Ozonation in advanced treatment of secondary municipal wastewater effluents for the removal of micropollutants.

The objective of this study was the experimental evaluation of ozonation as an additional treatment step for the removal emerging contaminants from secondary effluents of two wastewater treatment plants (WWTPs), one receiving a primarily domestic wastewater (WWTP-A), and the other one domestic sewage together with pretreated tannery wastewater streams (WWTP-B). The experimental runs were conducted at two different pH values (i.e., original pH and adjusted pH of 10) and at six different ozone doses ranging between 0.2 and 1.5 mg O3/mg DOC. A total of 20 compounds, including 12 micropollutants (MPs) and 8 metabolites, were selected as the target analytes for the evaluation of ozonation performance. When the tested MPs and metabolites were considered individually, the maximum elimination level for each compound was reached at different doses; therefore, optimum ozone doses were determined based on the reduction of the total MP content. Ozonation at the original pH with an ozone dose in the range of 0.4-0.6 and 0.8-1.0 mg O3/mg DOC was selected as the optimum operating condition for WWTP-A and WWTP-B, respectively, both resulting in an average overall removal efficiency of 55%. Ozone treatment yielded only poor elimination for o-desmethyl naproxen (15%), which was found to be by far the main contributor accounting alone for approximately 30% of the total MP concentration in the secondary effluents. The systematic approach used in this study could well be adopted as a guide to other domestic and municipal WWTPs, which are thought to have a highly variable composition in terms of the MPs and metabolites.

Effect of triclosan and its photolysis products on marine bacterium V. fischeri and freshwater alga R. subcapitata.

The use of antibacterial agents in consumer products may lead to adverse effects in waters receiving treated wastewater. Triclosan is one of the antibacterial agents used widely in the world and its high usage leads to relatively high concentrations in wastewater effluents. In this study, the probable effect of triclosan in receiving waters was assessed using different organisms. The EC50 values were 668 ±â€¯80 µg/L and 7.8 ±â€¯0.1 µg/L, for Vibrio fischeri and Raphidocelis subcapitata, respectively, indicating the higher sensitivity of the alga. The toxicity of triclosan upon exposure to UV light decreased for both species, as suggested by the increase in EC50 values (1300 ±â€¯50 µg/L and 8.7 ±â€¯0.6 µg/L for V. fischeri and R. subcapitata, respectively). The effect of photolysis on toxicity reduction was higher for V. fischeri and the EC50 values were similar for direct and indirect photolysis. LC-MS/MS analysis of samples with and without UV exposure suggested a decrease in triclosan concentration as well as formation of photolysis byproducts upon photolysis.

Seasonal variation of diclofenac concentration and its relation with wastewater characteristics at two municipal wastewater treatment plants in Turkey.

The pharmaceutically active compound diclofenac has been monitored during one year at separate treatment units of two municipal wastewater treatment plants (WWTPs) to evaluate its seasonal variation and the removal efficiency. Conventional wastewater characterization was also performed to assess the possible relationship between conventional parameters and diclofenac. Diclofenac concentrations in the influent and effluent of both WWTPs were detected in the range of 295-1376 and 119-1012ng/L, respectively. Results indicated that the higher diclofenac removal efficiency was observed in summer season in both WWTPs. Although a consistency in diclofenac removal was observed in WWTP_1, significant fluctuation was observed at WWTP_2 based on seasonal evaluation. The main removal mechanism of diclofenac in the WWTPs was most often biological (55%), followed by UV disinfection (27%). When diclofenac removal was evaluated in terms of the treatment units in WWTPs, a significant increase was achieved at the treatment plant including UV disinfection unit. Based on the statistical analysis, higher correlation was observed between diclofenac and suspended solids concentrations among conventional parameters in the influent whereas the removal of diclofenac was highly correlated with nitrogen removal efficiency.

Optimization of diclofenac quantification from wastewater treatment plant sludge by ultrasonication assisted extraction.

A rapid quantification method of diclofenac from sludge samples through ultrasonication assisted extraction and solid phase extraction (SPE) was developed and used for the quantification of diclofenac concentrations in sludge samples with liquid chromatography/tandem mass spectrometry (LC-MS/MS). Although the concentration of diclofenac in sludge samples taken from different units of wastewater treatment plants in Istanbul was below the limit of quantification (LOQ; 5ng/g), an optimized method for sludge samples along with the total mass balances in a wastewater treatment plant can be used to determine the phase with which diclofenac is mostly associated. Hence, the results will provide information on fate and transport of diclofenac, as well as on the necessity of alternative removal processes. In addition, since the optimization procedure is provided in detail, it is possible for other researchers to use this procedure as a starting point for the determination of other emerging pollutants in wastewater sludge samples.

Occurrence of THM and NDMA precursors in a watershed: Effect of seasons and anthropogenic pollution.

In pristine watersheds, natural organic matter is the main source of disinfection by-product (DBP) precursors. However, the presence of point or non-point pollution sources in watersheds may lead to increased levels of DBP precursors which in turn form DBPs in the drinking water treatment plant upon chlorination or chloramination. In this study, water samples were collected from a lake used to obtain drinking water for Istanbul as well as its tributaries to investigate the presence of the precursors of two disinfection by-products, trihalomethanes (THM) and N-nitrosodimethylamine (NDMA). In addition, the effect of seasons and the possible relationships between these precursors and water quality parameters were evaluated. The concentrations of THM and NDMA precursors measured as total THM formation potential (TTHMFP) and NDMA formation potential (NDMAFP) ranged between 126 and 1523µg/L THM and <2 and 1648ng/L NDMA, respectively. Such wide ranges imply that some of the tributaries are affected by anthropogenic pollution sources, which is also supported by high DOC, Cl(-) and NH(3) concentrations. No significant correlation was found between the water quality parameters and DBP formation potential, except for a weak correlation between NDMAFP and DOC concentrations. The effect of the sampling location was more pronounced than the seasonal variation due to anthropogenic pollution in some tributaries and no significant correlation was obtained between the seasons and water quality parameters.

Measurement of dissolved organic nitrogen forms in wastewater effluents: concentrations, size distribution and NDMA formation potential.

Dissolved organic nitrogen (DON), which may act as a nutrient and a disinfection by-product precursor, accounts for most of the dissolved nitrogen in nitrified-denitrified wastewater effluents. To gain insight into the behavior of wastewater-derived DON in engineered and natural systems, samples from treatment plants employing a range of different processes were characterized by several different methods. Dissolved free and combined amino acids accounted for the majority of the identifiable DON. Combined amino acids typically accounted for less than 10-20% of the wastewater-derived DON. Other organic-nitrogen containing species such as EDTA and humic substances from the water source only accounted for a few percent of the remaining DON. The remaining DON mainly consisted of hydrophilic, low-molecular weight compounds, capable of passing through a 1kDa ultrafilter. This fraction of the DON also contained most of the precursors of N-nitrosodimethylamine (NDMA). The chemical properties of wastewater-derived DON pose challenges to designers of wastewater treatment plants because most physical and chemical treatment processes will not remove low-molecular weight, hydrophilic compounds.

The fate of wastewater-derived NDMA precursors in the aquatic environment.

To assess the stability of precursors of the chloramine disinfection byproduct N-nitrosodimethylamine (NDMA) under conditions expected in effluent-dominated surface waters, effluent samples from four municipal wastewater treatment plants were subjected to chlorination and chloramination followed by incubation in the presence of inocula derived from activated sludge. Samples subjected to free chlorine disinfection showed lower initial concentrations of NDMA precursors than those that were not chlorinated or were disinfected with pre-formed chloramines. For chloraminated and control (unchlorinated) treatments, the concentration of NDMA precursors decreased by an average of 24% over the 30-day incubation in samples from three of the four facilities. At the fourth facility, where samples were collected on three different days, NDMA precursor concentrations decreased by approximately 80% in one sample and decreased by less than 20% in the other two samples. In contrast to the low reactivity of the NDMA precursors, NDMA disappeared within 30 days under the conditions employed in these experiments. These results and measurements made in an effluent-dominated river suggest that although NDMA may be removed after wastewater effluent is discharged, wastewater-derived NDMA precursors could persist long enough to form significant concentrations of NDMA in drinking water treatment plants that use water originating from sources that are subjected to wastewater effluent discharges.

Formation of nitrosodimethylamine (NDMA) during chlorine disinfection of wastewater effluents prior to use in irrigation systems.

The probable human carcinogen nitrosodimethylamine (NDMA) is produced when wastewater effluent is disinfected with chlorine. In systems where wastewater effluent is used for landscape or crop irrigation, relatively high chlorine doses (i.e., up to 2,000,mg-min/L) are often used to ensure adequate disinfection and to minimize biofouling in the irrigation system. To assess the formation of NDMA in such systems, samples were collected from several locations in full-scale wastewater treatment systems and their associated irrigation systems. Up to 460 ng/L of NDMA was produced in full-scale systems in which chloramines were formed when wastewater effluent was disinfected with chlorine in the presence of ammonia. Less than 20 ng/L of NDMA was produced in systems that used free chlorine (i.e., HOCl/OCl(-)) for disinfection in the absence of ammonia. The production of NDMA in ammonia-containing systems was correlated with the concentration of NDMA precursors in the wastewater effluent and the overall dose of chlorine applied. Much of the NDMA formation occurred in chlorine contact basins or in storage basins where water that contained chloramines was held after disinfection. When landscape or crop irrigation is practiced with ammonia-containing wastewater effluent, NDMA production can be controlled by use of lower chlorine doses or by application of alternative disinfectants.