Effect of Preozonation on the Formation of Chlorinated Disinfection By‐products for River Ruhr

The purpose of the study is to gain a better understanding about the formation of THM (trihalomethanes), HAA (haloacetic acids), and AOX (adsorbable organic halogen) in river water (river Ruhr, Essen) through a chlorination kinetics approach. The effect of chlorination time and preozonation on the formation of THM, HAA, and AOX substances was studied. Preozonation can reduce the chlorine demand and the precursors for AOX and THM. THM generation was reduced further, when the ozone dosage consumed increased from 3.5 to 12.5 mg in the 1.4 L reaction vessel. AOX and TCAA (trichloroacetic acid) concentrations also decreased dramatically when 3.5 mg of ozone had reacted with the river water, but a higher dose of ozone did not further reduce AOX and TCAA formations. Besides, the characteristics of organic matter in raw water, ozonated water, and preozonated/chlorinated water was investigated. The results suggest the formation of low‐molecular‐weight acids with low UV absorbance when high‐molecular refractive matter is oxidized.     

Influence of Oxidative Treatment on the AOX‐formation Potential of Aromatic Sulfonates

Aromatic sulfonates can be found in drinking water. Thus, they must have passed water treatment and survived ozonation. Degradation of aromatic sulfonates can be achieved by the UV/H2O2‐process. Since drinking water is often treated with chlorine as a disinfectant, the formation of disinfection by‐products has to be considered. Therefore, the production of AOX (on activated carbon adsorbable organic halogens) after chlorination of the sulfonates with and without preoxidation was investigated. Instead of the analysis of the individual degradation products, the determination of the sum parameter AOX was used as a fast screening method. The investigated sulfonates were: anthraquinone‐2‐sulfonate, naphthalene‐2‐sulfonate, 2‐aminonaphthalene‐1‐sulfonate, and 4,4′‐diaminostilbene‐2,2′‐disulfonate. All sulfonates containing amino groups showed high potentials of AOX formation. The preoxidation with ozone increased the potentials of AOX formation in general. Treating the sulfonates by using the UV/H2O2‐process, the formation potentials run to zero after going through a maximum value.     

Reactions of PAH with Chlorine and Chlorine Dioxide in Coal Tar Lined Pipes

In presence of disinfectants, PAH are remobilized from the coal tar lining of water distribution mains. Reactions of the PAH with chlorine and chlorine dioxide can lead to chlorinated PAH that might show higher mutagenic effects than the parent PAH. The application of the solid-phase microextraction as a sampling preparation method in combination with a gas chromatographic mass spectrometric device is a reliable and useful method to achieve detection limits in the lower nanogramme-per-liter level for PAH and chlorinated PAH. Thus, the reactions of four PAH (anthracene, fluoranthene, fluorene, and phenanthrene) with chlorine and chlorine dioxide under conditions prevalent in drinking water distribution systems could be investigated. In batch experiments with demineralized and drinking water at pH 7, the concentrations of fluoranthene, fluorene, and phenanthrene remained constant, whereas anthracene reacted quantitatively with both disinfectants. In these reactions, no chlorinated products could be detected, only mono-hydroxyanthracene and anthraquinone were formed. A reaction mechanism for both reaction products is proposed. The results suggest that oxidation is the major pathway of the reaction of PAH with disinfectants in the systems under investigation.     

Interactions of Chlorine with Natural Organic Matter and Formation of Intermediates: Evidence by Differential Spectroscopy

This communication describes the use of differential absorbance spectroscopy to explore the intermediates formed during halogenation of natural organic matter (NOM). The differential spectra of chlorinated NOM comprise two contributions. The primary component is negative and has a peak near 270 nm. The shape of this band is independent of chlorine dose, and its intensity increases monotonically with Cl₂ dose. The second component is positive, with a well‐defined peak near 280 nm and another, broader band in the 340...380 nm range. The second component is noticeable at low chlorine concentrations but disappears with increasing Cl₂ dose. We attribute this component to aromatic chlorinated intermediates formed prior to the release of identifiable smaller species such as haloacetic acids. We believe that this component of the differential spectra can be used to probe the identity, formation and breakdown of the halogenated intermediates.