Application of titration methods for measuring the contents of ammonium nitrogen and volatile fatty acids in agricultural biogas plants

•To evaluate volatile fatty acids, the Purser et al. method was positively validated.•Validation was done for the plant substrates.•Purser et al. method is recommended for agricultural biogas plants.•A method for evaluating the ammonium nitrogen (NH4-N) content was developed.•The NH4-N evaluation method gives good results for substrates with a stable composition. The aim of our research was to assess a relatively new method of estimating ammonium nitrogen concentration in anaerobic digestion of plant substrates. We analysed our own data, received from the anaerobic digestion of maize silage (PM), as well as data published by Purser et al. (2014) who measured energy crops and slurry (ECS), and food waste (FW). In our study, the process was monitored for VFA content that was determined by gas chromatography, and for the content of ammonium nitrogen determined using the HACH LANGE LCK 303 cuvette test. We created polynomial regression models that bind the content of ammonium nitrogen with the volume of H2SO4 used to titrate the sample from initial pH to pH 5. To estimate parameters of model, the PM dataset was used. The obtained models were positively validated using ECS and FW datasets. Our results confirmed the effectiveness of the Purser et al. method with an average absolute error of less than 223mgl−1 of the VFA concentration, which was approximately 20-times less than the level that caused inhibition. In conclusion, we can affirm the suitability of using titration methods to assess the ammonium nitrogen content of bioreactors with a stable composition.