United States Environmental Protection Agency National Risk Management Research Laboratory Research Triangle Park, NC 27711 Research and Development EPA/600/SR-97/094 January 1998 Project Summary Field Measurement of Greenhouse Gas Emission Rates and Development of Emission Factors for Wastewater Treatment Bart Eklund and Jeffrey LaCosse A research project was conducted to measure emissions of greenhouse gases (GHGs) from wastewater treat- ment (WWT) and disposal facilities. The overall objective of the research under the base statement of work area for this contract is to develop more reli- able estimates of GHG emissions from industrial and domestic WWT systems. Most previous research for these sources has used a mass balance ap- proach to estimate potential methane (CH4) emissions, but in this study emis- sions of CH4 and other GHGs were mea- sured under field conditions, which should improve the reliability of the emission estimates. Field sampling was performed at five sites, including WWT systems in the beef and chicken processing industries and two publicly owned treatment works (POTWs). Ambient air was mea- sured immediately downwind of the la- goons using a Fourier Transform Infra- red (FTIR) approach. The FTIR light beam was directed along a path of sev- eral hundred feet and the absorbance of gases was measured. The target compounds of interest included CH4, carbon dioxide (CO2), nitrous oxide (N2O), carbon monoxide (CO), ammo- nia (NH3), and certain volatile organic compounds (VOCs). The source term (i.e., emission rate) can be determined from information about the average downwind ambient concentration (mea- sured by the FTIR method) and the atmospheric dispersion characteristics at the time of sampling. In addition, samples of influent and effluent waste- water and sludge were collected. Emis- sion factors were developed in terms of grams of species emitted per gram of precursor in the influent wastewa- ter; e.g., g CH4/g biological oxygen de- mand (BOD). The emission factors will be combined with activity factor data to develop national and global emis- sions inventories. This Project Summary was developed by EPA's National Risk Management Research Laboratory's Air Pollution Prevention and Control Division, Re- search Triangle Park, NC, to announce key findings of the research project that is fully documented in a separate report of the same title (see Project Report ordering information at back.) Introduction A GHG generally can be defined as any molecule which absorbs infrared light in the spectral region of 5 to 20 |jm These molecules include water vapor (H2O), CO2, CO, CH4, certain VOCs, and N2O. Rea- sonably accurate global balances of GHGs are needed as input to climatic models for estimating long-term global temperature changes. A large number of natural and anthropic activities produce or release GHGs. The emphasis of this program was on emis- sions from WWT facilities. The decomposi- tion of organic waste may occur aerobi- cally (i.e., with oxygen) or anaerobically (i.e., without oxygen). Aerobic decomposi- tion of organic carbon results in the pro- duction of CO2, while anaerobic decompo- sition results in the production of CH4and CO2. Given a sufficient amount of time, essentially every atom of carbon in waste streams is converted to either CO2 or CH4. ------- In terms of their ability to retain heat in the atmosphere, however, CO2 and CH4 are not equivalent. A given mass of CH4 is 58 times stronger a GHG than the same mass of CO2 (it is 21 times stronger on a mo- lecular basis). Therefore, the relative amount of anaerobic versus aerobic de- composition is of interest. The overall objective of the research under the base statement of work area for this contract was to develop more reliable estimates of GHG emissions from indus- trial and domestic WWT systems. National and global inventories of CH4 emissions from WWT facilities have been published. These estimates, however, are based on various assumptions and very limited data. Most previous research for these sources has used a mass balance approach to estimate potential CH4 emissions, but in this study emissions of CH4 and other GHGs were measured under field condi- tions, which should improve the reliability of the emission estimates. The overall objectives of this study were: 1) Identify industries and WWT processes that have the greatest potential for mea- surable emissions of CH4; 2) Select the most promising sites for testing in those industries; 3) Perform ambient air mea- surements using an open path monitoring (OPM) approach with a FTIR spectros- copy instrument; 4) Collect and process data and characterize the influent and ef- fluent wastewater quality at the field sites; and 5) Use the field data to develop emis- sion factors for each target compound. The target compounds of interest included CH4, CO2, N2O, CO, NH3, and certain VOCs. A subset of WWT systems that employ anaerobic treatment processes was se- lected for testing. Within this subset, anaerobic lagoons were given priority over anaerobic digesters, tanks, and sludge dis- posal units because lagoons offered the fewest logistical constraints to testing. Al- though anaerobic lagoons are not exten- sively used to treat industrial and domes- tic waste in the U.S., other countries use anaerobic lagoons to treat wastewater. Because of difficulties associated with iden- tifying sites and the expense of conduct- ing field measurements in foreign coun- tries, sites in the U.S. that are representa- tive of treatment conditions in developing countries were selected for testing. Approach Site selection focused on U.S. WWT systems that employ open, anaerobic pro- cesses to achieve high levels of BOD or chemical oxygen demand (COD) removal. First, industries that treat large volumes of wastewater and remove large amounts of BOD/COD were identified. Approximately a dozen industries were identified as po- tential candidates for testing. Second, a telephone survey was conducted of in- dustry representatives, experts in the WWT area, and regulatory personnel to identify industries most likely to treat wastewater to remove high levels of BOD/COD in open, anaerobic lagoons. The most prom- ising candidates were beef and poultry processing plants, and pulp and paper mills. POTWs also were of interest be- cause they are used to treat a significant fraction of wastewater both nationally and globally and, also, are thought to be a potentially significant source of N2O emis- sions. Five sites were selected for testing. The selection intentionally included sites from several different industries: two beef pro- cessing plants, one chicken processing plant, and two POTWs. Two sites from certain industries were included to help determine the variability in emissions within a given industry. The field work involved being on site for about 5 days at each facility. Ambient air was measured immediately upwind and downwind of the lagoons using an OPM- transect method (OPM-TM) approach with detection by FTIR spectroscopy. The FTIR light beam was directed along a path of several hundred feet and the absorbance of gases was measured. Emission rates were determined from measurements of the downwind ambient concentration and the atmospheric dispersion characteristics at the time of sampling. In addition, a limited number of influent and effluent wastewater and sludge samples were col- lected. Emission factors were developed in terms of grams of GHG species emitted per gram of precursor in the influent waste- water (e.g., g CH4/g BOD). The emission factors will be combined with activity fac- tor data to develop national and global emission estimates. Results OPM-TM using the FTIR was used to determine emission rates. A very large data set was generated, and up to 300 separate valid, 5-minute average emis- sion rate determinations were made at a given site. The air measurement data were reviewed to identify compounds found in significantly greater concentrations in the downwind air versus the upwind air at each site. Any such compounds were likely to have been emitted from the lagoons being tested. Many of the target analytes were found at the same concentration lev- els upwind and downwind of the lagoons; i.e., they had no quantifiable emission rate. Only CH4, NH3, and the sulfur hexafluo- ride (SF6) tracer gas generally were present in greater amounts in the down- wind air. The minimum quantifiable emission rate varied from site to site and from one 5- minute period to another. The detection limit for a given compound, in terms of grams per second, is dependent on the smallest difference between downwind and upwind concentrations that could be iden- tified apart from the measurement vari- ability within each of the upwind and down- wind data sets. For each increment of 0.5 ppmv (500 ppbv) that a given compound was present in greater concentrations downwind than upwind, its emission rate was about 1 g/sec (depending on the mo- lecular weight of the compound). Typical detection limits were about 0.1 g/sec for most compounds, except for CO2, which had a minimum detection limit of about 150 g/sec. The high detection limit for CO2 was due to the high background con- centrations (e.g., 500 ppmv) and the mea- surement coefficient of variability (e.g., CV = 7.5%, or 37.5 ppmv). At all three meat processing plants, large amounts of CH4 were detected downwind of the WWT system. For the two beef processing plants, the concentration of CH4 (and NH3) exhibited an exponential rela- tionship with wind speed. The downwind CH4 concentration at the chicken process- ing plant did not show a clear relationship between concentration and wind speed. At the chicken processing plant, however, the range of wind speeds was much smaller than for the meat processing plants and the number of valid measurement pe- riods also was much smaller, making it more difficult to identify trends and rela- tionships. There also was a thick grease layer present on top of the lagoon which would tend to diminish the effect of sur- face winds on air emissions. The emission rates measured at each site for CH4, NH3, and other selected com- pounds are given in Table 1. Surprisingly, no emissions were detected from the POTWs. It was expected that either CH4 or CO2 would be detected. The dissolved oxygen (DO) level in the lagoons exceeds 2 mg/L, indicating that BOD removal is taking place under aerobic conditions. So it is highly probable that CO2 is being generated, but the levels were too small to detect given the very high background levels of CO2 and the measurement vari- ability. In general, anaerobic degradation can be expected to produce a mixture of CH4 and CO2 (somewhere between a 50:50 and a 70:30 ratio). Therefore, emissions of CO2 would be expected wherever quan- tifiable emission rates of CH4 were found. ------- Table 1. Measured Emission Rates of Selected Compounds for Each Field Site Site Beef Processing Plant inSWU.S. Beef Processing Plant in Midwest U.S. Compound CH4 NH3 NH! Average Downwind Cone. (ppm) 61.9 355 ppb 58.1 1.04 Average Upwind Cone. (ppm) 2.3 0 2.83 0.277 Maximum Downwind Cone. (ppm) 142 609 ppb 200 2.06 Average Emission Rate (g/sec) 280 2.2 230 3.5 Chicken Processing Plant in SE U.S. POTWfor Small Town in SWU.S.3 POTWfor Very Small Town in SWU.S.3 NH3 N20 CH NH C02 NH CO, 9.80 2.6 ppb 563 ppb 2.20 0.2 ppb 342 2.11 93.3 ppb 528 1.92 2.8 ppb 542 ppb 2.14 0 351 2.16 25.5 ppb 668 29.9 44.1 ppb 586 ppb 2.46 15.4 ppb 384 2.81 21 4 ppb 691 180 0.066 2.6 O.15 O.05 <150 O.15 O.05 <150 aMethane, carbon dioxide, and ammonia values are shown for the POTWs for comparison purposes. No quantifiable emissions of these compoundswere detected at either POTW. The lack of quantifiable CO2 emission rates may be due to the high detection limit for CO2 emission rates, as previously dis- cussed. The absence of CO2 emissions also could be due to the presence of cyanobacteria (blue-green algae) in the anaerobic lagoons. The wastewater data for all three meat processing plants are very similar, with the two beef processing plants showing very good agreement. All three WWT sys- tems have high BOD removal rates (88- 95%), as well as high removal rates for COD, total organic carbon (TOC), and ni- trates. All three WWT systems at meat processing plants generated large amounts of NH3 as a by-product of the biodegrada- tion of the wastewater. The only param- eter that showed variable behavior from system to system was total Kjeldahl nitro- gen (TKN). The two POTWs had similar influent wastewater and exhibited similar perfor- mance in terms of removal of BOD, COD, TOC, TKN, and NH3. Both systems gener- ated nitrates as a by-product of biodegra- dation. Activity factors were developed for each site based on information provided by the plant operators and from the wastewater data. Emission factors were developed for each site by dividing the average emis- sion rates by the activity factors for each site. The resulting emission factors are given in Table 2. For CH4, the emission factor based on COD should be a better predictor of emissions from other facilities than the emission factor based on BOD. The 5-day BOD test will not fully degrade all of the biological material in wastewa- ters containing proteins and fatty acids. The suspended solids associated with the wastewaters also are biodegradable, and their ultimate BOD would not be exerted in the 5 days it takes to run a standard BOD test. COD data, however, are not always available, and estimates based on other activity factors may be necessary. Therefore, a variety of emission factors are included in Table 2. Table 2. Average Emission Factors Compound Emission Factor Average Range Methane Ammonia Nitrous Oxide g CH4/head of cattle g CH4/chicken g CH4/kg meat g CH4/L of wastewater g CH4/g influent BOD g CH4/g BOD removed g CH4/g COD removed g NH3/head of cattle g NH3/chicken g NH3/kg meat g NH3/L of wastewater g NH3/g influent BOD g NH3/g NH3 in effluent g N2O/chicken g N2O/kg meat g N2O/L of wastewater g N2O/g BOD removed g TKN removed 4,200 120 37 2.7 1.5 1.6 0.96 46 0.046 0.14 0.014 0.40 0.072 1.8 1.1 0.067 0.051 1.7 3,500 - 4,800 N/A 15-74 1.6-4.6 0.40 - 3.2 0.43 - 3.4 0.26 - 2.0 37-54 N/A 0.027 - 0.24 0.0017-0.028 0.0031 - 1.2 0.020-0.13 N/A N/A N/A N/A N/A N/A = Not applicable. ------- An estimate of the uncertainty of the emission factors was developed through standard error propagation methods. The derived emission factors all appear to be reliable to within a factor of 2, based on random error in the measurements, and assuming that the sites and samples accurately represent the population of interest. It is possible that the lagoons are a sink for suspended and colloidal material (i.e., insoluble BOD) and this material builds up over time in the lagoon sediments. If so, sediments may degrade during summer months or whenever the sediment is re- suspended, thereby increasing the CH4 (and CO2) emissions. However, no sea- sonal trend is evident in the BOD effluent levels in the long-term wastewater data provided by the plants. A number of previously published stud- ies contain estimated or measured values for the emission fluxes of CH4 from liquid surfaces or slurries. The key comparison is the emission flux (i.e., emission rate per unit surface area). The average CH4 emis- sion flux for the three meat processing plants ranged from 6,100 to 23,000 \ig CH4/sec-m2. Results for livestock lagoons in previous studies (1,400 to 9,400), were within an order of magnitude, as were measurements at a manure tank (1,300 to 3,800). The emission flux from municipal WWT systems, industrial WWT systems, and rice paddies was substantially lower, as expected given the much lower BOD and COD levels in such waters. Very few published emission factors can be compared with the emission fac- tors developed in this study. The most widely reported emission factor for CH4 is 0.22 g CH4/g BOD. The reference for this factor does not provide information about how it was developed. It is very close to the theoretical value for the anaerobic deg- radation of glucose. The emission factors determined in this study are substantially higher than those based on glucose deg- radation. Glucose is a simple sugar and its biodegradation over short periods of time cannot be directly compared with the microbial degradation of complex mixtures of amino and fatty acids, such as are present in the wastewaters at the meat processing plants. Conclusions Several conclusions can be drawn from the study: • The FTIR measurement approach used in this study was successful for the simultaneous collection of large amounts of ambient concentration data for CH4 and NH3; • The use of the OPM-TM approach using FTIR for estimating emission rates has insufficient sensitivity for cer- tain compounds, such as hydrogen sulfide and total non-methane hydro- carbons, due to limitations in the FTIR analysis. For most of the sites, the sensitivity for CO2 was limited by the high background concentrations and the variability in the background con- centrations; • Anaerobic WWT lagoons are a sig- nificant source of CH sions; and • Lagoons at POTWs are not a signifi- cant source of any GHG, with the possible exception of CO2. and NH3 emis- ------- Bark Eklund and Jeffrey LaCosse are with Radian Corporation, Austin, TX 78720. Susan A. Thorneloe is the EPA Project Officer (see below). The complete report, entitled "Field Measurement of Greenhouse Gas Emission Rates and Development of Emission Factors for Wastewater Treatment," (Order No. PB98-117898; Cost: $67.00, 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: Air Pollution Prevention and Control Division National Risk Management Research Laboratory U.S. Environmental Protection Agency Research Triangle Park, NC 27711 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati, OH 45268 Official Business Penalty for Private Use $300 BULK RATE POSTAGE & FEES PAID EPA PERMIT NO. G-35 EPA/600/SR-97/094 ------- |