Natural fluorescence emission - an indirect measurement of applied ozone dosages to remove pharmaceuticals in biologically treated wastewater.

This study investigated the feasibility of UV-absorbance and fluorescence as monitoring tools for ozone dosages applied to effluents from wastewater treatment plans (WWTPs). Secondary treated effluents from five Swedish WWTPs underwent ozonation (at dosages ranging 0.5-12.0 mg O3/L) in bench-scale experiments. Correlations between ozone dosages and UV-absorbance at 254 and 272 nm were extrapolated with the first one being preferential for the wastewaters used because of its higher signal. UV-absorbance could detect differences in the applied ozone dosage as low as 1 mg/L, making it suitable to monitor effluent ozone treatment processes. Next, fluorescence was investigated at wavelength transitions that have being associated with humic-like fluorescents (Ex249Em450 and Ex335Em450) and protein-like fluorescents (Ex275Em340 and Ex231Em360 and Ex231Em315 and Ex275Em310). The Ex249Em450 transition was found to have the highest signal in all effluents and the best linear regression fitting with the ozone dosages over a wide range. However, low ozone dosages (0.5-3.0 mg O3/L), Ex335Em450 wavelength transition showed a more constant slope among the different domestic wastewater samples with slightly better R 2 values than the Ex249Em450 transition. Fluorescence removal via ozonation correlated with the pharmaceutical removal; however, the wellness of fitting was directly dependent on the pharmaceuticals' reactivity with ozone. Pharmaceuticals with moderate reactivity towards ozone appeared to be linearly correlated with the Ex249Em450 transition, while very reactive or recalcitrant pharmaceuticals had an exponential or a parabolic dependency. This means that fluorescence can potentially be used as a qualitative tool for pharmaceutical removal. Abbreviations: APIs, Active Pharmaceutical Ingredients; DOM, Dissolved organic matter; WWTPs, wastewater treatment plans; NOM, Natural organic matter; UV, Ultra-Violet light; DOC, Dissolved organic carbon.

Ozonation control and effects of ozone on water quality in recirculating aquaculture systems.

To address the undesired effect of chemotherapeutants in aquaculture, ozone has been suggested as an alternative to improve water quality. To ensure safe and robust treatment, it is vital to define the ozone demand and ozone kinetics of the specific water matrix to avoid ozone overdose. Different ozone dosages were applied to water in freshwater recirculating aquaculture systems (RAS). Experiments were performed to investigate ozone kinetics and demand, and to evaluate the effects on the water quality, particularly in relation to fluorescent organic matter. This study aimed at predicting a suitable ozone dosage for water treatment based on daily ozone demand via laboratory studies. These ozone dosages will be eventually applied and maintained at these levels in pilot-scale RAS to verify predictions. Selected water quality parameters were measured, including natural fluorescence and organic compound concentration changes during ozonation. Ozone reactions were described by first order kinetics. Organic matter, assessed as chemical oxygen demand and fluorescence, decreased by 25% (low O3), 30% (middle O3) and 53% (high O3), while water transmittance improved by 15% over an 8-day period. No fish mortality was observed. Overall, this study confirms that ozone can improve RAS water quality, provides a better understanding of the ozone decay mechanisms that can be used to define further safe ozone treatment margins, and that fluorescence could be used as a monitoring tool to control ozone. This study might be used as a tool to design ozone systems for full-scale RAS by analysing water sample from the specific RAS in the laboratory.

Use of fluorescence spectroscopy to control ozone dosage in recirculating aquaculture systems.

The aim of this study was to investigate the potential of fluorescence spectroscopy to be used as an ozone dosage determination tool in recirculating aquaculture systems (RASs), by studying the relationship between fluorescence intensities and dissolved organic matter (DOM) degradation by ozone, in order to optimise ozonation treatment. Water samples from six different Danish facilities (two rearing units from a commercial trout RAS, a commercial eel RAS, a pilot RAS and two marine water aquariums) were treated with different O3 dosages (1.0-20.0 mg/L ozone) in bench-scale experiments, following which fluorescence intensity degradation was eventually determined. Ozonation kinetic experiments showed that RAS water contains fluorescent organic matter, which is easily oxidised upon ozonation in relatively low concentrations (0-5 mg O3/L). Fluorescence spectroscopy has a high level of sensitivity and selectivity in relation to associated fluorophores, and it is able to determine accurately the ozone demand of each system. The findings can potentially be used to design offline or online sensors based on the reduction by ozone of natural fluorescent-dissolved organic matter in RAS. The suggested indirect determination of ozone delivered into water can potentially contribute to a safer and more adequate ozone-based treatment to improve water quality.

Secondary formation of disinfection by-products by UV treatment of swimming pool water.

Formation of disinfection by-products (DBPs) during experimental UV treatment of pool water has previously been reported with little concurrence between laboratory studies, field studies and research groups. In the current study, changes in concentration of seven out of eleven investigated volatile DBPs were observed in experiments using medium pressure UV treatment, with and without chlorine and after post-UV chlorination. Results showed that post-UV chlorine consumption increased, dose-dependently, with UV treatment dose. A clear absence of trihalomethane formation by UV and UV with chlorine was observed, while small yet statistically significant increases in dichloroacetonitrile and dichloropropanone concentrations were detected. Results indicate that post-UV chlorination clearly induced secondary formation of several DBPs. However, the formation of total trihalomethanes was no greater than what could be replicated by performing the DBP formation assay with higher chlorine concentrations to simulate extended chlorination. Post-UV chlorination of water from a swimming pool that continuously uses UV treatment to control combined chlorine could not induce secondary formation for most DBPs. Concurrence for induction of trihalomethanes was identified between post-UV chlorination treatments and simulated extended chlorination time treatment. Trihalomethanes could not be induced by UV treatment of water from a continuously UV treated pool. This indicates that literature reports of experimentally induced trihalomethane formation by UV may be a result of kinetic increase in formation by UV. However, this does not imply that higher trihalomethane concentrations would occur in pools that apply continuous UV treatment. The bromine fraction of halogens in formed trihalomethanes increased with UV dose. This indicates that UV removes bromine atoms from larger molecules that participate in trihalomethane production during post-UV chlorination. Additionally, no significant effect on DBP formation was observed due to photo-inducible radical forming molecules NO3- (potentially present in high concentrations in pool water) and H2O2 (added as part of commercially employed DBP reducing practices).

Required ozone doses for removing pharmaceuticals from wastewater effluents.

The aim of the this study was to investigate the ozone dosage required to remove active pharmaceutical ingredients (APIs) from biologically treated wastewater of varying quality, originated from different raw wastewater and wastewater treatment processes. Secondary effluents from six Swedish wastewater treatment plants (WWTP) were spiked with 42 APIs (nominal concentration µg/L) and treated with different O3 doses (0.5-12.0 mg/L ozone) in bench-scale experiments. In order to compare the sensitivity of APIs in each matrix, the specific dose of ozone required to achieve reduction by one decade of each investigated API (DDO3) was determined for each effluent by fitting a first order equation to the remaining concentration of API at each applied ozone dose. Ozone dose requirements were found to vary significantly between effluents depending on their matrix characteristics. The specific ozone dose was then normalized to the dissolved organic carbon (DOC) of each effluent. The DDO3/DOC ratios were comparable for each API between the effluents. 15 of the 42 investigated APIs could be classified as easily degradable (DDO3/DOC ≤ 0.7), while 19 were moderately degradable (0.7 < DDO3/DOC ≤ 1.4), and 8 were recalcitrant towards O3-treatment (DDO3/DOC >1.4). Furthermore, we predict that a reasonable estimate of the ozone dose required to remove any of the investigated APIs may be attained by multiplying the experimental average DDO3/DOC obtained with the actual DOC of any effluent.