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Claire Bougrier, Audrey Battimelli, Jean-Philippe
Delgenes & Hélène Carrere (2007)
Combined Ozone Pretreatment and Anaerobic
Digestion for the Reduction of Biological Sludge
Production in Wastewater Treatment, Ozone: Science &
Engineering, 29:3, 201-206.
• The ever-increasing amount of solid waste generated by wastewater treatment
plants highlights emerging economic and environmental issues. Disposal
routes are narrowing: landfill is now forbidden for biodegradable waste,
agricultural spreading is strictly regulated and incineration remains
expensive. This situation explains the emphasis on the development of
processes for sludge minimization.

• In order to develop new processes producing less sludge, the use of ozone
combined with anaerobic digestion was investigated for waste activated
sludge treatment. This paper was aimed at evaluating the impact of ozone
pretreatment on anaerobic digestion and particularly the enhancement of
biogas production
• Sludge - Ozonation was performed on excess activated sludge originating
from a municipal wastewater treatment plant.
• Ozonation -Eight different ozone doses were applied, ranging from 0.015
g O3/g TS to 0.18 g O3/g TS, in a completely mixed reactor. The ozone
concentration in gas phases was measured with UV analyzers.
• Physicochemical Characteristics -Solubilization was ascertained by
solid fraction analysis. Soluble and particulate fractions were obtained after
centrifugation. Chemical Oxygen Demand (COD), Total Nitrogen content
(TN), Total Solid and Suspended Solid (TS, SS), pH and turbidity were
determined in accordance with Standard Methods.
• Batch Anaerobic Digestion- Sludge biodegradability was evaluated using
batch anaerobic digestion and the measurement of biogas volumes.
• Solubilization of Ozonated Sludge
COD and solids were used for the quantification of ozone’s effect on organic
and mineral matter.
sCOD increased strongly with the ozone dose, reaching 8.5 g/L with an ozone
dose of 0.18 g O3/g TS. Thus, the COD ratio of 4% for untreated sludge
increased to 49% with an ozone dose of 0.18 g O3/g TS. But no significant
mineralization was observed.
A significant decrease in suspended solids concentrations was observed: the
initial SS/TS ratio was 96% (for untreated sludge) and the minimal SS/TS ratio,
obtained for an ozone dose of 0.18 g O3/g TS, was 51%.
• Anaerobic Biodegradability Test
 Specific biogas production was calculated by dividing the net volume of
biogas (volume produced minus endogenous production) by the amount of
COD added in each sample.
Whatever the ozone dose, biogas production was higher than that for
untreated sludge: a minimum increase of 15% in biogas volume was obtained
with all ozone doses. These volumes were always lower than those recorded
for a completely biodegradable substrate (ethanol).
 Thus ozonation led to an increase in sludge biodegradability but the sludge
was not fully biodegraded during the experiment. Ozone pretreatment also
led to an acceleration of biogas production as well as an increase in the
quantity produced.
• Batch anaerobic digestion of ozonated sludge confirmed the positive impact
of sludge solubilization on biogas production. COD, solid and nitrogen
solubilization increased with the ozone dose. For an ozone dose of 0.18 g O3/g
TS, the soluble fraction (COD and solids) represented more than 50% of total
• Bigger biogas production was linked to organic soluble matter released
during oxidation by ozone. As organic substances became more easily
available, their biodegradability could be improved. For biogas production,
the optimal ozone dose seemed to be 0.15 g O3/g TS. This ozone dose led to a
144% increase in specific biogas production. The results suggest that an even
higher ozone dose was responsible for a decrease in biogas production.
• At medium doses, ozonation could be a suitable technique for excess activated sludge
treatment combined with anaerobic digestion. For an optimized process, the cost of
ozone should be compared to the enhancement of biogas production. Finally, the
economic viability of the ozone process should be compared to other techniques such as
enzymatic treatment or a thermochemical process.
• In wastewater treatment, to optimize the cost of a combined process, the biological step
should be maximized and the chemical step minimized. When a process combines
anaerobic digestion and ozonation, the objective is to convert solids into more easily
biodegradable matter in order to facilitate treatment in the biological reactor.
• ozone influences pH and in this study, the pH decreased from 6.7 to 5.1 as ozone doses
rose from 0.015 to 0.18 g O3/g TS. This confirms the oxidation of organic matter into more
oxygenated molecules, such as carboxylic acids. With the highest doses, the decrease in
pH may inhibit the biological activity.