To estimate the expectable enhanced biological phosphorus removal value of a wastewater, the concentration of volatile fatty acids (VFAs) and the biochemical acidogenic potential (BAP) are generally determined on grab samples of wastewater, as these variables are prone to rapid change after sampling. However, such sampling technique do not take into account the variations of these parameters during the day. This work has evaluated the changes of VFAs and BAP occurring during sampling and storage in an automatic sampler over 24 h. The consequences of waterfall oxygen input during sampling, and changes during storage (fermentation and sulfatereducing process) were studied. The results for two wastewaters showed that the sampling technique used for daily flow proportional composite samples provided a correct estimation of VFAs, and underestimated BAP by up to 25%. For hourly-average composite samples of wastewaters, significant modifications of the concentrations of these two parameters were recorded around the daily average values.

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