Hilmar Börnick

Photoinitiated oxidation of geosmin and 2-methylisoborneol by irradiation with 254 nm and 185 nm UV light.

The degradation of geosmin and 2-methylisoborneol (2-MIB) by UV irradiation at different wavelengths was investigated under varying boundary conditions. The results showed that conventional UV radiation (254 nm) is ineffective in removing these compounds from water. In contrast to the usual UV radiation UV/VUV radiation (254+185 nm) was more effective in the removal of the taste and odour compounds. The degradation could be described by a simple pseudo first-order rate law with rate constants of about 1.2 x 10(-3) m(2)J(-1) for geosmin and 2-MIB in ultrapure water. In natural water used for drinking water abstraction the rate constants decreased to 2.7 x 10(-4) m(2)J(-1) for geosmin and 2.5 x 10(-4) m(2)J(-1) for 2-MIB due to the presence of NOM. Additionally, the formation of the by-product nitrite was studied. In the UV/VUV irradiation process up to 0.6 mg L(-1) nitrite was formed during the complete photoinitiated oxidation of the odour compounds. However, the addition of low ozone doses could prevent the formation of nitrite in the UV/VUV irradiation experiments.

Sorption influenced transport of ionizable pharmaceuticals onto a natural sandy aquifer sediment at different pH.

The pH-dependent transport of eight selected ionizable pharmaceuticals was investigated by using saturated column experiments. Seventy-eight different breakthrough curves on a natural sandy aquifer material were produced and compared for three different pH levels at otherwise constant conditions. The experimentally obtained K(OC) data were compared with calculated K(OC) values derived from two different logK(OW)-logK(OC) correlation approaches. A significant pH-dependence on sorption was observed for all compounds with pK(a) in the considered pH range. Strong retardation was measured for several compounds despite their hydrophilic character. Besides an overall underestimation of K(OC), the comparison between calculated and measured values only yields meaningful results for the acidic and neutral compounds. Basic compounds retarded much stronger than expected, particularly at low pH when their cationic species dominated. This is caused by additional ionic interactions, such as cation exchange processes, which are insufficiently considered in the applied K(OC) correlations.

Adsorption of geosmin and 2-methylisoborneol onto powdered activated carbon at non-equilibrium conditions: Influence of NOM and process modelling

The adsorption of the taste and odour (T&O) compounds geosmin and 2-methylisoborneol (2-MIB) onto powdered activated carbon (PAC) has been studied under conditions which are typical for a drinking water treatment plant that uses reservoir water for drinking water production. The reservoir water as well as the pre-treated water (after flocculation) contains NOM that competes with the trace compounds for the adsorption sites on the carbon surface. Although the DOC concentrations in the reservoir water and in the pre-treated water were different, no differences in the competitive adsorption could be seen. By using two special characterisation methods for NOM (adsorption analysis, LC/OCD) it could be proved that flocculation removes only NOM fractions which are irrelevant for competitive adsorption. Different model approaches were applied to describe the competitive adsorption of the T&O compounds and NOM, the tracer model, the equivalent background compound model, and the simplified equivalent background compound model. All these models are equilibrium models but in practice the contact time in flow-through reactors is typically shorter than the time needed to establish the adsorption equilibrium. In this paper it is demonstrated that the established model approaches can be used to describe competitive adsorption of T&O compounds and NOM also under non-equilibrium conditions. The results of the model applications showed that in particular the simplified equivalent background compound model is a useful tool to determine the PAC dosage required to reduce the T&O compounds below the threshold concentration.

UV-based advanced oxidation processes for the treatment of odour compounds: efficiency and by-product formation.

The occurrence of the taste and odour compounds geosmin and 2-methyl isoborneol (2-MIB) affects the organoleptic quality of raw waters from drinking water reservoirs worldwide. UV-based oxidation processes for the removal of these substances are an alternative to adsorption and biological processes, since they additionally provide disinfection of the raw water. We could show that the concentration of geosmin and 2-MIB could be reduced by VUV irradiation and the combination of UV irradiation with ozone and hydrogen peroxide in pure water and water from a drinking water reservoir. The figure of merit EE/O is an appropriate tool to compare the AOPs and showed that VUV and UV/O(3) yielded the lowest treatment costs for the odour compounds in pure and raw water, respectively. Additionally, VUV irradiation with addition of ozone, generated by the VUV lamp, was evaluated. The generation of ozone and the irradiation were performed in a single reactor system using the same low-pressure mercury lamp, thereby reducing the energy consumption of the treatment process. The formation of the undesired by-products nitrite and bromate was investigated. The combination of VUV irradiation with ozone produced by a VUV lamp avoided the formation of relevant concentrations of the by-products. The internal generation of ozone is capable to produce ozone concentrations sufficient to reduce EE/O below 1 kWh m(-3) and without the risk of the formation of nitrite or bromate above the maximum contaminant level.

Laboratory tests for simulating attenuation processes of aromatic amines in riverbank filtration

Based on a two-step laboratory test including biodegradation and adsorption, it is possible to derive a prognosis of the behaviour of organic compounds during riverbank filtration and to prioritise the substances with regard to drinking water quality. It is shown for aromatic amines, used as an example of organics found in River Elbe water, Germany, how the simulation methods provide basic information about rate constants of biological degradation and adsorption equilibrium constants under conditions that are as realistic as possible. Biodegradation of nitroanilines and higher chlorinated anilines is relatively slow and adsorption onto the sandy aquifer material is weak. Accordingly, occurrence of these compounds in the production wells of the waterworks cannot be excluded.

Challenges of an integrated water resource management for the Distrito Federal, Western Central Brazil: climate, land-use and water resources

Land-use/cover change (LUCC) and climate change are major controlling factors for water resources in the Distrito Federal in Western Central Brazil. Dynamic LUCC in the region has severe impacts on water resources, while climate changes during the last three decades is thought to have only moderate effects. LUCC affects water quantity mostly during base flow conditions. River basins with substantial expansion of agriculture since the end 1970s show a dramatic decrease of base flow discharge by 40–70%, presumably due to irrigation. In contrast, the effects of urbanization on runoff are less distinct, since factors controlling runoff generation might be more variable. For water quality, we found urban areas to have a strong influence on the parameters CSB, NH4+, and suspended solids. In addition, we assume emerging pollutants, e.g. organic (micro)pollutants, might play a major role in the future. The project IWAS-ÁGUA DF focuses on creating the scientific base to face these problems in frame of an IWRM concept for the region. Results of our study will be a contribution to an IRWM concept for the Distrito Federal and will help to maintain high standards in water supply for the region.

Simulation of Biological Degradation of Aromatic Amines in River Bed Sediments

Testfilter experiments are reported for river Elbe water spiked with aromatic amines in order to determine biodegradation rates. For river Elbe water the mean degradation rate of DOC (C0 = 6.64 mg l-1) was 26.7 +/- 8.8% after 6.8 days. No significant effect on the DOC degradation rate was observed with the addition of aromatic amines. Large differences in the biodegradation behaviour of the aromatic amines were observed: aniline was eliminated within 3 h, whereas the degradation of 2-nitroaniline was only 40% after 14 h effective contact time. Degradation curves were mostly of a simple logarithmic type, demonstrating first-order kinetics. The degradation rate of 2,4,6-trichloraniline increased by a factor of 20 within 6 weeks due to the adaptation of the testfilter biofilm. A linear relationship between available pKa-values and the logarithm of the experimental degradation rates was found. Thus, the results of the testfilter experiments may be extended to the estimation of the biodegradability of non-tested aromatic amines.

Influence of competing inorganic cations on the ion exchange equilibrium of the monovalent organic cation metoprolol on natural sediment

The aim of this study was to systematically investigate the influence of the mono- and divalent inorganic ions Na(+) and Ca(2+) on the sorption behavior of the monovalent organic cation metoprolol on a natural sandy sediment at pH=7. Isotherms for the beta-blocker metoprolol were obtained by sediment-water batch tests over a wide concentration range (1-100000 μg L(-1)). Concentrations of the competing inorganic ions were varied within freshwater relevant ranges. Data fitted well with the Freundlich sorption model and resulted in very similar Freundlich exponents (n=0.9), indicating slightly non-linear behavior. Results show that the influence of Ca(2+) compared to Na(+) is more pronounced. A logarithmic correlation between the Freundlich coefficient K(Fr) and the concentration or activity of the competing inorganic ions was found allowing the prediction of metoprolol sorption on the investigated sediment at different electrolyte concentrations. Additionally, the organic carbon of the sediment was completely removed for investigating the influence of organic matter on the sorption of metoprolol. The comparison between the experiments with and without organic carbon removal revealed no significant contribution of the organic carbon fraction (0.1%) to the sorption of metoprolol on the in this study investigated sediment. Results of this study will contribute to the development of predictive models for the transport of organic cations in the subsurface.

Sorption of organic cations onto silica surfaces over a wide concentration range of competing electrolytes.

The fundamental understanding of organic cation-solid phase interactions is essential for improved predictions of the transport and ultimate environmental fates of widely used substances (e.g., pharmaceutical compounds) in the aquatic environment. We report sorption experiments of two cationic model compounds using two silica gels and a natural aquifer sediment. The sorbents were extensively characterized and the results of surface titrations under various background electrolyte concentrations were discussed. The salt dependency of sorption was systematically studied in batch experiments over a wide concentration range (five orders of magnitude) of inorganic ions in order to examine the influence of increasing competition on the sorption of organic cations. The organic cation uptake followed the Freundlich isotherm model and the sorption capacity decreases with an increase in the electrolyte concentration due to the underlying cation exchange processes. However, the sorption recovers considerably at high ionic strength (I>1M). To our knowledge, this effect has not been observed before and appears to be independent from the sorbent characteristics and sorbate structure. Furthermore, the recovery of sorption was attributed to specific, non-ionic interactions and a connection between the sorption coefficient and activity coefficient of the medium is presumed. Eventually, the reasons for the differing sorption affinities of both sorbates are discussed.

Sorption of cationic organic substances onto synthetic oxides: Evaluation of sorbent parameters as possible predictors

Knowledge on the sorption behavior of cationic organic substances in aquatic systems is vital for their risk assessment due to the increasing detection of such chemicals in the hydrosphere. Their sorption behavior is strongly influenced by sorption processes onto mineral surfaces (e.g., oxides, clays). To contribute to the development of prediction tools, the impact of sorbent characteristics on the sorption strength was studied in a highly-idealized model system. In addition to the properties of the solid phase, the concentration of other ions in direct competition for sorption sites and the molecular structure of the sorbate were changed to separate ion exchange and non-ion exchange processes. The study includes in total 120 systematic column experiments using five extensively characterized synthetic oxides (three silica gels, two aluminum oxides), three probe molecules (two structurally related cationic substances, one neutral compound), and four distinctively different NaCl concentrations. The results show that the concentration of OH groups on the sorbent surface is a meaningful descriptor for the observed variations in sorption capacity onto different oxides. Compound-specific linear correlations were obtained, enabling the prediction of sorption coefficients. In addition, a more complex sorption behavior of organic cations compared to uncharged molecules were observed as demonstrated by the sorption results at different electrolyte concentrations. Thus, the study provides an important step towards a better principal mechanistic understanding of organic cation sorption. However, further work using other sorbents including natural ones and other probe molecules is needed to verify the identified relationships within the scope of developing reliable prediction models for cation sorption.