5.5 Biochemical Oxygen Demand 199 urban oe - hydrologic modification (which includes such things as flow reg~ ulation and dredging) are also very important. Because more than one pollutant or process may impact a given lake or river, the percentages in Figures 5.7 and 5.8 add up to more than 100 percent 5.5 Biochemical Oxygen Demand a Surface water is obviously highly susceptible to contamination. It has historically been the most convenient sewer for industry and municipalities alike, while at the same time, it is the source of the majority of our water for all purposes. One partic- ular category of pollutants, oxygen-demanding wastes, has been such a pervasive surface-water problem, affecting both moving water and still water, that it will be given special attention. When biodegradable organic matter is released into a body of water, microor- ganisms, especially bacteria, feed on the wastes, breaking them down into simpler organic and inorganic substances. When this decomposition takes place in an aerobic environment—that is, in the presence of oxygen—the process produces nonobjectionable, stable end products such as carbon dioxide (COs), sulfate (SO), orthophosphate (PO4), and nitrate (NOs). A simplified representation of aerobic decomposition is given by the following: Organic matter + Op Microoreaniem’, CO, + HO + New cells + Stable products (NOs, POs, SO. When insufficient oxygen is available, the resulting anaerobic decomposition is performed by completely different microorganisms. They produce end products thar can be highly objectionable, including hydrogen sulfide (F13S), ammonia (NH), and methane (CH,). Anaerobic decomposition can be represented by the following: Organic matter “228, CO, + H,O + New cells + Unstable products (HS, NH, CHy, «- -) The methane produced is physically stable, biologically degradable, and a potent greenhouse gas. When emitted from bodies of water, itis often called swamp gas. It weetgo generated in the anaerobic environment of landfills, where it is sometimes collected and used as an energy source. VThe amount of oxygen required by microorganisms to oxidize organic wastes aerebically is called the biochemical oxygen demand (BOD). BOD may have various nits, but most often, itis expressed in milligrams of oxygen required per liter of wastewater (mg/L). The BOD, in turn, is made up of two parts: the carbonaceous deogen demand (CBOD) and the nitrogenous oxygen demand (NBOD). Those dis- tinctions will be clarified later. Five-Day BOD Test ‘The total amount of oxygen that will be required for biodegradation is an important ressure of the impact that a given waste will have on the receiving body of water. While we could imagine a test in which the oxygen required to degrade completely a sample of waste would be measured, for rourine purposes, such a test would rake too long to be practical (atleast several weeks would be required). As a result, it has200 Chapter 5 Water Pollution become standard practice simply to measure and report the oxygen demand over a shorter, restricted period of five days, realizing that the ultimate demand may be considerably higher. The five-day BOD, or BOD,, is the total amount of oxygen consumed by microorganisms during the first five days of biodegradation. In its simplest form, a BOD; test would involve putting a sample of waste into a stoppered bottle and ‘measuring the concentration of dissolved oxygen (DO) in the sample at the begin- ning of the test and again five days later. The difference in DO divided by the volume of waste would be the five-day BOD. Light must be kept out of the bottle to keep algae from adding oxygen by photosynthesis, and the bottle is sealed to keep air from replenishing DO that has been removed by biodegradation. To standardize the Procedure, the test is run at a fixed temperature of 20°C. Since the oxygen demand of typical waste is several hundred milligrams per liter, and the saturated value of DO for water at 20°C is only 9.1 mg/L, itis usually necessary to dilute the sample to keep the final DO above zero. If during the five days, the DO drops to zero, the test s invalid because more oxygen would have been removed had more been available. The five-day BOD of a diluted sample is given by BOD, = DOTEIDO; ~Z% (5.2) where DO, = the initial dissolved oxygen (DO) of the diluted wastewater DO, = the DO of the diluted wastewater, 5 days later volume of wastewater volume of wastewater plus dilution water. A standard BOD bottle holds 300 mL, so P is just the volume of wastewater divided by 300 mL. P = the dilution fraction = EXAMPLE 5.1 Unseeded Five-Day BOD Test A 10.0-mL sample of sewage mixed with enough water to fill a 300-mL. bottle has an initial DO of 9.0 mg/L. To help assure an accurate test, it is desirable to have at least a 2.0-mg/L drop in DO during the five-day run, and the final DO should be at least 2.0 mg/L. For what range of BOD would this dilution produce the desired results? Solution The dilution fraction is P = 10/300. To get at least a 2.0-mg/L. drop in DO, the minimum BOD needs to be DO,-DO; _ 2.0 mg/L P (10/300) To assure at least 2.0 mg/L of DO remains after five days requires that (9.0 ~ 2.0) mg/L (10/300) This dilution will be satisfactory for BODs values between 60 and 210 mg/L. BOD; = = 60 mg/L BOD; = = 210 mg/L ———ome 5.5 Biochemical Oxygen Demand 201 ntial nutrients ; Bact Seeded dilution water istilled water > ip! Sample bottle filled with waste sample and seeded dilution water Seeded dilution water 300-mL BOD bottles FIGURE 5.9 Laboratory test for BOD using seeded dilution water. So far, we have assumed that the dilution water added to the waste sample has no BOD of its own, which would be the case if pure water were added. In some cases it is necessary to seed the dilution water with microorganisms to assure that there is an adequate bacterial population to carry out the biodegradation. In such cases, to find the BOD of the waste itself, it is necessary to subtract the oxygen demand caused by the seed from the demand in the mixed sample of waste and dilution water. To sort out the effect of seeded dilution water from the waste itself, two BOD bottles must be prepared, one containing just the seeded dilution water and the other containing the mixture of both the wastewater and seeded dilution water (Fig- tee 5.9), The change in DO in the bottle containing just seeded dilution water (called the “blank”) as well as the change in DO in the mixture are then noted. The oxygen demand of the waste itself (BOD,,) can then be determined as follows: BOD_Vm = BODyVw + BODsVa (5.3) where BOD,, = BOD of the mixture of wastewater and seeded dilution water BOD,, = BOD of the wastewater alone BOD, = BOD of the seeded dilution water alone (the blank) V.. = the volume of wastewater in the mixture Vj = the volume of seeded dilution water in the mixture V,, = the volume of the mixture = Vy + Vw Let P = the fraction of the mixture that is wastewater = Viy/Vy, So that (1 = P) = the fraction of the mixture that is seeded dilution water = V/V. Rearranging (5.3) gives Vin Va Ym) _ go) BOD,, BoD, ( v, ) Ke dal Ve (S.4)202 Pter S— Water Pollution where the last term has been multiplied by unity (Vin/Vm)- A slight rearrangement of (5.4) yields BOD. = Wea) PUTT i Substituting the definitions of P and (1 — P) into (5.5) gives Bop, = BOP» ~ BODg(I = P) ea _ P Because BOD,, = DO, — DO; and BODy = where B, = initial DO in the seeded dilution water (blank) B final DO in the seeded dilution water our final expression for the BOD of the waste itself is thus (DO, — DO» = (Bi = By) = P) BOD, eee eee (5.7) EXAMPLE 5.2 A Seeded BOD Test A test bottle containing just seeded dilution water has its DO level drop by 1.0 mg/L in a five-day test. A 300-mL BOD bottle filled with 15 mL of waste- water and the rest seeded dilution water (sometimes expressed as a dilution of 1:20) experiences a drop of 7.2 mg/L in the same time period. What would be the five-day BOD of the waste? Solution The dilution factor P is P = 15/300 = 0.05 Using (5.7), the five-day BOD of the waste would be 7.2 — 1.0(1 — 0.05) BODs = = 125 mg/L Modeling BOD as a First-Order Reaction Suppose we imagine a flask with some biodegradable organic waste in it. As bacte- ria oxidize the waste, the amount of organic matter remaining in the flask will decrease with time until eventually it all disappears. Another way to describe the organit matter in the flask is to say as time goes on, the amount of organic matter already oxidized goes up until finally all of the original organic matter has been oxidized. Figure 5.10 shows these two equivalent ways to describe the organic mat- ter. We can also describe oxygen demand from those same two perspectives. We could say that the remaining demand for oxygen to decompose the wastes de with time until there is no moré demand, or we could say the amount of oxygen5.§ Biochemical Oxygen Demand 203 Time, days FIGURE 5.10 ‘Two equivalent ways to describe the time dependence of organic matter ina flask demand already exerted, or utilized, starts at zero and rises until all of the original oxygen demand has been satisfied. a Translating Figure 5.10 into a mathematical description is straightforward. To do so, itis assumed that the rate of decomposition of organic wastes is proportional to the amount of waste that is left it the flask. If we let L, represent the amount of oxygen demand left after time ¢, then, assuming a first-order reaction, we can write dL, “= kL, 5.8 a (5.8) where k = the BOD reaction constant {time~ The solution to (5.8) is 1 Ly = Lye (5.9) where Lo is the ultimate carbonaceous oxygen demand. It is the total amount of oxygen requiréd by microorganisms to oxidize the carbonaceous portion of the waste to simple carbon dioxide and water. (Later, we will se that there is an addi- tional demand for oxygen associated with the oxidation of nitrogen compounds.) The ultimate carbonaceous oxygen demand is the sum of the amount of oxygen already consumed by the waste in the first ¢days (BOD), plus the amount of oxygen remaining to be consumed after time ¢. That is, Ly = BOD, + Ly (5.10) Combining (5.9) and (5.10) gives us BOD, = loll =e) (5.11) A graph of Eqs. (5.9) and (5.11) is presented in Figure 5.11. If these two figures are combined, the result would look exactly lke Figure 5.10. Notice that oxygen demand can be described by the BOD remaining (you might want to think of L, as how isuch oxygen demand is Left at time f), as in Figure 5.114, or equivalently as oxy- gen demand already satisfied (or utilized, or exerted), BOD,, as in Figure 5.11. Also notice how the five-day BOD is more easily de cribed using the BOD utilized curve. Sometimes the analysis leading to (5.11) is made using logarithms to the base 10 rather than the base e, as they were here. The relationship equivalent to (5.11),204 Chapter $ Water Pollution 1D remaining, L, ultimate carkonaceous BOD uf BOD,= Ly (1-e*) so Time, days (b) BOD uilized FIGURE 5.11 Idealized carbonaceous oxygen demand: (a) The BOD remaining as a function of time, and (b) the oxygen already consumed as a function of time. bur in base 10, is BOD, = Lo(1 - 107%) (5.12) where uppercase K is the reaction rate coefficient to the base 10. It is easy to show that k = K In 10 = 2.303K (5.13) EXAMPLE 5.3 Estimating Lo from BOD; The dilution factor P for an unseeded mixture of waste and water is 0.030. The DO of the mixture is initially 9.0 mg/L, and after five days, it has dropped to 3.0 mg/L. The reaction rate constant k has been found to be 0.22 day”. a. What is the five-day BOD of the waste? b. What would be the ultimate carbonaceous BOD? c. What would be the remaining oxygen demand after five days?5.5. Biochemical Oxygen Demand 205 solution a, From (5.2), the oxygen consumed in the first five days is B DO, - DO; _ 9.0 - 3.0 ODs ee P p03 7 200 melt bh. The total amount of oxygen needed to decompose the carbonaceous portion of the waste can be found by rearranging (5.11) _ _BoDs _ __ 200 ed c. Alter five days, 200 mg/L of oxygen demand out of the total 300 mg/L ‘would have already been used. The remaining oxygen demand would there- fore be (300 — 200) mg/L = 100 mg/L. = 300 mg/L. The BOD Reaction Rate Constant ken eae The BOD reaction rate Constant k is a factor that indicates the rate of biodegrada- tion of wastes. As k increases, the rate at which dissolved oxygen is used increases, although the ultimate amount required, Lo, does not change. The reaction rate will depend on a number of factors, including the nature of the waste itself (for example, simple sugars and starches degrade easily while cellulose does not), the ability of the available microorganisms to degrade the wastes in question (it may take some time for a healthy population of organisms to be able to thrive on the particular vaste in question), and the temperature (as temperatures increase, SO does the rate of biodegradation). Some typical values of the BOD reaction rate constant, at 20°C are given it Table 68 Novice that raw sewage has a higher rate constant than ether well-treated sewage or polluted river wate. This is because raw sewage conrains larger propor- tion of easly degradable organics that exert their oxygen demand quite quickly, leaving a remainder that decays more slowly. care of biodegradation of wastes increases with increasing temperatute, Fo accoun fa these changes, the reaction rate constant k is often modified using the following equation: a yg) (5.14) TABLE 5.8 ‘Typical Values for the BOD Rate Constant at 20°C ee ie Sample kiday” |" Kiday ')? Raw sewage 0.35-0.70 0.15-0.30 Well-treated sewage 0.12-0.23 0.05-0.10 0.12-0,23 0.05-0.10 Polluted river water Lowercase k reaction rates 10 the base ¢ “Uppercase K reaction rates 10 the hase 10. Source; Davis and Cornwell, 1991Se 206 Chapter 5 Water Pollution where kyo is the reaction rate constant at the standard 20°C laboratory referen -— temperature, and ky is the reaction rate at a different temperature T (expresso in °C). The most commonly used value for @ is 1.047, and although @ is somewhay temperature dependent, that single value will suffice for our purposes. EXAMPLE 5.4 Temperature Dependence of BODs In Example 5.3, the wastes had an ultimate BOD equal to 300 mg/L. At 20°C, the five-day BOD was 200 mg/L, and the reaction rate constant was 0.22/day. What would the five-day BOD of this waste be at 25°C? Solution First we will adjust the reaction rate constant with (5.14) using a value of @ equal to 1.047: ys = ky99'T 2) = 0,22 x (1.047)25-2) = 0.277/day So, from (5.12), BODs = Lo(1 — e-*5) = 300(1 — e°?77*5) = 225 mg/L Notice that the five-day BOD at 25°C is somewhat higher than the 20°C value of 200 mg/L. The same total amount of oxygen is required at either temperature, but as temperature increases, it gets used sooner. Nitrification So far, it has been assumed that the only oxygen demand is associated with the biodegradation of the carbonaceous portion of the wastes. There is a significant ad- ditional demand, however, caused by the oxidation of nitrogen compounds. Nitrogen is the critical element required for protein synthesis and, hence, is essential to life. When living things die or excrete waste products, nitrogen that was tied to complex organic molecules is converted to ammonia (NH3) by bacteria and fungi. Then, in aerobic environments, nitrite bacteria (Nitrosomonas) convert ammonia to nitrite (NOz), and nitrate bacteria (Nitrobacter) convert nitrite t0 nitrate (NO5). This process, called nitrification, can be represented with the follow- ing two reactions: 2. NH; + 30, 2Noz +0, SME. 2 NOs This conversion of ammonia to nitrate requires oxygen, so nitrification exerts its own oxygen demand. Thus, we have the combination of oxygen requirements. The oxygen needed to oxidize organic carbon to carbon dioxide is called the carbonaceous oxygen demand (CBOD), and the oxygen needed to convert ammonia to nitrate is called the nitrogenous oxygen demand (NBOD). Nitrification is just one part of the biogeochemical cycle for nitrog atmosphere nitrogen is principally in the form of molecular nitrogen (N:) with @ ua Nitrosomonas (5.15) (5.16) en, In the266 = Chapter 5 Water Pollution degrade the target pollutant. Isolation techniques, such as impermeable barriers, vitrification, encapsulation, and soil solidification, attempt to permanently immobi lize the contaminant. Abiotic chemical degradation uses injected compounds such as Potassium permanganate or hydrogen peroxide to oxidize subsurface pollutants, Many variations of bioremediation and combination biotic/abiotic processes have been reported, including phytoremediation, biosparging, biofiltration, and sequen- tial anaerobic-aerobic techniques. Further discussion of these and other alternative approaches is beyond the scope of this text, but details can be found in references such as by Bedient (1999) or from the resources listed by EPA (2001). PRO BLEMS - S.1 Ina standard five-day BOD test, (a) Why is the BOD bottle stoppered? (b) Why is the test run in the dark (or in a black bottle}? (c) Why is it usually necessary to dilute the sample? (d) Why is it sometimes necessary to seed the sample? (ec) Why isn’t ultimate BOD measured? 5.2, Incoming wastewater, with BOD; equal to about 200 mg/L, is treated in a well-run sec- ondary treatment plant that removes 90 percent of the BOD. You are to run a five-day BOD test with a standard 300-mL bottle, using a mixture of treated sewage and dilution ; water (no seed). Assume the initial DO is 9.2 mg/L. b (a) Roughly what maximum volume of treated wastewater should you put in the bottle if you want to have at least 2.0 mg/L of DO at the end of the test (filling the rest of the bottle with water)? (b) If you make the mixture half water and half treated wastewater, what DO would you expect after five days? 5.3. A standard five-day BOD test is run using a mix consisting of four parts distilled warer \ and one part wastewater (no seed). The initial DO of the mix is 9.0 mg/L, and the DO after five days is determined to be 1.0 mg/L. What is BOD;? 5.4 ABOD test is to be run on a sample of wastewater that has a five-day BOD of 230 mg/L. If the initial DO of a mix of distilled water and wastewater is 8.0 mg/L, and the res: requires a decrease in DO of atleast 2.0 mg/L with atleast 2.0 mg/L. of DO remaining at the end of the five days, what range of dilution factors (P) would produce acceptable results? In 300-mL bottles, what range of wastewater volumes could be used? 5.5 The following data have been obtained in a BOD test that is made to determine how well / A wastewater treatment plant is operating: Volume of Volume of Initial DO (mg/L) Final DO (mg/L) Wastewater (mL) Dilution Water mL) ‘i Untreated sewage 60 20 5 295 Treated sewage 9.0 4.0 1s 3855.6 5.77 58 59 Problems 267 What percentage of the BOD is being removed by this treatment plant? If this is a second ary treatment plant that is supposed to remove 85 percent of the BOD, would you say it is operating properly? Figure P5.6 shows a plot of BOD remaining versus time for a sample of effluent taken from a wastewater treatment plant. BOD remaining (mg/L) Days FIGURE P5.6 (a) What is the ultimate BOD (Ly)? (b) What is the five-day BOD? (c) What is Ls? If the BODs for some wastewater is 200 mg/L, and the ultimate BOD is 300 mg/L, find the reaction rate constants k (base e) and K (base 10). A BOD test is run using 100 mL of treated wastewater mixed wita 200 mL of pure water. The initial DO of the mix is 9.0 mg/L. After 5 days, the DO is 4.0 mg/L. After a long period of time, the DO is 2.0 mg/L, and it no longer seems to be dropping. Assume nitrification has been inhibited so the only BOD being measured \s carbonaceous. (a) What is the five-day BOD of the wastewater? (b) Assuming no nitrification effects, estimate the ultimate carbonaceous BOD. (c) What would be the remaining BOD after five days have elapsed? (d) Estimate the reaction rate constant k (day~'). Suppose you are to measure the BOD removal rate for a primary wastewater treatment plant. You take two samples of raw sewage on its way into the plant and two samples of the effluent leaving the plant. Standard five-day BOD tests are ran on the four samples, with no seeding, producing the following data: 1 Raw 1:30 92 2 2 Raw LS wae 3 Treated 1:20 a0 4 Treated 2 20 a 1 ee268 5.10 vA 5.12 Chapter $ Water Pollution (a) Find BODs for the raw and treated sewage, and the percent removal of BOD in the treatment plant. (b) Find the DO that would be expected in Sample 2 at the end of the test. (c)_ What would be the maximum volume of treated sewage for Sample 4 that could be Put into the 300-mL BOD bottle and still have the DO after five days remain above 2 mg/L? A standard BOD test is run using seeded dilution water. In one bottle, the waste sample is mixed with seeded dilution water giving a dilution of 1:30. Another bottle, the blank, Contains just seeded dilution water. Both bottles begin the test with DO at the saturation value of 9.2 mg/L. After five days, the bottle containing waste has DO equal to 2.0 mg/L, while that containing just seeded dilution water has DO equal to 8.0 mg/L. Find the fi day BOD of the waste. ‘A mixture consisting of 30 mL of waste and 270 mL of seeded dilution water has an ini- tial DO of 8.55 mg/L; after five days, it has a final DO of 2.40 mg/L. Another bottle con- taining just the seeded dilution water has an initial DO of 8.75 mg/L and a final DO of 8.53 mg/L. Find the five-day BOD of the waste. Some wastewater has a BODs of 150 mg/L at 20°C. The reaction rate k at that tempera- ture has been determined to be 0.23/day. (a) Find the ultimate carbonaceous BOD. (b) Find the reaction rate coefficient at 15°C. (c) Find BOD, at 15°C. Some waste has a five-day BOD at 20°C equal to 210 mg/L and an ultimate BOD of 350 mg/L. Find the five-day BOD at 25°C. A clever approach for finding Lo involves daily measurements of BOD (that is, BOD,, BOD>, BOD). A straight line is fitted to a plot of BOD,,; vs. BOD,, and the intersection point of that line with a line drawn through the origin with slope = 1 is then found. That intersection point occurs where BOD,,, = BOD,; that is, it is the point where BOD is no longer changing; hence it is Lo, as shown in Figure PS.14. a _ T I TT = 200 | —}—} 2 | é _+ é Ave $ 10 o 1 0 100 BOD, (mg/L) FIGURE PS.14Problems 269 The following are BOD data for the sample waste graphed in P.5.14, along with three additional wastes. Determine Lo for each of the additional wastes using this graphical procedure: t Example t Waste I Waste 2 Waste 3 (day) BOD, BOD,,; (day) BOD, BOD, BOD, 0 0 57 0 0 0 9 1 s7 102 1 62 38 41 2 102 134 2 104 72 79 3 134 160 3 142 104 101 4 160 184 4 179 123 121 5 184 199 5 200 142 140 6 199 207 6 222 181 152 7 207 7 230 167 159