Abteilung Umweltchemie

In treated municipal wastewater, residual organic compounds are of high relevance especially if water recycling and potable water reuse is envisaged. After biological treatment, such as the activated sludge process, some organic compounds remain that are either non-biodegradable, or are minimally biodegradable. If these chemicals are polar, they are commonly poorly absorbable, and are therefore identified as persistent polar organic compounds (also persistent polar pollutants, PPPs).
In the last decade, there have been important analytical improvements in detecting trace levels of pollutants, and within the water reuse community, new "hazardous" compounds are frequently discussed. This includes consideration of which organic residuals are really of health concern, which transformation products can be generated, and what is their human and environmental impact? Within the present chapter relevant PPPs and their fate during (advanced) wastewater treatment and managed aquifer recharge are identified and discussed as results of measuring campaigns at technologically different demonstration sites within the European research project RECLAIM WATER. Such PPPs mainly belong in the group of pharmaceuticals but also industrial chemicals. [...]

Source control or elimination of precursors of NDMA and other nitrosamines in wastewater requires information on their physicochemical properties, which is still limited. Thus we developed a multistep fractionation method based on a combination of consecutive filtration steps to <1 μm, <0.2 μm, and <2.5 kDa followed by solid-phase extraction on a C18 column and validated it using model NDMA precursors covering a wide polarity range. The membrane filtration to 2.5 kDa was suitable to separate a low-molecular weight precursor fraction but partially removed hydrophobic compounds by sorption. Fractionation on a C18 column allowed distinguishing highly polar precursors (such as dimethylamine) from less polar ones (such as ranitidine or other pharmaceuticals). Application of the fractionation procedure together with the formation potential test revealed that in the influent of one studied wastewater treatment plant about 50% of all precursors were associated with colloids or macromolecules, suggesting that these fractions comprise sorbed hydrophobic precursors. During activated sludge treatment small polar and charged NDMA and other nitrosamines’ precursors were removed to about 80%. In contrast, less polar precursors were more recalcitrant. In advanced treatment steps, only small fractions of the precursors were removed by the prechlorination/ultrafiltration step, while reverse osmosis removed >98% of all precursors.

Membrane bioreactor (MBR) technology is an interesting option for single-house wastewater treatment or small communities. Because typically a very high effluent quality is achieved with respect to pathogens, suspended solids, organics and nitrogen, the permeate is well suited for reuse. Little is known about the fate of micropollutants in such small systems. The differences between centralized and decentralized biological wastewater treatment with respect to micropollutants are manifold: besides the operational parameters like hydraulic and sludge retention time, the main difference is in the load variation. While the influent load is expected to be more or less constant in large catchments, it varies strongly in small MBRs due to irregular consumption (e.g. of medication by individuals). Concentrations of micropollutants are higher by a factor 50–1000 than in centralized treatment. It is also unknown how reliable degradation of micropollutants is in case of irregular exposure.
In this study, two experiments were conducted in a small MBR treating the wastewater of a three-person household. During normal operation of the treatment plant, 25 pharmaceuticals (antibiotics, antiphlogistics, lipid regulators, iodinated contrast media and hormones) that had not been used by members of the household were added in concentrations typical for municipal wastewater. The removal of most substances was in the same range as for centralized wastewater treatment. It was shown that biological transformation was the main elimination process while adsorption to the activated sludge was negligible for most substances due to the low sludge production at high sludge retention time. No appreciable lag for inducing biological degradation was observed. The high hydraulic and sludge residence time had a positive effect on the elimination of slowly degradable substances, but this was partly compensated by the lower biological activity.
An experiment with antibiotics concentrations typical for decentralized treatment (between 500 and 1000 μg l⁻¹; sulfamethoxazole, sulfapyridine, trimethoprim, clarithromycin, roxithromycin) did not show an inhibitory effect on either nitrification or denitrification.

The presence of nitrosamines in wastewater might pose a risk to water resources even in countries where chlorination or chloramination are hardly used for water disinfection. We studied the variation of concentrations and removal efficiencies of eight N-nitrosamines among 21 full-scale sewage treatment plants (STPs) in Switzerland and temporal variations at one of these plants. N-nitrosodimethylamine (NDMA) was the predominant compound in STP primary effluents with median concentrations in the range of 5–20 ng/L, but peak concentrations up to 1 μg/L. N-nitrosomorpholine (NMOR) was abundant in all plants at concentrations of 5–30 ng/L, other nitrosamines occurred at a lower number of plants at similar levels. From concentrations in urine samples and domestic wastewater we estimated that human excretion accounted for levels of <5 ng/L of NDMA and <1 ng/L of the other nitrosamines in municipal wastewater, additional domestic sources for <5 ng/L of NMOR. Levels above this domestic background are probably caused by industrial or commercial discharges, which results in highly variable concentrations in sewage. Aqueous removal efficiencies in activated sludge treatment were in general above 40% for NMOR and above 60% for the other nitrosamines, but could be lower if concentrations were below 8–15 ng/L in primary effluent. We hypothesize that substrate competition in the cometabolic degradation explains the occurrence of such threshold concentrations. An additional sand filtration step resulted in a further removal of nitrosamines from secondary effluents even at low concentrations. Concentrations released to surface waters were largely below 10 ng/L, suggesting a low impact on Swiss water resources and drinking water generation considering the generally high environmental dilution and possible degradation. However, local impacts in case a larger fraction of wastewater is present cannot be ruled out.

A method was developed to determine nine N-nitrosamines in wastewater on the basis of solid-phase extraction and liquid chromatography mass spectrometry using a linear ion trap-orbitrap hybrid instrument at high mass resolution. Analytes and five deuterated internal standards were preconcentrated by solid-phase extraction. Positive electrospray ionization resulted in protonated molecular ions of all nitrosamines. One to three product ions were formed by collision-induced dissociation or higher energy C-trap dissociation. The signal intensity of the product ions differed up to a factor of 3 between the two techniques. The molecular ions were usually used for quantification, because of the better sensitivity, and the product ions for confirmation. An actual mass resolving power of 25 000-40 000 ensured a sufficient selectivity to distinguish all molecular and product ions from interfering background ions. Only for N-nitrosomorpholine was a coeluting isobaric molecular ion detected in wastewater samples, which, however, formed different product ions. The mass accuracy was between -12 ppm at m/z 55 and 0 ppm at m/z 205 and did not change for more than 5 ppm over a sample sequence of 20 h analysis time. The optimized method allowed quantifying nine N-nitrosamines in drinking water and wastewater samples down to method detection limits of 0.3-3.9 ng/L at instrumental detection limits of 2-14 pg on column. Recoveries over the whole method were between 75 and 125% for six compounds, but considerably lower for three compounds, probably due to strong matrix effects causing a signal suppression of up to 95% in wastewater samples. N-Nitrosodimethylamine and N-nitrosomorpholine were the most abundant compounds (3-22 ng/L) in samples from two wastewater treatment plants, another four nitrosamines (N-nitrosopyrrolidone, -piperidine, -diethylamine, and -dibutylamine) were also detected. Our study demonstrates that the LTQ Orbitrap is a powerful instrument to quantify low molecular weight compounds at the picogram level in complex matrixes with both a high sensitivity and selectivity.