Co-metabolism of nonylphenol ethoxylate in sequencing batch reactor under aerobic conditions.

The study evaluated the co-metabolism of nonylphenol polyethoxylate (NPEO) within a main substrate stream subjected to biodegradation in an activated sludge system. Peptone mixture simulating sewage was selected as the synthetic substrate. As a novel approach, the NPEO concentration was magnified to match the COD level of the peptone mixture, so that co-metabolism could be evaluated by respirometry and modeling. A sequencing batch reactor (SBR) set-up at high sludge age to also allow nitrification was operated for this purpose. A long acclimation phase was necessary to start NPEO biodegradation, which was completed with 15% residual by-products. Modeling of respirometric data could identify COD fractions of NPEO with corresponding process kinetics for the first time, where the biodegradation of by-products could be interpreted numerically as a hydrolysis mechanism. Nonylphenol diethoxylate (NP2EO) was observed as the major by-product affecting the biodegradation of NPEO, because NPEO and NP2EO accounted for 60 to 70% of the total soluble COD in the solution during the course of biological reactions. The co-metabolism characteristics basically defined NPEO as a substrate, with no appreciable inhibitory action on the microbial culture both in terms of heterotrophic and autotrophic activities.

A comprehensive evaluation of process kinetics: A plant-wide approach for nutrient removal and biogas production.

The present study investigated the deviations of operational parameters of a large-scale wastewater treatment plant (WWTP) from design basis through combining dedicated batch experiments with full-scale dynamic modeling results. The long-term process performance of a full-scale biological nutrient removal (BNR) plant equipped with anaerobic sludge digestion system was monitored to evaluate the process kinetics of both carbon and nutrient removal and anaerobic sludge digestion. In this respect, plant-specific characterization; chemical oxygen demand (COD) fractionation, batch kinetic studies and sludge settling velocity tests were performed together with plant-wide SUMO model simulation. Results showed that nitrification and anaerobic hydrolysis were found to be 30% and 70% lower than literature values, respectively. The anaerobic digestion test coupled with plant-wide model calibration showed that anaerobic hydrolysis was the bottleneck in biogas production. Correspondingly, performance of the anaerobic digestion in the full-scale plant was poor as low biogas production yields were observed. In addition, the degradation rate via anaerobic hydrolysis of primary sludge was found to be higher (∼2-2.5) compared to anaerobic hydrolysis of biological sludge. The results of this study provide insight into model-based experimental characterization as well as plant-wide modeling approach. Coupling model-based batch experiments with full-scale modeling enabled to reduce the number of kinetic parameters to be fine-tuned. Moreover, the information gathered from kinetic batch tests to the simulation platform yielded a satisfying prediction of long-term performance of the plant operation.

Theoretical investigation of the sequential reductive dechlorination pathways of chlorobenzenes and chloroanilines.

The distribution of product isomers during the sequential reductive dechlorination of pentachloroaniline (PCA) and pentachlorobenzene (PeCB) was examined based on calculated thermodynamic, chromatographic, and electronic properties and then compared to the product distribution achieved by enrichment cultures. The dechlorination pathway analysis based on free energy considerations matched 78% and 67% of the experimental results for the sequential reductive dechlorination of chlorobenzenes (CBs) and chloroanilines (CAs), respectively. Chromatographic properties of CBs and CAs were able to explain some but not all of the reactions in the observed dechlorination pathways. Correlations between the observed dechlorination pattern and electronic properties of the parent compounds were able to explain most of the formation of the observed products. Experimentally observed sequential reductive dechlorination of CBs and CAs were similar to predicted dechlorination pathways based on the charge differential values calculated for the carbon-chloride bonds. Chlorine atoms were removed from the carbon atom that has the highest charge differential or the second highest charge differential. However, although thermodynamic, electronic as well as chromatographic properties of the CBs and CAs are certainly important factors, they may not be sufficient to completely describe the sequential microbial reductive dechlorination. Enzymatic specificity, as well as other factors (i.e., culture acclimation, environmental factors) should be considered for the interpretation of observed sequential reductive dehalogenation pathways of haloorganic compounds. This work provides the most comprehensive analysis to date of theoretical factors that control the sequential reductive chlorination of two homologous series of single-ring chloroaromatic species.

Microbial transformation of pentachloronitrobenzene under nitrate reducing conditions.

The effect of pentachloronitrobenzene (PCNB) on denitrification was assessed with two denitrifying cultures (PCNB-free control and PCNB-acclimated) developed from a contaminated estuarine sediment. PCNB was transformed to pentachloroaniline (PCA) in the PCNB-acclimated culture repeatedly amended with 0.1 muM PCNB, but further dechlorination or degradation of PCA was not observed for almost 1 year. The effect of PCNB on denitrification was also investigated with the PCNB-free control culture. PCNB at an initial concentration of 13 muM was transformed to PCA simultaneously with nitrate reduction but only after the nitrate concentration was at or below 20 mg N/l. PCNB addition at an initial concentration of 13 muM to the control denitrifying culture developed as PCNB-free culture resulted in a transient accumulation of nitric oxide (NO) and nitrous oxide (N(2)O). Similarly to the PCNB-acclimated culture, PCNB transformation to PCA started when the nitrate concentration decreased to about 20 mg N/l. A low degree of nitro group removal resulting in the formation of pentachlorobenzene (PeCB) was also observed in the control culture when amended with 13 muM PCNB. Further transformation or degradation of PCA was not observed in all cultures maintained under active nitrate reducing conditions. Based on the results of this study, the presence of nitrate at low concentrations in anoxic/anaerobic soil and sediments is not expected to negatively affect the biotransformation of PCNB to PCA, but dechlorination or degradation of PCA is not expected under active nitrate reducing conditions.

Acute and chronic responses of denitrifying culture to diclofenac.

Acute and chronic effect as well as biodegradation potential at different sludge retention times (SRTs) of a priority pollutant, diclofenac on denitrification process was assessed. The continuous amendment of the culture for 6months with 1µg/L diclofenac resulted in 30% decrease in gas production. The average diclofenac removal observed in the diclofenac-acclimated culture was less than 15%. Batch tests showed that nitrate was removed in diclofenac free-control reactor at a higher rate compared to diclofenac amended reactor. Although, SRT did not have any progressive effect on diclofenac degradation, the system operated at low SRT was more sensitive to diclofenac and resulted in an increase in N2O emission. Wastewater treatment plants (WWTPs) operated at higher SRTs may tolerate and recover from the adverse effects of such micropollutants. The study can lead to other researchers to understand the fate and effect of other emerging pollutants in the anoxic unit of WWTPs.

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.

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.

Influence of quaternary ammonium compounds on the microbial reductive dechlorination of pentachloroaniline.

The inhibitory effect of two widely used quaternary ammonium compounds (QACs)--alkyl benzyl dimethyl (AB) and hexadecyl trimethyl (HD) ammonium chloride--on fermentation, methanogenesis and pentachloroaniline (PCA) dechlorination was assessed using a mixed, methanogenic, PCA-dechlorinating culture amended with AB or HD at a concentration range from 5 to 70 µM. PCA dechlorination was inhibited at 5 µM AB and was completely inhibited at 25 or 5 µM by AB or HD, respectively. However, the PCA dechlorination pathway was the same in both the QACs-free and QACs-amended culture series. Fermentation (acidogenesis) and methanogenesis were inhibited by both AB and HD at and above 25 µM but to a lesser degree than PCA dechlorination. Overall, HD resulted in a more severe inhibition of the mixed culture than AB. Adsorption of both QACs to the mixed culture biomass followed the Freundlich isotherm model. The adsorption affinity of HD for the mixed culture biomass was significantly higher than that of AB, which may be related to the observed higher inhibitory effects of HD compared to AB. Both AB and HD were not degraded in the mixed, dechlorinating culture used in this study.

Effect of stabilization on biomass activity.

The study aimed to compare aerobic and aerobic/anoxic stabilization processes in terms of organic matter and the biomass removal efficiencies using a municipal sludge sample. The efficiency of stabilization process was assessed monitoring suspended solids (SS), volatile suspended solids (VSS), total and dissolved organic carbon (TOC, DOC), nitrate, nitrite, and phosphate parameters. The oxygen uptake rate (OUR) measurements were conducted to determine active biomass concentration. On the 30th day of the aerobic stabilization, the SS, VSS and TOC removal efficiencies were 22%, 28% and 55%, respectively. Under aerobic/anoxic conditions, removal efficiencies for SS, VSS and TOC were 25%, 27% and 67%. On the 17th day of the stabilization, SS and VSS removal rates were 60 mg SS/L day and 47 mg VSS/L day for aerobic and 102 mg SS/L day and 63 mg VSS/L day for aerobic/anoxic conditions, respectively. These findings reflected the higher stabilization performance of the aerobic/anoxic conditions. Based on respirometric results, the ratios of the active biomass were decreased to 30% and 24% for the 17th and 30th day of the aerobic stabilization, respectively. Such results have significant implications relative to the activity decrease quantification of the biomass as well as its further application potentials after aerobic or aerobic/anoxic sludge stabilization.