Oxidation of 51 micropollutants during drinking water ozonation: Formation of transformation products and their fate during biological post-filtration.

Micropollutants (MP) with varying ozone-reactive moieties were spiked to lake water in the influent of a drinking water pilot plant consisting of an ozonation followed by a biological sand filtration. During ozonation, 227 transformation products (OTPs) from 39 of the spiked 51 MPs were detected after solid phase extraction by liquid chromatography high-resolution mass spectrometry (LC-HRMS/MS). Based on the MS/MS data, tentative molecular structures are proposed. Reaction mechanisms for the formation of a large number of OTPs are suggested by combination of the kinetics of formation and abatement and state-of-the-art knowledge on ozone and hydroxyl radical chemistry. OTPs forming as primary or higher generation products from the oxidation of MPs could be differentiated. However, some expected products from the reactions of ozone with activated aromatic compounds and olefins were not detected with the applied analytical procedure. 187 OTPs were present in the sand filtration in sufficiently high concentrations to elucidate their fate in this treatment step. 35 of these OTPs (19%) were abated in the sand filtration step, most likely due to biodegradation. Only 24 (13%) of the OTPs were abated more efficiently than the parent compounds, with a dependency on the functional group of the parent MPs and OTPs. Overall, this study provides evidence, that the common assumption that OTPs are easily abated in biological post-treatment is not generally valid. Nevertheless, it is unknown how the OTPs, which escaped detection, would have behaved in the biological post-treatment.

Effect of operational and water quality parameters on conventional ozonation and the advanced oxidation process O3/H2O2: Kinetics of micropollutant abatement, transformation product and bromate formation in a surface water.

The efficiency of ozone-based processes under various conditions was studied for the treatment of a surface water (Lake Zürich water, Switzerland) spiked with 19 micropollutants (pharmaceuticals, pesticides, industrial chemical, X-ray contrast medium, sweetener) each at 1 µg L-1. Two pilot-scale ozonation reactors (4-5 m3 h-1), a 4-chamber reactor and a tubular reactor, were investigated by either conventional ozonation and/or the advanced oxidation process (AOP) O3/H2O2. The effects of selected operational parameters, such as ozone dose (0.5-3 mg L-1) and H2O2 dose (O3:H2O2 = 1:3-3:1 (mass ratio)), and selected water quality parameters, such as pH (6.5-8.5) and initial bromide concentration (15-200 µg L-1), on micropollutant abatement and bromate formation were investigated. Under the studied conditions, compounds with high second-order rate constants kO3>104 M-1 s-1 for their reaction with ozone were well abated (>90%) even for the lowest ozone dose of 0.5 mg L-1. Conversely, the abatement efficiency of sucralose, which only reacts with hydroxyl radicals (OH), varied between 19 and 90%. Generally, the abatement efficiency increased with higher ozone doses and higher pH and lower bromide concentrations. H2O2 addition accelerated the ozone conversion to OH, which enables a faster abatement of ozone-resistant micropollutants. Interestingly, the abatement of micropollutants decreased with higher bromide concentrations during conventional ozonation due to competitive ozone-consuming reactions, except for lamotrigine, due to the suspected reaction of HOBr/OBr- with the primary amine moieties. In addition to the abatement of micropollutants, the evolution of the two main transformation products (TPs) of hydrochlorothiazide (HCTZ) and tramadol (TRA), chlorothiazide (CTZ) and tramadol N-oxide (TRA-NOX), respectively, was assessed by chemical analysis and kinetic modeling. Both selected TPs were quickly formed initially to reach a maximum concentration followed by a decrease of their concentrations for longer contact times. For the studied conditions, the TP's concentrations at the outlet of the reactors ranged from 0 to 61% of the initial parent compound concentration, CTZ being a more persistent TP against further oxidation than TRA-NOX. Finally, it was demonstrated in both reactors that the formation of bromate (BrO3-), a potentially carcinogenic oxidation by-product, could be controlled by H2O2 addition with a general improvement on micropollutant abatement. Post-treatment by granular activated carbon (GAC) filtration enabled the reduction of micropollutants and TPs concentrations but no changes in bromate were observed. The combined algae assay showed that water quality was significantly improved after oxidation and GAC post-treatment, driven by the abatement of the spiked pesticides (diuron and atrazine).

Development and laboratory-scale testing of a fully automated online flow cytometer for drinking water analysis.

Accurate and sensitive online detection tools would benefit both fundamental research and practical applications in aquatic microbiology. Here, we describe the development and testing of an online flow cytometer (FCM), with a specific use foreseen in the field of drinking water microbiology. The system incorporated fully automated sampling and fluorescent labeling of bacterial nucleic acids with analysis at 5-min intervals for periods in excess of 24 h. The laboratory scale testing showed sensitive detection (< 5% error) of bacteria over a broad concentration range (1 × 10(3) -1 × 10(6) cells mL(-1) ) and particularly the ability to track both gradual changes and dramatic events in water samples. The system was tested with bacterial pure cultures as well as indigenous microbial communities from natural water samples. Moreover, we demonstrated the possibility of using either a single fluorescent dye (e.g., SYBR Green I) or a combination of two dyes (SYBR Green I and Propidium Iodide), thus broadening the application possibilities of the system. The online FCM approach described herein has considerable potential for routine and continuous monitoring of drinking water, optimization of specific drinking water processes such as biofiltration or disinfection, as well as aquatic microbiology research in general.

Development of biomass in a drinking water granular active carbon (GAC) filter.

Indigenous bacteria are essential for the performance of drinking water biofilters, yet this biological component remains poorly characterized. In the present study we followed biofilm formation and development in a granular activated carbon (GAC) filter on pilot-scale during the first six months of operation. GAC particles were sampled from four different depths (10, 45, 80 and 115 cm) and attached biomass was measured with adenosine tri-phosphate (ATP) analysis. The attached biomass accumulated rapidly on the GAC particles throughout all levels in the filter during the first 90 days of operation and maintained a steady state afterward. Vertical gradients of biomass density and growth rates were observed during start-up and also in steady state. During steady state, biomass concentrations ranged between 0.8-1.83 x 10(-6) g ATP/g GAC in the filter, and 22% of the influent dissolved organic carbon (DOC) was removed. Concomitant biomass production was about 1.8 × 10(12) cells/m(2)h, which represents a yield of 1.26 × 10(6) cells/µg. The bacteria assimilated only about 3% of the removed carbon as biomass. At one point during the operational period, a natural 5-fold increase in the influent phytoplankton concentration occurred. As a result, influent assimilable organic carbon concentrations increased and suspended bacteria in the filter effluent increased 3-fold as the direct consequence of increased growth in the biofilter. This study shows that the combination of different analytical methods allows detailed quantification of the microbiological activity in drinking water biofilters.