The use of naturally generated volatile fatty acids for pesticide removal during the denitrification process
Thesis DisciplineCivil Engineering
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
The effect of naturally produced volatile fatty acids (VFAs) on the removal of 2, 4-D from a wastewater during the denitrification process was studied in this thesis. The VFAs were generated from an anaerobic digester using soya flour solution as a synthetic feed. The digester was operated at an SRT and HRT of 10 days. The pH (4.8 ± 0.2) and temperature (32 ± 3 ℃) of the digester were not controlled. A mean VFA concentration of 3153 ± 801 mg/L was achieved with acid speciation results of acetic (51.4 %), propionic (27.5 %), n-butyric (19.6 %) and iso-valeric (1.4 %). The specific VFA production rate was 0.014 mg VFA/mg VSS/day. The extent of the digestion process converting the substrate from a particulate to soluble form was evaluated as the specific TOC solubilization rate (0.007 mg TOC/mg VSS/day), soluble COD production rate (0.022 mg SCOD/mg VSS/day) and percent VSS reduction (14 %). The low solubilization rate is possibly due to high feed solids (3.4%) which led to a heavily overloaded bioreactor. It also suggests that the particulate substrate was not entirely amenable to solubilization. The acclimation of 2, 4-D degrading bacteria was developed successfully in an SBR fed with sewage and 2, 4-D (30-100 mg/L) as carbon and energy sources. A mean MLSS of 3653 ± 547 mg/L and an SRT of 20 ± 9 days were observed during the research period. The settleability of the SBR sludge was excellent evidenced by a low sludge volume index (SVI) of 101 ± 50 mL/g and less than 5 mg/L of effluent suspended solids. The specific 2, 4-D degradation rate was 0.046 ± 0.018 mg/mg MLSS/day. However, the removal of 2, 4-D during 60 minutes of non-aerated phase was negligible while more than 90 % of the 2, 4-D was removed within 240 minutes of the aerated phase. The successful degradation of 2, 4-D is related to the length of the acclimation period, as the acclimation period increased, the specific biodegradation rate increased. A biosorption study using ultrasound pre-treatment of the SBR acclimated biomass suggested that less than 10 % of the removal of 2, 4-D was due to biosorption, while more than 90 % removal of the 2, 4-D was likely due to biodegradation. Denitrification batch tests (using SBR-acclimated biomass) demonstrated that the addition of a digester effluent rich in naturally-produced VFAs increased both the 2 specific denitrification rate and the 2, 4-D degradation efficiency, as compared to that using 2, 4-D as a sole carbon source. In particular, the specific denitrification rates increased from 0.0119 ± 0.0039 to 0.0192 ± 0.0079 to 0.024 ± 0.003 g NO₃-N/g VSS per day, when using 2, 4-D alone, 2, 4-D plus natural VFAs and natural VFAs alone as carbon sources. The percent 2, 4-D removal increased from 28.33 ± 11.88 using 2, 4-D alone as a carbon source to 54.17 ± 21.89 using 2, 4-D plus natural VFAs as carbon sources. The specific 2, 4-D degradation rate and 2, 4-D removal efficiency of unacclimated biomass were 2.0 to 2.5 times less than those of the acclimated biomass. Natural VFAs and synthetic VFAs were found to be identical in denitrification batch tests in terms of their use as a carbon source. The mean specific denitrification and VFA-C consumption rates as well as the mean specific 2, 4-D degradation rate derived from experiments using natural VFAs and 2, 4-D as carbon sources were close to the valuess from experiments using synthetic VFAs and 2, 4-D as carbon sources. Further exploration of 2, 4-D degradation behaviour with pulsed additions of NO₃-N did not find further significant 2, 4-D removal, although almost all of NO₃-N was used by the end of the experimental run due to endogenous carbon sources used for cell maintenance and growth. However, the higher the concentration of biomass used in the denitrification batch system, the larger the amount of 2, 4-D degraded and the faster the VFA-C and NO₃-N were consumed. Further research with respect to optimisation of the acid-phase anaerobic digestion process (e.g. to adjust SRT and HRT or to lower the solid content of synthetic feed) would improve the specific VFA production rate and the solubilization rate. More research on the SBR could be carried out to investigate its maximum 2, 4-D removal capability as well as the removal of other structurally related herbicides. Attempts could be made to stimulate the growth of denitrifiers in the SBR (e.g. to add certain amounts of NO₃-N according to proper C: N ratios or to increase the length of non-aerated time). More microbiological studies of 2, 4-D degrading bacteria may also be helpful to understand the combined SBR/denitrification and 2, 4-D degradation process. More theoretical aspects of modelling kinetics could be developed to apply the combined process in-situ at 2, 4-D contaminated sites.