Methane Emissions at a Wastewater Treatment Plant in Western Australia

Mark Goldstone1, Nick Turner2, Christopher Gwynne3 1GHD 2Water Corporation 3GHD EXECUTIVE SUMMARY Methane is a significant greenhouse gas and also represents a useful surrogate for certain odorous compounds found in wastewater treatment. In terms of greenhouse issues methane is radiatively active and has been reported at 21 times stronger at heat adsorption than carbon dioxide. There are many methane sources, both natural and anthropogenic and emissions at WWTPs are cited in the literature as representing less than 10% of all emissions. However, this is by no means certain and will strongly depend on the septicity of sewers, which is directly related to temperature and residence times in rising mains. It is clear from a preliminary understanding of methane formation that the conditions for methane generation are unlikely to exist in many places in a wastewater treatment plant except at the anaerobic digesters. Therefore emissions from other areas of a wastewater treatment plant are likely to be due to removal of methane entrained in the wastewater entering the plant. In terms of odour, methane itself is not odorous, but can act as a surrogate for a number of odorous methane precursors. These precursors include the volatile fatty acids, all of which are known to be odorous. Methane can therefore describe the emissions behaviour of a range of compounds and suggest where these might be important. An investigation of methane emissions from a wastewater treatment plant (90 ML/D, 400,000 EP) was undertaken as part of a baseline odour survey. The study included the use of continuous instrumentation for the measurement of methane and total oxidisable sulphur (a surrogate for hydrogen sulphide), as well as a significant number of grab samples for odour. Methane emissions appear to be significant amongst the point sources. This is expected because the point sources include a number of locations where methane generation is encouraged and where the generated methane is stored or flared. Measurement of these point sources is difficult, because the concentrations in emissions are very high and collected samples were sometimes too high in methane to be accurately measured by the instrumentation available. Another cause for concern is that many of these point sources are fugitive sources and are therefore difficult to characterise in terms of flow rate and exit velocity. For instance, leaks in the anaerobic digester seals give high concentrations of methane, but it is very difficult to fully quantify the flow rate from these sources. Characterisation of area sources demonstrates that limited or no methane generation is occurring in the area sources methane emissions gradually decrease until the remaining entrained methane is finally stripped at the head of the aerated zone. Ambient monitoring data from a nearby residence was used in order to provide an alternative measure of true methane emissions from the plant. Whenever low wind speeds blew emissions from the plant towards the residence levels of methane and total oxidisable sulphur increased in a reasonably consistent ratio. Characterisation of total oxidisable sulphur total emissions had been more successful due to the ability to accurately measure point source concentrations and therefore this ratio could be back calculated to give an estimate of total CO2 equivalent of 2560 tonnes/yr as compared a state emission of 683,000 tonnes/yr (AGO, 1999).

KEYWORDS

Methane, greenhouse, wastewater treatment, odours, measurement

INTRODUCTION Water Corporation is in the process of undertaking extensive odour control at Beenyup Wastewater Treatment Plant. As part of this process, Water Corporation commissioned GHD to undertake a gas emissions survey of the plant. Part of this program included an assessment of methane emissions from within the plant. Methane is chemically and radiatively active in the atmosphere. It has a relatively long half-life in the atmosphere and so can build up rapidly in the environment. Even its breakdown path, by reaction with the OH (hydroxyl radical) can lead to further production of greenhouse gas, because the resultant peroxy radical can contribute to photochemical ozone increase, ozone being another radiatively active gas. Methane is considered to be capable of absorbing 21 times as much heat as carbon dioxide and whilst its global concentrations are considerably below that of CO2, changes in levels can nevertheless have a significant impact on warming. A number of research establishments have considered the impact of methane and determined the key natural and anthropogenic sources. Augenbraun at al., (1999) indicate the breakdown of emissions shown in Figure 1. The basis for the 5% of emissions from wastewater treatment is not clear.

Figure 1 - Estimated Global Methane Emissions (after Augenbraun et al., 1999). Researchers indicate that the impact of these emissions has been to increase background levels of methane from 300 ppb to 1600 ppb. This concurs very well with background urban background levels measured recently in WA (Gwynne et al., 2002). Methane, also known as natural gas, is produced biologically from acetic acid. Research into the chemical pathways for methane generation is still ongoing because they are highly complex. In simple terms large insoluble organic molecules can be broken down by

hydrolysis to increase the amount of soluble organic material (fatty acids, amino acids and sugars). This material then undergoes fermentation by two main pathways; Acidogenesis produces longer chain fatty acids (butyric acid, propionic acid etc) which are then broken down to acetic acid; Acetogenesis produces acetic acid directly. The acetic acid is then broken down, in the presence of water, by only three classes of bacteria to form methane and carbon dioxide. This process is relatively slow, meaning that, in an uncontrolled system, there will be significant quantities of the intermediate products (all of which are strongly odorous). Methanogenesis by currently understood pathways is strongly temperature dependent and requires strict anaerobic conditions to occur. The bacteria required for methanogenesis are relatively robust and can exist in other more oxygenated environments, but the process can be stopped immediately by the presence of oxygen or, indeed, excessive levels of contaminants (e.g. heavy metals) or shock loading of such contaminants. Consequently, the presence of methane emissions does not necessarily mean that methanogenesis is occurring in the area under study. Rather, it may indicate the release of entrained methane that could have been produced at some stage prior to the WWTP. Background of Beenyup WWTP The history and configuration of Beenyup WWTP plant is outlined elsewhere (Goldstone et al., 2002). METHODOLOGY A process flow diagram outlining the major equipment used in sampling and continuous analysis is shown elsewhere (Gwynne et al., 2002). A photograph of the system is shown in Figure 2. A floating sampling hood was used to collect emissions from areas under the controlled conditions of a simulated wind speed of 0.3 m/s. The simulated wind was generated using an odourless neutral gas (zero air), which matches the requirements of the Draft Australian Standard 99306.

Figure 2 Continuous monitoring wind tunnel sampling system The study included the requirement to maintain continuous measurement of emissions over a multi-day period and this eliminated the ability to supply this gas using a

compressed cylinder supply. Therefore, a scrubbed air supply using activated carbon was developed using a small blower capable of maintaining a constant flow of up to 90 L/s. This flow rate matches closely with the flow requirements for blowers used in high volume dust samplers and therefore an air supply could be obtained using standard, pre-tested, instrumentation. It is noted that GAC does not scrub methane to a high degree and therefore, every six hours the background levels of methane were measured by diversion of the sampling line to a port at the inlet end of the wind tunnel. A variable baseline of approximately 0.2ppm methane was present in this data. The baseline was most affected when the scrubbing system was impacted by high methane sources The sampling hood was constructed of stainless steel and fitted inside a float constructed of glass reinforced plastic (GRP) coated foam. Air passed from the scrubber to the inlet port of the hood. At the inlet port was an off-take for a zero line, which was run back through a PTFE (teflon) sampling line to the instrument housing. Inside the sampling hood, fins were used to distribute the air and ensure an even flow over the surface of the water. A baffle was constructed at the outlet end of the hood to reduce the likelihood of water passing into the sampling line, and to turbulently mix the gas. Two sample ports were installed behind the baffle and connected to the instrument housing using a PTFE sampling line. Sensors in the hood measured hood pressure and temperature, as well as fluid temperature. The hood air pressure and temperature readings were important in calculating the actual hood wind velocity. Gas Sample Collection System The sample collection system comprised two parts: A continuous (on-line) sampling and gas detection system; and A bag filling device (using the lung principle) for collection of air samples for gas analysis of point source samples. Methane Analysis An Horiba APHA 350-E Flame Ionising Detection (FID) instrument capable of measuring Methane and Non Methane Hydrocarbons continuously to a lower detection limit of 0.1 parts per million was used to measure sampled hydrocarbons. Data Collection Data output from these instruments was logged continuously and converted to five-minute average concentrations, which were then used for analysing trends. The majority of the time, the continuous system was analysing gas collected from the areal sources, using the sampling hood, however it was possible to collect bag samples from point and volume sources and introduce them to the analyser bank and collect gas readings. Sampling and Analysis of Point and Volume Sources The bag sampling device consisted of a plastic drum with a sealed lid, a PTFE inlet tube and valve connected to the sample line and an evacuation tube connected to a suction pump. The negative pressure produced inside the drum as air was evacuated from the drum allowed the sample bag to fill without the need to introduce a sampling pump into the sample line. The samples required approximately 3 5 minutes for collection. Samples were then introduced manually to the instrument and allowed to stabilise before a reading was recorded.

RESULTS

Table 1 indicates the emission rates from all sources found at Beenyup WWTP. This indicates that the point sources are as significant as the areas sources, although this is really based on the emissions from two poorly quantified sources; the flare and the screenings room. Measurement of these sources led to off-scale readings and therefore there was a need to estimate these concentrations on the basis of known sulphide to methane ratios. It is clear from the overscale readings, however that these are not negligible sources. Methane emissions also increase at the primary sedimentation tank inlets suggesting that methanogenesis may be occurring at this location. Whilst this seems unlikely, it should be noted that the PSTs receive sludge dewatering liquors that are likely to be high in volatile fatty acids giving a ready feedstock. Table 1 - Summary Methane Emission Rates Methane Emission Rate Source (mg/s) Soil Bed 75 Grit Tanks 7 Inlet Channels 12 PSTs 641 AST Anoxic Zones 279 AST Aerobic Zones 879 Mixed Liquor Channels 4 Secondary Sedimentation Tanks 267 Sludge Thickening (DAF) Tank 16 Primary Effluent Distribution Chamber 0 Area Sources (Total) 2180 Screenings Room Inlet Works Fugitives Digester Gas Flare Sludge Handling Building Sludge Digester Seals Point Sources (Total) Plant Total 105 137 788 1760 49 105 5,010

% of Total 1% 0% 0% 13% 6% 18% 0% 5% 0% 0% 43% 2% 3% 16% 35% 1% 57%

Time Variability Time variability of emissions from the plant area sources and a comparison of emissions with chlorine turned on and off can be seen in Figures 2 to 5. Figure 2 clearly demonstrates that emissions from the primary sedimentation tank inlet are quite variable and do not follow an obvious consistent trend in emissions, although the October 2000 data appears to be flow controlled. There is also a clear increase in emissions when chlorine is turned off. This may be due to ongoing methanogenesis in the last few meters of the sewer and in the headworks, but might also be due to methanogenesis in the sludge.

Figures 3 and 5 demonstrate clear diurnal trends for methane emissions that are probably flow controlled or controlled indirectly by aeration rates, which follow closely the flow rates. Diurnal variations are less clear in the anoxic zone, but this is a very noisy source due to the slow mixing and associated turbulence. There is, incidentally, little evidence that methane generation is occurring through between the inlet to the primary sedimentation tank and anoxic zones because the overall emissions drop significantly across the various stages of the plant. Emissions increase significantly at the head of the aeration zone, but this is due to stripping of dissolved gases by the bubbles. The difference in emissions between the chlorine on and chlorine off scenario in the aeration tank could be due to the re-commissioning of an additional module resulting in less aeration being required to meet set points for dissolved oxygen.

Figure 2. Time Variability in Methane Emissions from the Primary Sedimentation Inlet

Figure 3 - Time Variability in Methane Emissions from the Primary Sedimentation Outlet

Figure 4 - Time Variability in Methane Emissions from the Anoxic Zone

Figure 5. Time Variability in Methane Emissions from the Aeration Zone Spatial Variability Figure 6 shows the drop in emissions across the primary sedimentation tanks for methane total oxidisable sulphur and odour. It can be seen that of these gases methane maintains the most constant emissions, showing little variation between the two monitoring programs and a much smaller decrease along the length of the tank. This may occur because total oxidisable sulphur (and associated odour) is generated reasonably rapidly in the slightly reducing conditions of the headworks. However, the conditions for methanogenesis are much more stringent and therefore the methane generation is limited to specific sites or is due to methane imported from the rising main sewers. In this respect it is interesting to note that total oxidisable sulphur emissions increase in the anoxic zone, whilst methane continues to fall. Figure 7 indicates that gaseous compounds are stripped rapidly at the head of the aeration zone, however, there is a clear difference in the rate of stripping that occurs between odour, total oxidisable sulphur and methane.

Figure 6. Emissions of Methane and Other Gases along the Primary Sedimentation Tanks

Figure 7. Emissions of Methane and Other Gases along the Aeration Zone. Assessment of Fugitives Review of modelling data undertaken elsewhere (Gwynne et al., 2002b) suggested that there was a possibility of significant methane emissions that were not characterised by this study. This would be possible because there are a number of high methane point sources that were poorly characterised in terms of exit velocity, overall volume of emission and concentration of methane. These sources include; the flare, which was calculated on the basis of input flow rate and combustion efficiency, the anaerobic digester seals, which were known to leak at an undetermined rate, fugitives in the inlet sewer to the plant, the sludge drying room and emissions from the gas handling infrastructure. The latter of these were not characterised at all. It should be noted that high concentration sources of this nature are very difficult to accurately assess because the flow assessment must be precise or the total emission can be significantly in error. Characterisation of area sources demonstrated that limited or no methane generation was occurring in most area sources, although there is a suggestion that it may occur in the sludge at the inlet to the PSTs. Ambient monitoring data from a nearby residence could therefore be used in order to provide an alternative measure of total methane emissions from the plant. Whenever low wind speeds blew emissions from the plant towards the residence, levels of methane and total oxidisable sulphur increased in a reasonably consistent ratio. Characterisation of total oxidisable sulphur emissions had been more

successful due to the ability to accurately measure concentrations in the point sources and therefore this ratio could be back calculated to give an estimate of total methane emissions. The time series plot of the measured methane and total oxidisable sulphur levels can be seen in Figure 8. Note that a background value of 2.5 ppm has been removed from the methane trend so that the ratios calculated were purely on the basis of elevated levels when the wind blew from the plant to the monitoring site (approximately 160 degrees). Table 2 outlines the selected episodes from the ambient monitoring data. It can be seen that methane/sulphur ratios varied between 48 and 117 giving an average ratio of 71, the latter being a reasonably robust figure. These ratios can then be compared to the total oxidisable sulphur emission for the plant of 54.2 mg/s to give a methane emission of between 2600 6300 mg/s and averaging 3900 mg/s (122 tonnes/year or a CO2 equivalent of 2560 tonnes per year). This compares to an estimated state emission of 683,000 tonnes per year CO2 equivalent. On the basis of the equivalent population of Western Australia this indicates that WWTPs account for approximately 1.1% of anthropogenic methane emissions in the state. This percentage is somewhat at odds with the estimate of 7% of anthropogenic emissions given by Augenbraun et al. (1999). Table 2. Ratio of Methane to total oxidisable sulphur during ambient Monitoring Methane/ Average Average Sulphur Wind Wind Episode Start Sulphur Methane Concentration Speed Direction Number of 3 3 Time (mg/m ) (mg/m ) Ratio (m/s) (Deg) Hours 11-Jun-01 14:00 0.017 0.8 48 156 24 12-Jun-01 16:00 0.018 1.0 59 157 19 15-Jun-01 17:00 0.017 1.2 71 0.45 160 15 17-Jun-01 17:00 0.008 0.6 76 0.59 166 21 18-Jun-01 16:00 0.039 1.9 50 0.35 164 17 19-Jun-01 13:00 0.015 1.7 117 0.62 172 20 21-Jun-01 17:00 0.017 1.3 79 0.46 143 17 Min 0.008 0.6 48 0.35 143 15 Average 0.018 1.2 71 0.49 159 19 Max 0.039 1.9 117 0.62 172 24

Figure 8 - Time series plot of ambient monitoring data for methane and total oxidisable sulphur CONCLUSIONS Methane emissions at WWTPs are balanced between point sources and area sources, the former being mainly associated with inlet fugitives and anaerobic digestion. Examination of area sources indicates that the strict conditions of methanogenesis may have been met in the inlet area of the primary sedimentation tanks. It is postulated that this may be due to the collection of settled primary sludge directly below this point. Point sources are particularly difficult to quantify in a WWTP and it is important to recognise the potential for fugitives. Ambient monitoring at a point close to the WWTP can provide a useful means of assessing total emissions from the plant and comparing them with on site emission measurements. Methane emissions from this plant appear to represent approximately 122 tonnes/yr or a carbon dioxide equivalent of 2560 tonnes/yr. Assuming that the equivalent population of this plant can be expanded to represent the entire state this gives a statewide emission of approximately 7600 tonnes/yr (CO2e) or 1.1% of total anthropogenic methane contributions. ACKNOWLEDGEMENTS The authors would like to acknowledge the Water Corporation and Steve Wills (Ecotech Pty Ltd) who designed, installed and maintained the continuous monitoring equipment. REFERENCES Augenbraun H., Matthews E and Sarma D. (1999). Inventory of Methane Emissions Institute of Climate and Planets and published on the Web http://icp.giss.nasa.gov/research/methane/inventory/html. Australian Greenhouse Office (2001), State Emission Inventories, as published on the Web - http://www.greenhouse.gov.au/inventory/inventory/stateinv/wa.html Gwynne C., Phillips L., Turner N. and Goldstone M. (2002) Temporal and spatial variability of wastewater treatment plant odours in Western Australia. Enviro 2002, Melbourne Vic. 2002.

CONTACT Mark Goldstone GHD Pty Ltd 239 Adelaide Terrace, Perth 6004, Western Australia 08 9429 6558 08 9429 6555 mgoldstone@ghd.com.au