ihaerobic Suspended and984 —Chopler 10 Anoerobie Suspended end Atached Growsh Biological Treatment Processes Anaerobic treatment processes include anaerobic suspended growth, upflow and down- flow anaerobic attached growth, fluidized-bed attached growth, upflow anaerobic sludge blanket (UASB), anaerobic lagoons, and membrane separation anaerobic processes. Anaerobic suspended growth processes associated with biological phosphorus removal are discussed in Chap. 8. The anaerobic digestion of sludge is presented in Chap. 14. ‘The purpose of this chapter is to present process designs for other anaerobic treatment processes used to remove organic material from liquid streams. The various types of processes are described along with their typical design loadings and treatment process capabilities. Before considering the individual anaerobic treatment processes, it will be helpful to consider the rationale for the use of anaerobic treatment processes. 10-1 THE RATIONALE FOR ANAEROBIC TREATMENT ‘The rationale for and interest in the use of anaerobic treatment processes can be explained by considering the advantages and disadvantages of there processes. The principal advantages and disadvantages of anaerobic treatment are listed in Table 10-1 and are discussed below. Advantages of Anaerobic Treatment Processes Of the advantages cited in Table 10-1, energy considerations, lower biomass yield, fewer nutrients required, and higher volumetric loadings are examined further in the following discussion. Energy Considerations. Anaerobic processes may be net energy producers instead of energy users, as is the case for aerobic processes. An energy balance com- parison for a high-strength wastewater at 20°C is presented in Table 10-2. For the con- AAdvertoges ond tages an Gaadvonages of anaerobic processes compared to aerobic + Fewer nutrients required Processes *+ Methane production, « potential energy source + Smaller reactor volume required * Elimination of off gas cir pollution + Ropid response to substrate eddion after long periods without feeding Disadvantages + Longer startup fime fo develop necessary biomass inventory + May require alkalinity addition Secor rhe recent ‘with an aerobic treatment process to meet * Biological nirogen and phosphorus removal is not possible ‘+ Much more sensitive fo the adverse effect of lower temperatures on resicfion rates '* May be more susceptible to upsets due to toxic substances + Potentol for production of odors and corrosive gasesTable 10-2 Comparison of energy balance for aerobic and anaerobic processes for the treatment of a wastewater with the following choracteristics: wastewater flowrate = 100 m3/d; wastewater strength = 10 kg/m; and temperature = 20°C 10-1 The Rationale for Anoerobic Treatment 985, Valve, ki/d 395 Energy _ Rnasrebie Acration®® Methane produced? 12.5 x 10# Increase wastewater —2.1 x 10# temperature to 30°C Net energy, b/d 14x 108 1.9.x 108 Oxygen required = 0.8 kg/kg COD removed. * Aeration efficiency VhWh, Methane production = 0.35 m®/kg COD removed, Energy content of methane = 35,846 Kl/m? fot O°C ond, 1 ot 1.52 kg O,/kWh ond 3600 KI = ditions given in Table 10-2, the aerobic process requires 1.9 x 10° ki/d. On the other hand, the anaerobic process produces a total of 12.5 X 10° kI/d. Of the total energy pro- duced anaerobically, about 2.1 X 10° ki/d is required to raise the temperature of the ‘wastewater from 20 to 30°C, the low end of the mesophilic temperature range, a more desirable temperature for anaerobic treatment. Thus, the potential net energy produc- tion that can be achieved with anaerobic treatment is on the order of 10.4 X 10° kI/d, or about 5 times the energy required for aerobic treatment. ‘The wastewater strength is important for comparing energy balances for aerobic and anaerobic processes, where the wastewater temperature must be increased. With the same assumptions used to gerierate the energy balance presented in Table 10-2, both the aerobic and anaerobic processes would require the same amount of energy input if the wastewater biodegradable COD concentration is 1270 mg/L. At lower COD con- centrations, the aerobic process requires less energy. However, heat recovery from the anaerobic effluent stream can modify these values. Further, the lower biomass yield dis- cussed below is still a major advantage offered by anaerobic treatment. Lower Biomass Yield. Because the energetics of anaerobic processes result in lower biomass production by a factor of about 6 to 8 times, sludge processing attd dis- posal costs are reduced greatly. The major environmental and economic issues associ ated with the reuse and disposal of biomass produced from aerobic processes are dis- cussed in Chap. 14. The fact that less sludge is produced in anaerobic treatment is a significant advantage over aerobic treatment. Fewer Nutrients Required. Many industrial wastewaters lack sufficient nutri- ents to support aerobic growth. The cost for nutrient addition is much less for anaero- bic processes because less biomass is produced. Higher Volumetric Loadings. Anaerobic processes generally have higher vol- umetric organic loads than aerobic processes, so smaller reactor volumes and less space ‘may be required for treatment. Organic loading rates of 3.2 to 32 kg COD/m?-d may be986 ‘Chapter 10 Anaerobic Suspended ond Attached Growth Biological Treatment Processes 10-2 used for anaerobic processes, compared to 0.5 to 3.2 kg COD/m*d for aerobic pro- cesses (Speece, 1996). Disadvantages of Anaerobic Treatment Processes Potential disadvantages also exist for anaerobic processes as reported in Table 10-1 Operational considerations, the need for alkalinity addition, and the need for further treatment are highlighted further in the following discussion. Operational Considerations. ‘The major concerns with anaerobic processes are their longer start-up time (months for anaerobic versus days for aerobic processes), their sensitivity to possible toxic compounds, operational stability, the potential for odor production, and corrosiveness of the digester gas. However, with proper wastewater characterization and process design these problems can be avoided and/or managed, Need for Alkalinity Addition. ‘The most significant negative factor that can affect the economics of anaerobic versus aerobic treatment is the possible need to add alkalinity. Alkalinity concentrations of 2000 to 3000 mg/L as CaCO, may be needed in anaerobic processes to maintain an acceptable pH with the high gas phase CO, con- centration. If this amount of alkalinity is not available in the influent wastewater or can- not be produced by the degradation of proteins and amino acid, a significant cost may be incurred to purchase alkalinity, which can affect the overall economics of the process. Need for Further Treatment. Anaerobic processes can also be followed by aerobic processes for effluent polishing to utilize the benefits of both processes. Series reactors of anaerobic-aerobic processes have been shown feasible for treating munici pal wastewaters in warmer climates resulting in lower energy requirements and less sludge production (Goncalves and Avaujo, 1999; Garuti et al., 1992). Summary Assessment In general, for municipal wastewaters with lower concentrations of biodegradable COD, lower temperatures, higher effluent quality needs, and nutrient removal require- ments, aerobic processes are favored at present. For industrial wastewaters with much higher biodegradable COD concentrations and elevated temperatures, anaerobic processes may be more economical. In the future, as more is learned about anaerobic ‘treatment processes, itis anticipated that their use will become more widespread in a variety of applications. GENERAL DESIGN CONSIDERATIONS FOR ANAEROBIC TREATMENT PROCESSES ‘The type of wastewater and its characteristics are important in the evaluation and design of anaerobic processes. The characteristics presented here apply to the suspended ‘growth, sludge blanket, attached growth, and membrane separation anaerobic processes presented in subsequent sections. Important factors and wastewater characteristics that need to be considered in the evaluation of anaerobic processes for wastewater treatment are discussed below.Table 10-3 Examples of types of wastewater treated by anaerobic processes 10-2 Goneral Design Considerations for Anaerobic Treatment Processes 9B7- Alcohol distillation Landfill leachate Breweries Pharmaceuticals Chemical manufoctring Pulp ond poper Dairy ond cheese processing Slaughterhouse ond meatpacking Domestic wastewater Soft drink beverages Fish and seafood processing __Sugor processing Characteristics of the Wastewater A wide variety of wastewaters have been treated by anaerobic processes including those reported in Table 10-3. Anaerobic processes are attractive, especially for high strength ‘and warm temperature wastewaters because: (1) aeration is not required, thus saving ‘energy cost, and (2) the low amount of solids generated. Food processing and distillery wastewaters, for example, can have COD concentrations ranging from 3000 to 30,000 mg/L. Other considerations that may apply to different wastewater sources are the presence of potential toxic streams, flow variations, inorganic concentrations, and sea- sonal load variations. Anaerobic processes are capable of responding quickly to waste- water feed after long periods without substrate addition, In some cases with warmer cli- ‘mates, anaerobic treatment has also been considered for municipal wastewater treatment. Flow and Loading Variations. Wide variations in influent flow and organic, loads can upset the balance between acid fermentation and methanogenesis in anaero- bic processes. For soluble, easily degradable substrates, such as sugars and soluble starches, the acidogenic reactions can be much faster at high loadings and may increase the reactor volatile fatty acids (VFA) and hydrogen concentrations and depress the pH. Higher hydrogen concentrations can inhibit propionic and butyric acid conversion. The lower pH can inhibit methanogenesis. Flow equalization or additional capacity must be provided to meet peak flow and loading conditions. Organic Concentration and Temperature. As discussed in Sec. 10-1, the wastewater strength and temperature greatly affect the economics and feasibility of anaerobic treatment. Reactor temperatures of 25 to 35°C are generally preferred to sup- port more optimal biological reaction rates and to provide more stable treatment. Gen- erally, COD concentrations greater than 1500 to 2000 mg/L are needed to produce suf- ficient quantities of methane to heat the wastewater without an external fuel source. At 1300 mg/L COD or less, aerobic treatment may be the preferred selection. ‘Anaerobic treatment can be applied at lower temperatures and has been sustained at 10 to 20°C in suspended and attached growth reactors. At the lower temperatures, slower reaction rates occur and longer SRT, larger reactor volumes, and lower organic COD loadings are needed (Banik and Dague, 1996; Collins et al., 1998). Further, at temperatures in the range from 10 to 20°C, the degradation of long chain fatty acids is often rate limiting. If long chain fatty acids accumulate, foaming may occur in the reac- tor. When higher SRTs are needed, the solids loss in an anaerobic reactor can become a critical limiting factor. Anaerobic reactors generally produce more dispersed, less flocculent solids than aerobic systems, with effluent TSS concentrations for suspended988 —Chopter 10. Anaerobic Suspended ond Atached Growth Biological Treokment Processes ‘growth processes in the 100 to 200 mg/L range. For dilute wastewaters, the effluent TSS concentration will limit the possible SRT of the process and treatment potential. Either a lower treatment performance occurs or itis necessary to operate the reactor at a higher temperature. Thus, the method used to retain solids in the anaerobic reactor is impor- tant in the overall process design and performance. Fraction of Nondissolved Organic Material. The composition of the ‘wastewater in terms of its particulate and soluble fractions affects the type of anaerobic reactor selected and its design. Wastewaters with high solids concentrations are treated more appropriately in suspended growth reactors than by upflow or downflow attached growth processes. Where greater conversion of particulate organic matter is required, longer SRT values may be needed if solids hydrolysis is the rate-limiting step as com- pared to acid fermentation or methanogenesis in anaerobic treatment. Wastewater Alkalinity. With the high CO, content (typically in the range from 30 to 50 percent) in the gas produced in anaerobic treatment, alkalinity concentrations in the range from 2000 to 4000 mg/L. as CaCO, are typically required to maintain the pH at or near neutral. The level of alkalinity needed is seldom available in the influent wastewater, but may be generated in some cases by the degradation of protein and amino acids (e.g., meatpacking wastewaters). The requirement to purchase chemicals for pH control can have a significant impact on the economics of anaerobic treatment. The relationship between pH and alkalinity as outlined in Appendix F is controlled. by the bicarbonate chemistry as follows: (HCO; ][H"] THco,) 7 & (10-1) where K,, = first acid dissociation constant, which is a function of ionic strength and temperature ‘The carbonic acid (HCO) concentration is determined using Henry's law (Eq. (2-46)] and the partial pressure of the CO, in the atmosphere above the water. Pr HPe A (2-46) where x, = mole fraction of gas in water, mole gas/mole water mole gas (n,) ~ mole gas (n,) + mole water (n,.) P; = total pressure, usually 1.0 atm atm (mole gas/mole air) : (mole gas/mole water) P, = mole fraction of gas in air, mole gas /mole of. H = Henry's law constant, Once the carbonic acid concentration is known, the bicarbonate (HCO3) alkalinity needed to maintain the required pH can be estimated, The use of the above equations is illustrated in Example 10-110-2 General Design Considerations for Anaerobic Treatment Processes 989 EXAMPLE 10-1 pH and Alkalinity in an Anaerobic Process Determine the alkalinity required in kg CaCO,/d to maintain a pH value of 7.0 in an anaerobic suspended growth process at 35°C, with a 30 percent CO, content in the gas above the water. The influent waste- water flowrate is 2000 m4, the alkalinity is 400 mg/L. as CaCO;, and no alkalinity pro- ducing substances are present. At 35°C, Henry’s constant for CO,, computed using Eq. (248) and the data given in Table 2-8, is 2092 atm and the value of K,, is 4.85 X 10-? mole/L (see Table F-2 in Appendix F). Solution 1, Determine the concentration of HCO} required to maintain the pH at or near a value of 7.0. ‘a. Deteimine the concentration of H,CO, using Eq. (2-47). Py _ (latm)(0.30) _ 4 Huo, = aia = 1434 x 10 : “ Because liter of water contains $5.6 mole (1000 g/(18 g/mole)], the mole fraction of H,CO, is equal to mole gas (n,) 7H. = mmole gas (n,) + mole water (n,) [H2CO5} tue [H3CO,] + [55.6 mole/L} ae Because the number of moles of dissolved gas in alter of waters much Jess than the number of moles of water, {H,003] ~ (1.434 x 10*)[55.6 mole/L] ~ 7.97 10°? b. Determine the concentration of HCO} required {0 maintain the pH ator near 2 Value of 7.0 using Eq. (10-1). a ee [4.85 % 10°? mole/LI[7.97 x 10°! mole/L} [10-7 mole/L] i ‘ 0.0387 mole/L os ee oe HCO}; = (0.0387 mole/L)(61 g/mole)(10° mg/g) = 2361 ‘mg/L 2. Determine the amount ca lean required per day. ee (2.361 g/Ly "Gi g/eq) my _ (100 g/mole) 2 2 1.434 x 10" {HCo5] = Equivalents of HCO3 0.0387 eq/L, 1eq CaCO, = = 50.8 CaCOs/eq Alkalinity as CaCO; = (0.0387 eq/L) (50 g/eq)(10° mg/g), ire s . = 1925 mg/L as CaCO, e990 Chapter 10 Anaerobic Suspended ond Attached Growth Biological Teeotment Processes Alkalinity needed = (1935 — 400) mg/L = 1535 mg/L as CaCO, a Daily alkalinity addition = (1535 g/m*) (2000 m*/d) (1 kg/10° g) = 3070 kg/d Z Comment Based on the results of the above analysis, it is clear that a large quantity of alkalinity may be required and, as a consequence, a significant cost can be incurred, Because the addition of lime for alkalinity can lead to the formation of precipitates, form of alkalinity to be added is sodium bicarbonate. ‘The results of similar calculations to those presented in Example 10-1 for differ- cent temperatures and gas phase CO, concentrations are reported in Table 10-4. The data presented in Table 10-4 were derived using the carbonate equilibrium constants given in Table 6-16 in Chap. 6 and Henry's constants derived from the data given in Table 2-8 in Chap. 2. The values presented in Table 10-4 can be used to estimate the alka- linity requirements. For wastewaters with a higher total dissolved solids concentration and ionic strength, the alkalinity requirements will generally be much greater. Nutrients. Though anaerobic processes produce less sludge and thus require less nitrogen and phosphorus for biomass growth, many industrial wastewaters may lack sufficient nutrients. Thus, the addition of nitrogen and/or phosphorus may be needed. Depending on the characteristics of the substrate and the SRT value, typical nutrient requirements for nitrogen, phosphorus, and sulfur are in the range from 10 to 13, 2 to 2.6, and 1 to 2 mg per 100 mg of biomass, respectively. ‘The values for nitrogen and phosphorus are consistent with the values for these constituents estimated on the basis of the composition of the cell biomass (see Sec. 8-3 in Chap. 8). Further, to maintain ‘maximum methanogenic activity, liquid phase concentrations of nitrogen, phosphorus, and sulfur on the order of 50, 10, and 5 mg/L, respectively are desirable (Speece, 1996). Macronutrients. ‘The importance of trace metals to stimulate methanogenic activ- ity has been noted and discussed by Speece (1996). The recommended requirements for iron, cobalt, nickel, and zinc are 0.02, 0.004, 0.003, and 0.02 mg/g acetate produced, Table 10-4 Estimated minimum alkalinity as CaCO, required to maintain 20 900 51050 1200 1400 ape Oe 25 1100 ‘1300 15001700 od 20 1300 1400-—«1800.-—2100 percent carbon 35 1500 1800 2100 2400 dioxide during 40 1700 210024002800 onaerobic digestionTable 10-5 Toxic and inhibitory inorganic ‘compounds of concern for ‘anaerobic processes? 10-2 General Design Considerations for Anoerobic Treatment Processes 991 respectively. Examples of increased anaerobic activity were noted after trace additions of iron, nickel, or cobalt, The exact amounts of trace nutrients needed can vary for dif- ferent wastewaters, and thus trial approaches are used to assess their benefit for anaer- bic processes with high VFA concentrations. A recommended dose of trace metals per liter of reactor volume is 1.0 mg FeCl,, 0.1 mg CoCly, 0.1 mg NiCl,, and 0.1 ZnCl, Inorganic and Organic Toxic Compounds. Proper analysis and treatat ity studies are needed to assure that a chronic toxicity does not exist for wastewater treated by anaerobic processes. At the same time, the presence of a toxic substance does not mean the process cannot function. Some toxic compounds inhibit anaerobic methanogenic reaction rates, but with a high biomass inventory and low enough load- ing, the process can be sustained. Toxic and inhibitory inorganic and organic com- pounds of concern for anaerobic processes are presented in Tables 10-5 and 10-6, respectively. Acclimatization to toxic concentrations has also been shown (Speece, 1996). Pre~ treatment steps may be used to remove the toxic constituents, and, in some cases, phase separation can prevent toxicity problems by providing for degradation of the toxic con- stituents in the acid phase, before exposure of the more sensitive methanogenic bacte- ria to the toxic constituents (Lettinga and Hulshoff Pol, 1991). Solids Retention Time The solids retention time is a fundamental design and operating parameter for all anaer- obic processes. In general, SRT values greater than 20 d are needed for anaerol processes at 30°C for effective treatment performance, with much higher SRT values at Tower temperatures. Substance Ne « cor Mat “Ammonirnirogen NH ‘Sulfide, S?- Copper, Cu* 0.5 (soluble) 50-70 (total) ‘Chromium, Cr{Vi) 3.0 (soluble) 200-250 (total) ‘Chromium, Crflll) 180-420 (total) 2.0 {soluble} Nickel, Ni?* 30.0 (total) Zine, Zn?* 1.0 (soluble) ‘From Parkin and Owen (1986).992 Chapter 10 Anaerobic Suspended and Attoched Growth Biological Treatment Processes Table 10-6 Toxic and inhibitory ‘organic compounds ‘of concern for anaerobic processes? Concentration “resulting in "50 percent reduction Sle activity, mit on on 02 19 24 26 Ethyl benzer 32 Acrylonitrile 4 '3-Chlorol-1,2-propanediol ‘ Crotonaldehyde 65 2-Chloropropionic acid 8 Vinyl acetate 8 ‘Acetaldehyde 10 Ethyl acetate nv Acrlic ocid 12 ‘Catechol 24 Phenol 2% Anil % Resorcinol 2» Propanol 90 fom Parkin and Owen (1986) 'mM = millimole, Expected Methane Gas Production Higher-strength wastewaters will produce a greater amount of methane per volume of liquid treated to provide a relatively higher amount of energy to raise the liquid temper- ature, if needed. As derived in Sec. 7-12 in Chap. 7, the amount of methane (CH,) pro- duced per unit of COD converted under anaerobic conditions is equal to 0.35 L CHy/g COD at standard conditions (0°C and 1 atm). The quantity of methane at other than stan- dard conditions is determined by using the universal gas law [Eq. (2-44)] to determine the volume of gas occupied by one mole of CH, at the temperature in question. (2-44) volume occupied by the gas, L moles of gas, mole10-2 General Design Considerations for Anaerobic Treatment Processes 993 R = universal gas law constant, 0.082057 atm-L/moleK T= temperature, K (273.15 + °C) P = absolute pressure, atm ‘Thus, at 35°C, the volume occupied by one mole of CH, is (mole) (0.082057 atm )[(273.15 + 35)K] = 25.29L 1.0 atm Because the COD of one mole of CH, is equal to 64 g, the amount of CH, produced per unit of COD converted under anaerobic conditions at 35°C is equal to 0.40 L as deter- mined below. 25.29 L(64 g COD/mole CH.) = 0.40 L CHJ/g COD If the composition of the waste is known, and neglecting the amount of the constituent used for cell synthesis, the following relationship, first proposed by Buswell and Boruff (1932) and subsequently extended by Sykes (2000), can be used to estimate the amount of methane (CH,), carbon dioxide (CO,), ammonia (NH,), and hydrogen sulfide (H,S) that will be produced under anaerobic conditions. »y wie z C\H,O,N,S, + (0 Fost at 2).0-+ w +S)en, + (g-2 + (10-2) ‘The gaseous ammonia (NH,) that is formed will react with the carbon dioxide to form the ammonium ion and bicarbonate according to the following relationship. + 2)co, + yNH + 2H,S NH, + H,0 + CO, NH + HCO; (10-3) ‘The reaction given by Eq. (10-3) is representative of the formation of alkalinity urider anaerobic conditions, due to the conversion of organic compounds containing proteins (ie., nitrogen). The expected mole fractions of methane, carbon dioxide, and hydrogen sulfide are given by the following three expressions, respectively. In general, the mole fraction of hydrogen sulfide will be somewhat less because of metal complexation/pre- cipitation. 4u—wt 2 - Sy +2 Se Ce 110-4) Seo, 8 -y +2) (o-4) Av + w— 2x — Sy - 2z Sox 8 —y +2) (10-5) z er (10-6) Sins = As noted previously, the percentage of carbon dioxide in the gas can be as high as 50 percent. For carbohydrate and starch wastes, alkalinity will be a problem,994 Chapter 10 Anaerobic Suspended and Attached Growth Biclogical Treatment Processes Treatment Efficiency Needed Anaerobic treatment processes are capable of high COD conversion efficiency to meth- ane with minimal biomass production, At SRT values greater than 20 to 50d, maximum conversion of solids may occur at temperatures above 25°C. However, high-effluent suspended solids (50 to 200 mg/l.) are common for anaerobic processes. Without pilot- plant studies and extreme measures to control effluent suspended solids concentrations, such as chemical flocculation or membrane separation, anaerobic processes alone can- not be depended on to achieve secondary treatment levels. Some form of aerobic treat- ment would be necessary to provide effluent polishing, either attached growth or sus- pended growth processes. For high-strength wastewaters the combination of anaerobic and aerobic treatment can be economical (Obayashi et al., 1981). Sulfide Production Oxidized sulfur compounds, such as sulfate, sulfite, and thiosulfate, may be present in significant concentrations in various industrial wastewaters and to some degree in municipal wastewaters. These compounds éan serve as electron acceptors for sulfate~ reducing bacteria, which consume organic compounds in the anaerobic reactor and pro- duce hydrogen sulfide (H,S). For example, using methanol as the electron donor and an f, value of 0.05 (see Sec. 7-4 in Chap. 7), the overall reaction for the reduction of sul- fate to H,S can be illustrated by the following expression: 0.119S02> + 0.167CH,OH + 0.010CO, + 0.003NHj + 0.003HCO; + 0.178H* = 0.003C,H,NO, + 0.060H,S + 0.060HS~ + 0.3311,0 (10-7) From Eq. (10-7), the amount of COD used for sulfate reduction is 0.89 g COD/g sul- fate, which is in the range of 0.67 g COD/g sulfate reduced as reported by Arceivala (1998). The higher value is due to the lower biomass yield coefficient associated with methanol oxidation. Based on the following stoichiometry for H,S oxidation, 2 moles of oxygen are required per mole of HS, as was the case for methane oxidation, H,S + 20, > H,S0, (10-8) Thus, the amount of H,S produced per unit COD is the same as that for methane (0.40 L H,S/g COD used at 35°C). Hydrogen sulfide is malodorous and corrosive to metals. Combustion products formed from sulfur oxidation are considered air pollutants. In contrast to methane, HS is highly soluble in water, with a solubility of 2650 mg/L at 35°C, for example. ‘The concentration of oxidized sulfur compounds in the influent wastewater to an anaerobic treatment process is important, as high concentrations can have a negative effect on anaerobic treatment. Sulfate-reducing bacteria compete with the methano- genic bacteria for COD and thus can decrease the amount of methane gas production. While low concentrations of sulfide (less than 20 mg/L) are needed for optimal meth- anogenic activity, higher concentrations can be toxic (Speece, 1996). Methanogenic activity has been decreased by 50 percent or more at HS concentrations ranging from 50 to 250 mg/L. (Arceivala, 1998). A comprehensive evaluation of the dynamics of com- petition betwéen sulfate-reducing and methanogenic bacteria and toxicity effects is given in Maillacheruvu et al. (1993).