Development of headspace-gas chromatography-flame ionization detection procedure to determine volatile fatty acids in zoo organic waste leachates

In order to determine volatile fatty acids (short chain monocarboxylic acids with 2 to 6 carbon atoms in a molecule) in leachates formed in organic waste piles a procedure based on static headspace (HS) coupled with gas chromatography (GC) have been proposed and optimized. The conditions of HS extraction and sample introduction into a gas chromatograph as well as of chromatographic separation were considered. Using flame ionization detection LODs were of the order of 0.02-0.37 mg/L. The analyzed leachate collecting on and close to a zoo organic waste pile contained VFAs (Volatile Fatty Acids) at a concentration ranging from 5.5 mg/L to 0.88 g/L and from below LOD to 10.1 mg/L for pool water at some distance from the pile, respectively.     

The effect of temperature on the performance and stability of thermophilic anaerobic digestion.

Sustainable operation of an anaerobic sewage sludge digester requires the effective shuttling of carbon from complex organic material to methane gas. The accumulation of intermediates and metabolic products such as volatile fatty acids and hydrogen gas not only reveal inefficiency within the digestion process, but can be detrimental to reactor operation at sufficiently high levels. Eight anaerobic digesters (1 mesophilic and 7 thermophilic) were operated in order to determine the effect of steady-state digestion temperature on the operational stability and performance of the digestion process. Replicate reactors operated at 57.5 degrees C, the highest temperature studied, were prone to accumulation of volatile fatty acids (4052 and 3411 mg/L as acetate) and gaseous hydrogen. Reactors operated at or below 55 degrees C showed no such accumulation of intermediate metabolites. Overall methanogenesis was also greatly reduced at 57.5 degrees C (0.09 L CH4/g VS fed) versus optimal methane formation at 53 degrees C (0.40 L CH4/g VS fed). Microbial community assessment and free energy calculations suggest that the accumulation of fatty acids and hydrogen, and relatively poor methanogenic performance at 57.5 degrees C are likely due to temperature limitations of thermophilic aceticlastic methanogens.     

Odour emission ability (OEA) and its application in assessing odour removal efficiency

Odourous emissions from sewer networks and wastewater treatment plants (WWTPs) can significantly impact a local population. Sampling techniques such as wind tunnels and flux hood chambers are traditionally used to collect area source samples for subsequent quantification of odour emission rates using dilution olfactometry, however these methods are unsuitable for assessing liquid samples from point sources due to the large liquid volumes required. To overcome this limitation, a gas phase sample preparation method was developed for assessing the total Odour Emission Ability (OEA) from a liquid sample. The method was validated using two volatile organic sulphur compounds (VOSCs), dimethyl-trisulphide (DMTS) and bismethylthiomethane (BMTM) that are frequently detected from sewers and WWTPs and are relatively stable compared with common VOSCs like mercaptan or methyl mercaptan. The recovery rates of DMTS and BMTM were quantified by injecting a known volume of a standard liquid sample into Tedlar bags using a static injection and a dynamic injection methodology. It was confirmed that both dynamic and static injection methods at ambient condition achieved high recovery rates with no need to consider increasing evaporation by elevating the temperature. This method can also be used to assess odour removal effectiveness of liquids by comparing the OEA before and after the treatment tests. Two application examples were presented.     

Optimizing volatile fatty acid production in partial acidogenesis of swine wastewater.

This research has been conducted based on the fact that acetic and butyric acids are favorable substrates for methanogens, and that a low level of propionic acid production during acidogenesis minimizes the inhibition effect on methanogenic growth. Raw swine wastewater was pretreated with ammonia stripping to enhance acidogenesis. The ammonia nitrogen concentration of less than 1.2 g/L did not significantly affect the biochemical acidogenic potential of swine wastewater. For acidogenesis of swine wastewater, a set of experiments were carried out to produce short chain volatile fatty acids (VFA) in laboratory-scale continuously stirred tank reactors. The production of acetic, propionic, and butyric acids associated with simultaneous changes in hydraulic retention time (HRT) and temperature was investigated. Response surface methodology was successfully applied to approximate the responses of the VFA productions. The optimum physiological conditions where the maximum acetic and butyric acids production occurred were 2.4 days HRT at 34 degrees C and 2.1 days HRT at 35 degrees C, respectively. The propionic acid production linearly increased as both HRT and temperature increased.     

Effect of primary sludge fermentation products on mass balance for biological treatment.

Laboratory batch experiments were conducted at 20 degrees C to investigate the potential of primary sludge fermentation for the generation of readily biodegradable substrate and to evaluate the effect of fermentation products on mass balance for organic carbon, nitrogen and phosphorus, emphasizing COD fractionation. Fermentation converted between 18 to 30% of the initial volatile suspended solids in the sludge into soluble biodegradable COD. The volatile fatty fraction of the soluble COD was approximately 85% after the fermentation process. The average volatile fatty acid composition in fermentation involved 50% acetic acid, 33% propionic acid, 9% butyric acid and 8% valeric acid, indicating that the most important volatile fatty acid obtained during the biological fermentation process was acetate with more than half of total VFA concentration, which is one of the most important carbon sources for denitrification and biological nutrient removal processes. The recoverable fraction of the fermented sludge supernatant could potentially increase the readily biodegradable COD content of the primary effluent by 5%, together with a potential increase of the soluble nitrogen and phosphorus content by 2%.     

Intracellular biopolymer productions using mixed microbial cultures from fermented POME.

This study aimed to produce polyhydroxyalkanoates (PHAs) from organic wastes by mixed bacterial cultures using anaerobic-aerobic fermentation systems. Palm oil mill effluent (POME) was used as an organic source, which was cultivated in a two-step-process of acidogenesis and acid polymerization. POME was operated in a continuous flow anaerobic reactor to access volatile fatty acids (VFAs) for PHAs production. During fermentation, VFA concentration was produced in the range of 5 to 8 g/L and the COD concentration reduced up to 80% from 65 g/L. The VFA from anaerobic fermentation was then utilised for PHA production using a mixed culture in availability of aerobic bioreactor. Production of PHAs was recorded high when using a high volume of substrates because of the higher VFA concentration. Even though the maximum PHA content was observed at only 40% of the cell dried weight (CDW), their production and performance are significant in mixed microbial culture.     

Effects of solids concentration, pH and carbon addition on the production rate and composition of volatile fatty acids in prefermenters using primary sewage sludge.

Increasing evidence is emerging that the performance of enhanced biological phosphorus removal (EBPR) systems relies on not only the total amount but also the composition of volatile fatty acids (VFAs). Domestic wastewater often contains limited amounts of VFAs with acetic acid typically being the dominating species. Consequently, prefermenters are often employed to generate additional VFAs to meet the demand for carbon by EBPR and/or denitrification processes. Limited knowledge is currently available on the effects of operational conditions on the production rate and composition of VFAs in prefermenters. In this study, a series of controlled batch experiments were conducted with sludge from a full-scale prefermenter to determine the impact of solids concentration, pH and addition of molasses on prefermentation processes. It was found that an increase in solids concentration enhanced total VFA production with an increased propionic acid fraction. The optimal pH for prefermentation was in the range of 6-7 with significant productivity loss when pH was below 5.5. Molasses addition significantly increased the production of VFAs particularly the propionic acid. However, the fermentation rate was likely limited by the biological activity of the sludge rather than by the amount of molasses added.     

Modifying ADM1 to include formation and emission of odourants.

A mathematical model that is based upon the ADM1 structure has been developed to describe the formation and emission of odourous compounds in anaerobic sludge digestion. Special emphasis is given to the general mechanisms for the formation of common odorous sulfur compounds that are found in anaerobic digesters: methyl mercaptan, dimethyl sulfide and hydrogen sulfide, as well as volatile fatty acids and ammonia. The model includes multiple-reaction stoichiometry, microbial growth kinetics and conventional material balances for an ideally mixed reactor. Simulations that were performed with the model revealed that changes in common operational parameters such as temperature, HRT and sludge metal content can dramatically impact upon the gas phase concentrations of odourants. Additional research is required to reduce uncertainty in the model formulation.     

Understanding odorants associated with compost, biomass facilities, and the land application of biosolids.

Odorous water and air can result from compost, biomass facilities and land application of biosolids. Common odorous compounds from these biodegradation systems include alcohols, aldehydes, fatty acids, solvents and various sulfur and nitrogen compounds. Each odorant possesses a unique individual odor signature i.e. odor character or quality, odor threshold concentration and chemical concentration. This paper develops an initial understanding of how the volatile odorous chemicals and their relative concentrations produced are related to the total odor quality from the process by their odor threshold concentrations. The compost process is used as an example. It was estimated, that on day 1 and 7, the primary fatty acids controlling the fermented and rotten odors were butyric acid and valeric acids, individually, unpleasant and rancid odors, respectively, although acetic acid had the highest fatty acid concentration on both days. In the same way, aldehydes and ketones controlled the disappearance of the sweet odor from day 1 to 7.     

Determination of long chain fatty acids in anaerobic digesters using a rapid non-derivatisation GC-FID method

A rapid non-derivatisation gas chromatographic (GC) method for quantification of palmitic, stearic and oleic acids was achieved using a flame ionisation detector and a highly polar capillary column at elevated temperature. These long chain fatty acids (LCFA) can accumulate in anaerobic digesters and a simple extraction method was also developed to permit a more rapid sample turn-around time, facilitating more frequent monitoring. The GC method was satisfactory in terms of peak separation, signal response, reproducibility and linearity range. The extraction method achieved recoveries of 103.8, 127.2 and 84.2% for palmitic, stearic and oleic acid respectively. The method was tested on digestate from mesophilic laboratory-scale digesters fed with source-segregated domestic food waste, and showed good repeatability between replicate samples. It was observed that the concentrations of stearic and palmitic acid in digesters routinely supplemented with trace elements were lower in proportion to the applied lipid loading than those without supplementation.     

Population dynamics of anaerobic microbial consortia in thermophilic methanogenic sludge treating paper-containing solid waste.

To maintain a stable thermophilic (55 degrees C) anaerobic digestion treating toilet paper-containing garbage, it is necessary to operate the digester at long hydraulic retention time (HRT) and low organic loading rate (OLR). Critical conditions of the digestion were investigated by operating the digester at HRT 23 days and OLR 3.4 gCOD(Cr)/L/d (R1) or HRT 14 days and OLR 5.6 gCOD/Cr)/L/d (R2) separately. Characteristics of methanogenesis of the two digesters were examined by measuring gas generation volume and volatile fatty acids (VFA) concentration, and the populations of four anaerobic acidogens and three methanogens were analyzed using quantitative PCR method. In digester R1, methanogenic activity was unstable but it could be recovered by stopping feeding as though VFA accumulation occurred. The population of acidogens and two methanogens were maintained at 10(11) - 10(13) copies/L, however, the population of Methanoculleus could not be recovered after methanogenesis recovering. In digester R2, the period of methanogenesis was significantly shorter than that in digester R1. Both the acidogens and the methanogens could not be maintained at a stable concentration. It is suggested that the critical HRT to sustain the population of acidogens in this process should be longer than 14 days and for all kinds of methanogens, HRT should be longer than 23 days.     

Continuous hydrogen production from organic waste.

The antibiotic effects of lactic acid bacteria, Lactobacillus paracasei, on hydrogen production were investigated using glucose as the substrate for the batch experiments. The effects of lactic acid bacteria on hydrogen fermentation depended on pH and the inhibition of hydrogen-producing bacteria was prevented by keeping the pH over 5.0. Then, a continuous hydrogen production experiment was conducted by using bean curd manufacturing waste as an actual organic waste at pH 5.5 at 35 degrees C. The increase of the substrate concentration and the addition of nitrogen gave precedence to acetic and butyric acids production in the metabolic pathway and suppressed propionic acid production. As the result, continuous hydrogen production from municipal organic waste was enabled.     

Anaerobic monodigestion of poultry manure: determination of operational parameters for CSTR

In this work the anaerobic monodigestion for the treatment of turkey manure was evaluated, without its codigestion with another substrate. The effect of the organic loading rate (OLR) and the substrate concentration (high total solids (TS) concentration) or product concentration (high volatile fatty acids (VFA) and/or ammonia (NH(3)-N) concentrations) was studied. The results show that for a continuous stirred tank reactor (CSTR) operation, a maximum of 40 g/L of TS and 4.0 g/L of ammonium (NH(4)(+)) was required. In addition, the maximum organic loading rate (OLR) will not exceed 1.5 kg VS/m(3)d. Higher TS and NH(4)(+) concentrations and OLR lead to a reduction on the methane productivity and volatile solids (VS) removal. During the CSTR operation, a high alkalinity concentration (above 10 g/L CaCO(3)) was found; this situation allowed maintaining a constant and appropriate pH (close to 7.8), despite the VFA accumulation. In this sense, the alkalinity ratio (α) is a more appropriate control and monitoring parameter of the reactor operation compared to pH. Additionally, with this parameter a VS removal of 80% with a methane productivity of 0.50 m(3)(CH4)/m(3)(R)d is achieved.     

Application of Methanobrevibacter acididurans in anaerobic digestion.

To operate anaerobic digesters successfully under acidic conditions, hydrogen utilizing methanogens which can grow efficiently at low pH and tolerate high volatile fatty acids (VFA) are desirable. An acid tolerant hydrogenotrophic methanogen viz. Methanobrevibacter acididurans isolated from slurry of an anaerobic digester running on alcohol distillery wastewater has been described earlier by this lab. This organism could grow optimally at pH 6.0. In the experiments reported herein, M. acididurans showed better methanogenesis under acidic conditions with high VFA, particularly acetate, than Methanobacterium bryantii, a common hydrogenotrophic inhabitant of anaerobic digesters. Addition of M. acididurans culture to digesting slurry of acidogenic as well as methanogenic digesters running on distillery wastewater showed increase in methane production and decrease in accumulation of volatile fatty acids. The results proved the feasibility of application of M. acididurans in anaerobic digesters.     

Effects of transient temperature increases on odor production from thermophilic anaerobic digestion.

The City of Los Angeles, Bureau of Sanitation, has implemented thermophilic anaerobic sludge digestion at the Hyperion and Terminal Island Treatment Plants (HTP and TITP). A two-stage continuous-batch process was established at HTP, while a single-stage sequencing batch process was established at TITP. This was to evaluate compliance with the Class A pathogen reduction requirements of U.S. EPA 40 CFR Part 503. A rapid increase of the digester temperature at TITP from 57.5 to 65.5 degrees C caused an increase of the volatile fatty acid to alkalinity ratio, a decline in digester performance, and an elevated production of methyl mercaptan and hydrogen sulfide. A rapid increase of the digester temperature at HTP from 54 to 58 degrees C caused an elevated production of methyl mercaptan, but the effect on the volatile fatty acid to alkalinity ratio and digester performance was insignificant. It is likely that these effects observed at TITP and HTP were transient responses to rapid changes in temperature.     

Use of headspace solid-phase microextraction to characterize odour compounds in subsurface flow constructed wetland for wastewater treatment.

A headspace solid-phase microextraction (HS-SPME) preconcentration method was applied to the analysis of some of the major odorous compounds occurring in wastewater using GC/MS or GC/NPD detection. The detection limit for volatile amines, volatile fatty acids, and volatile alkylsulphides ranged from 3 to 100, 2 to 150, and 0.0006 to 0.035 microg/L, respectively. The SPME method was used to examine the fate of odorous compounds in the subsurface flow constructed wetlands (SFCW) operated under different hydraulic loading rate (HLR), bed aspect ratio, and granular medium size. Among the experimental conditions evaluated in the SFCW beds, HLR was found to be the most important factor influencing the evolution of the studied compounds. There were also significant differences among bed types in the behaviour of ammonia (NH3), acetic acid (Ac), isovaleric acid (IsoA), propionic acid (PrA), and dimethylsulphide. Aspect ratio and medium granular size were minor factors influencing SFCW performance. The major odour compounds by mass in the effluent of SFCW with different operational conditions were NH3 and Ac. Further removal of these two compounds is considered as very important from the viewpoint of chemical composition. On the other hand, Relative Odour Intensity (ROI: ratio between the absolute concentration to the odour threshold concentration) suggested that PrA and IsoA were the two major compounds responsible for odour intensity. Thus, further removal of these two compounds is viewed as very important for the effluent deodorization, especially for PrA. From our results, this compound appears to be produced by processes occurring in the SFCW.     

Acidogenic fermentation of municipal solid waste and its application to bio-electricity production via microbial fuel cells (MfCs)

Acidogenic fermentation of organic municipal solid waste (MSW) and the bio-electricity production potential from its volatile fatty acid (VFA)-rich leachate using an air-cathode microbial fuel cell (MFC) was investigated in this study. The acidogenic fermentation of 2 kg of MSW has been carried out in a 6 L anaerobic leach-bed reactor (LBR) under mesophilic conditions (30 degrees C). Total production of 92 g VFA expressed as chemical oxygen demand (COD) in 3 L leachate mainly containing acetic, propionic, butyric, and valeric acids has been achieved with manual leachate recirculation and without pH control in 74 days of incubation. Leachate collected on day 32 was used as a feed to an air-cathode MFC after being diluted and supplemented with NaCl or NaHCO3. The maximum power density in the diluted leachate was only 5.9 W/m3, but reached up to 8.6 W/m3 upon the addition of 7 mmol/L NaCl. Increase in coulombic efficiency from 6 to 22% was also observed as a result of NaCl supplementation. On the other hand, NaHCO3 addition did not improve the power output.     

Modelling anaerobic digestion of concentrated black water and faecal matter in accumulation system

A dynamic mathematical model based on anaerobic digestion model no. 1 (ADM1) was developed for accumulation (AC) system treating concentrated black water and faecal matter at different temperatures. The AC system was investigated for the treatment of waste (water) produced from the following systems: vacuum toilet for black water (VBW), vacuum toilet for faeces with urine separation (VF), dry toilet (DT), dry toilets for faeces with urine separation (DF), separated faecal matter from conventional black water by filter bag (FB). For evaluation of the AC system treating the proposed waste (water) sources at 20 and 35 degrees C, two options were studied: (1) The filling period of the AC system was constant for all waste (water) sources (either 1, 3 or 6 months) and for each period, the seed sludge volume was varied; (2) The volume of the AC system was constant for all proposed waste (water) sources. The results showed that the filling period of the AC system was the main parameter affecting the system performance, followed by operational temperature, while the increase of the seed sludge volume slightly enhanced the performance of the system. The model results indicated that the filling period of the AC system should be higher than 150 days for obtaining a stable performance. It was found that the hydrolysis of biodegradable particulate chemical oxygen demand (COD) is the rate limiting step, as volatile fatty acid concentration is very low in all experimental conditions (< 200 mgCOD/L at 20 degrees C and < 100 mgCOD/L at 35 degrees C). Based on the results of the two options, it was found that the concentrated waste (water) sources have better performance than the diluted waste (water) sources, like VBW waste (water). Furthermore, smaller volume will be required for the AC system.     

Effect of operating conditions and reactor configuration on efficiency of full-scale biogas plants.

A study on 18 full-scale centralized biogas plants was carried out in order to find significant operational factors influencing productivity and stability of the plants. It was found that the most plants were operating relatively stable with volatile fatty acids (VFA) concentration below 1.5 g/l. VFA concentration increase was observed in occasions with dramatic overloading or other disturbances such as operational temperature changes. Ammonia was found to be a significant factor for stability. A correlation between increased residual biogas production and high ammonia was found. When ammonia was higher than approx. 4g-N/l the degradation efficiency of the plant decreased and as a consequence, the residual methane potential was high. Decrease of the residual methane potential with increasing hydraulic retention time was found. Digestion temperature was very important for effective post-digestion. Post-digestion for recovering the residual methane potential at temperatures below 15 degrees C was very inefficient.     

Automated equipment for anaerobic sludge parameters determination.

Methanogenic activity, anaerobic biodegradability and toxicity are key parameters in the design and operation of anaerobic bioreactors. A large variety of methods exist for the determination of these parameters but a normalized method has not been established so far. This paper presents the development of an automated manometric system for the determination of these anaerobic sludge parameters. The system is based on monitoring the production of methane by using a pressure transducer that measures the pressure in a gas-collecting chamber of known adjustable volume, which is independent of the space where biogas production takes place. The evolution of pressure generated by the accumulation of methane relates to the conversion of COD. In this way, the methanogenic activity of the sludge can be determined, as well as the biodegradability of solids and liquid, as well as the methanogenic toxicity of compounds. The equipment permits gas sampling, as well as extraction and introduction of liquid, without losing the anaerobic conditions. Various assays have been conducted to test the reliability and reproducibility of the obtained results, showing a high level of both. The methanogenic activities obtained in the assays ranged between 0.1 and 1.8 g COD g(-1) VSS d(-1), and the biodegradability of the organic compounds tested ranged between 20 and 90%.