC adsorption may extend the lifetime of GAC columns, presumably by direct oxi- dative reduction of THMFP and by en- couragement of microbiological removal mechanisms in the GAC columns. Under the conditions used in this study, the addition of ozone was not cost effective in extending the time between reactiva- tions of the GAC. An analysis of the chemical and micro- biological data from the pilot study sug- gests that the following conclusions may be drawn regarding the pilot plant operation. 1. Traditional treatment consisting of alum flocculation, sedimentation and mixed-media filtration results •Mention of trade names or commercial products! does not constitute endorsement or recommenda-" tion for use. ------- in the removal of 30% to 40% THMFP, with more efficient removal occurring in the summer periods. Except for occasional periods in the winter months, the product of this treatment has THMFP values well in excess of 0.10 mg/L. 2. Oxidation with ozone is not an effec- tive method per se for the removal of THMFP. For the relatively low doses (applied ozone dose range = 2.0 to 6.3 mg/L) used in this work, 5% to 20% destruction of THMFP was observed. When combined with traditional treatment, ozonation produced water that met the 0.10 mg/L THMFP criterion only 20% of the time. 3. The addition of GAC columns to traditional treatment is an effective means for controlling THM precur- sor levels. Various data point to the following mechanisms as those re- sponsible for the sustained removal of natural organics from the GAC columns: (a) Physical Adsorption. This pro- cess is prevalent during the early stages of operation and shows the expected decline in rate as macropore sites become satu- rated and the process is limited by pore diffusion. But as other workers have shown, the ca- pacity of GAC for natural organ- ics is very large if the micropore capacity is fully utilized. (b) Microbiological Degradation. This process is temperature depen- dent and accounted for the re- moval of approximately 0.21 moles of carbon/m3 GAC-hr (or approximately 0.13 mg THMFP/ m3 GAC-hr) during its optimum period. These two processes combine to yield a sustained period of THMFP removal. During the early stages, the removal is largely due to physical adsorption; but in the latter part of the study, microbiologi- cal processes appear to prevail. The in- termediate period (referred to by some as a pseudo-steady-state period) is apparently due to a combination of the two processes. 4. Results of the parallel study at the T. L. Amiss plant are incomplete, but they suggest the following conclu- sions: (a) Instantaneous THM concentra- tions in the Amiss distribution system are extremely high by Federal standards, ranging ap- proximately from 0.10 mg/L in the winter to 0.35 mg/L in the summer. (b)A substantial fraction of the THM's is produced upon pre- chlorination—a common practice at the Amiss plant. During sum- mer months, concentrations above 0.10 mg/L often occur after a detention time of only 10 to 20 min beyond prechlorina- tion. (c) Elimination of prechlorination results in more effective coagu- lation of precursors in the sedi- mentation basins. The result is not only lower THM concentra- tions leaving the Amiss plant, but lower ultimate values in the distribution system. (d) Control of pH levels after lime stabilization is an ineffective means of minimizing THM for- mation. (e) Control of chlorination practice alone cannot solve the THM problem in systems such as the Amiss plant. Other measures that may be used are GAC ad- sorption (as indicated by the pilot study) and substitution of an alternative disinfectant for chlorine. (f) If chloramination is to be used in place of chlorination, it must be substituted throughout the plant, at least during summer periods. The control of primary producers in the plant basins, taste and odor problems, and manganese levels in the product water then become management problems that will require renewed atten- tion. Recommendations This project has shown that biologically enhanced removal of THM precursors is possible. Full-scale studies should be en- couraged to optimize the process. Par- ticular attention should be given to the development of regimes for partial reac- tivation of the GAC beds in some type of rotary fashion so that biological and physical adsorption can be coordinated and the entire process optimized. The full report was submitted in fulfill- ment of Cooperative Agreement No. CR- 806157 by The University of Texas at Dallas, Richardson, Texas, under the sponsorship of the U.S. Environmental Protection Agency. William H. Glaze is with the University of Texas at Dallas, Richardson, TX 75080; James L. Wallace, Kenneth L. Dickson, Douglas P. Wilcox, K. R. Johansson. Eichin Chang, and Arthur W. Busch are with North Texas State University, Denton, TX 76203; Bobby G. Scalf, Roger K. Noack, and David P. Smith, Jr., are with Henningson, Durham and Richardson, Dallas, TX 75230. J. Keith Cars well is the EPA Project Officer (see below). The complete report, entitled "Pilot Scale Evaluation of Biological Activated Carbon for the Removal of THM Precursors," (Order No. PB 82-230 301; Cost: $16.50, 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 « U.S QOVERNMEm-pRIMTINO OFFICE: 1»K-559-017/0767 ------- 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 Third-Class Bulk Rate LOU \fi REGION V EPA LIBRARIAN 230 S DEARBORN ST CHICAGO IL 60604 ------- |