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).

A comparison study of two different control criteria for the real-time management of urban groundwater works.

We present the comparison of two control criteria for the real-time management of a water well field. The criteria were used to simulate the operation of the Hardhof well field in the city of Zurich, Switzerland. This well field is threatened by diffuse pollution in the subsurface of the surrounding city area. The risk of attracting pollutants is higher if the pumping rates in four horizontal wells are increased, and can be reduced by increasing artificial recharge in several recharge basins and infiltration wells or by modifying the artificial recharge distribution. A three-dimensional finite elements flow model was built for the Hardhof site. The first control criterion used hydraulic head differences (Δh-criterion) to control the management of the well field and the second criterion used a path line method (%s-criterion) to control the percentage of inflowing water from the city area. Both control methods adapt the allocation of artificial recharge (AR) for given pumping rates in time. The simulation results show that (1) historical management decisions were less effective compared to the optimal control according to the two different criteria and (2) the distribution of artificial recharge calculated with the two control criteria also differ from each other with the %s-criterion giving better results compared to the Δh-criterion. The recharge management with the %s-criterion requires a smaller amount of water to be recharged. The ratio between average artificial recharge and average abstraction is 1.7 for the Δh-criterion and 1.5 for the %s-criterion. Both criteria were tested online. The methodologies were extended to a real-time control method using the Ensemble Kalman Filter method for assimilating 87 online available groundwater head measurements to update the model in real-time. The results of the operational implementation are also satisfying in regard of a reduced risk of well contamination.

Characterization of natural organic matter adsorption in granular activated carbon adsorbers.

The removal of natural organic matter (NOM) from lake water was studied in two pilot-scale adsorbers containing granular activated carbon (GAC) with different physical properties. To study the adsorption behavior of individual NOM fractions as a function of time and adsorber depth, NOM was fractionated by size exclusion chromatography (SEC) into biopolymers, humics, building blocks, and low molecular weight (LMW) organics, and NOM fractions were quantified by both ultraviolet and organic carbon detectors. High molecular weight biopolymers were not retained in the two adsorbers. In contrast, humic substances, building blocks and LMW organics were initially well and irreversibly removed, and their effluent concentrations increased gradually in the outlet of the adsorbers until a pseudo-steady state concentration was reached. Poor removal of biopolymers was likely a result of their comparatively large size that prevented access to the internal pore structure of the GACs. In both GAC adsorbers, adsorbability of the remaining NOM fractions, compared on the basis of partition coefficients, increased with decreasing molecular size, suggesting that increasingly larger portions of the internal GAC surface area could be accessed as the size of NOM decreased. Overall DOC uptake at pseudo-steady state differed between the two tested GACs (18.9 and 28.6 g-C/kg GAC), and the percent difference in DOC uptake closely matched the percent difference in the volume of pores with widths in the 1-50 nm range that was measured for the two fresh GACs. Despite the differences in NOM uptake capacity, individual NOM fractions were removed in similar proportions by the two GACs.

Real-time management of an urban groundwater well field threatened by pollution.

We present an optimal real-time control approach for the management of drinking water well fields. The methodology is applied to the Hardhof field in the city of Zurich, Switzerland, which is threatened by diffuse pollution. The risk of attracting pollutants is higher if the pumping rate is increased and can be reduced by increasing artificial recharge (AR) or by adaptive allocation of the AR. The method was first tested in offline simulations with a three-dimensional finite element variably saturated subsurface flow model for the period January 2004-August 2005. The simulations revealed that (1) optimal control results were more effective than the historical control results and (2) the spatial distribution of AR should be different from the historical one. Next, the methodology was extended to a real-time control method based on the Ensemble Kalman Filter method, using 87 online groundwater head measurements, and tested at the site. The real-time control of the well field resulted in a decrease of the electrical conductivity of the water at critical measurement points which indicates a reduced inflow of water originating from contaminated sites. It can be concluded that the simulation and the application confirm the feasibility of the real-time control concept.

Mechanistic and kinetic evaluation of organic disinfection by-product and assimilable organic carbon (AOC) formation during the ozonation of drinking water.

Ozonation of drinking water results in the formation of low molecular weight (LMW) organic by-products. These compounds are easily utilisable by microorganisms and can result in biological instability of the water. In this study, we have combined a novel bioassay for assessment of assimilable organic carbon (AOC) with the detection of selected organic acids, aldehydes and ketones to study organic by-product formation during ozonation. We have investigated the kinetic evolution of LMW compounds as a function of ozone exposure. A substantial fraction of the organic compounds formed immediately upon exposure to ozone and organic acids comprised 60-80% of the newly formed AOC. Based on experiments performed with and without hydroxyl radical scavengers, we concluded that direct ozone reactions were mainly responsible for the formation of small organic compounds. It was also demonstrated that the laboratory-scale experiments are adequate models to describe the formation of LMW organic compounds during ozonation in full-scale treatment of surface water. Thus, the kinetic and mechanistic information gained during the laboratory-scale experiments can be utilised for upscaling to full-scale water treatment plants.