The degradation kinetics of normal and branched chain butyrate and valerate are important in protein-fed anaerobic systems, as a number of amino acids degrade to these organic acids. Including activated and primary wastewater sludge digesters, the majority of full-scale systems digest feeds with a significant or major fraction of COD as protein. This study assesses the validity of using a common kinetic parameter set and biological catalyst to represent butyrate, n-valerate, and i-valerate degradation in dynamic models. The i-valerate degradation stoichiometry in a continuous, mixed population system is also addressed, extending previous pure-culture and batch studies. A previously published mathematical model was modified to allow competitive uptake of i-valerate, and used to model a thermophilic manure digester operated over 180 days. The digester was periodically pulsed with straight and branched chain butyrate and valerate. Parameters were separately optimized to describe butyrate, i-valerate, and n-valerate degradation, as well as a lumped set optimized for all three substrates, and nonlinear, correlated parameter spaces estimated using an F distribution in the objective function (J). Each parameter set occupied mutually exclusive parameter spaces, indicating that all were statistically different from each other. However, qualitatively, the influence on model outputs was similar, and the lumped set would be reasonable for mixed acid digestion. The main characteristic not represented by Monod kinetics was a delay in i-valerate uptake, and was compensated for by a decreased maximum uptake rate (k(m)). Therefore, the kinetics need modification if fed predominantly i-valerate. Butyrate (i- and n-) and n-valerate could be modeled using stoichiometry consistent with beta-oxidation degradation pathways. However, i-valerate produced acetate only, supporting the stoichiometry of a reaction determined by other researchers in pure culture. Therefore, lumping i-valerate stoichiometry with that of n-valerate will not allow good system representation, especially when the feed consists of proteins high in leucine (which produces i-valerate), and the modified model structure and stoichiometry as proposed here should be used. This requires no additional kinetic parameters and one additional dynamic concentration state variable (i-valerate) in addition to the variables in the base model.

A complex and fast dynamic response of the anaerobic biogas system was observed when the system was subjected to pulses of volatile fatty acids (VFAs). It was shown that a pulse of specific VFAs into a well-functioning continuous stirred tank reactor (CSTR) system operating on cow manure affected both CH(4) yield, pH, and gas production and that a unique reaction pattern was seen for the higher VFAs as a result of these pulses. In this study, two thermophilic laboratory reactors were equipped with a novel VFA-sensor for monitoring specific VFAs online. Pulses of VFAs were shown to have a positive effect on process yield and the levels of all VFA were shown to stabilize at a lower level after the biomass had been subjected to several pulses. The response to pulses of propionate or acetate was different from the response to butyrate, iso-butyrate, valerate, or iso-valerate. High concentrations of propionate affected the degradation of all VFAs, while a pulse of acetate affected primarily the degradation of iso-valerate or 2-methylbutyrate. Pulses of n-butyrate, iso-butyrate, and iso-valerate yielded only acetate, while degradation of n-valerate gave both propionate and acetate. Product sensitivity or inhibition was shown for the degradation of all VFAs tested. Based on the results, it was concluded that measurements of all specific VFAs are important for control purposes and increase and decrease in a specific VFA should always be evaluated in close relationship to the conversion of other VFAs and the history of the reactor process. It should be pointed out that the observed dynamics of VFA responses were based on hourly measurements, meaning that the response duration was much lower than the hydraulic retention time, which exceeds several days in anaerobic CSTR systems.

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A key parameter for understanding and controlling the anaerobic biogas process is the concentration of volatile fatty acids (VFA). However, this information has so far been limited to off-line measurements using labor-intensive methods. We have developed a new technique that has made it possible to monitor VFA on-line in one of the most difficult media: animal slurry or manure. A novel in situ filtration technique has made it possible to perform microfiltration inside a reactor system. This filter enables sampling from closed reactor systems without large-scale pumping and filters. Furthermore, due to its small size it can be placed in lab-scale reactors without disturbing the process. Using this filtration technique together with commercially available membrane filters we have constructed a VFA sensor system that can perform automatic analysis of animal slurry at a frequency as high as every 15 minutes. Reproducibility and recovery factors of the entire system have been determined. The VFA sensor has been tested for a period of more than 60 days with more than 1,000 samples on both a full-scale biogas plant and lab-scale reactors. The measuring range covers specific measurements of acetate, propionate, iso-/n-butyrate and iso-/n-valerate ranging from 0.1 to 50 mM (6-3,000 mg). The measuring range could readily be expanded to more components and both lower and higher concentrations if desired. In addition to the new VFA sensor system, test results from development and testing of the in situ filtration technique are being presented is this article.