Treatment of waste sludge has become an important issue in recent years around the world. However, the trend of waste sludge treatment has shifted from volume minimization and stabilization to reuse of the sludge and recover the energy potential of it. Therefore, anaerobic treatment of sludge is gaining popularity because of byproduct methane production and high percentage of VSS reduction. Pre-treatment of sludge before anaerobic digestion in order to increase methane production, and ozone pre-treatment in this context, is one such option. Domestic sludge also contains the recently recognized, so called, emerging compounds such as Endocrine Disrupting Compounds (EDCs). Therefore treatment of EDCs in sludge is another challenge in waste sludge treatment since direct discharge of such chemicals may harm the environment by causing gender shifts within the fauna. In this context two hormones (estrone and progesterone), three pharmaceuticals (acetaminophen, carbamazepine and diltiazem) and one plasticizer (benzyl-butyl phthalate) were routinely analyzed in sludge samples which were subjected to treatment during this study. Treatment of EDCs during anaerobic digestion and the effect of ozonation both on the performance of digestion and the treatability of EDCs were investigated in this study. Four 2.5L anaerobic jars were used for anaerobic digestion connected to four 1L plastic graduated cylinders immersed in salt-water to collect the off gas. Anaerobic sludge culture of the reactor and the sludge feed to the reactors were obtained from Ankara Tatlar Wastewater Treatment Plant anaerobic digester and return activated sludge (RAS) line, respectively. One of the anaerobic digesters was used as control (no ozonation) and the others were fed with sludge samples ozonated at three different ozone doses 0.65, 1.33 and 2.65 mg ozone/g biomass. Sludge ages of the reactors were initially set to 25 days and the reactors were fed once every 2 days. The TSS, VSS, total gas volume, COD, pH, CH4 percentage and EDCs were analyzed routinely. In the reactors, operated at 25 days, because of the observation of reduction of TSS, SRT was set to infinity / thus, sludge wastage was terminated. Following the startup it was seen that at 2.65 mg ozone/g biomass dose TSS and VSS did not stay constant in the reactor and dropped sharply in the course of operation, indicating that system was not steady at this SRT. However, upon stoppage of sludge wastage from the reactors, thereby setting SRT to infinity, a steady culture could be maintained in the reactors. Both total gas production and CH4 percentage increased with the increasing doses of ozone with respect to control reactor. For 2.65 mg/g ozonated reactor total gas volume doubled the amount produced in the control reactor. All the EDCs within the scope of this study were analyzed in sludge using ultrasound-aided sequential sludge extraction method twice a week and the results showed that ozonation affected treatment of EDCs for up to 96%. The highest removal rate was obtained with natural hormones. Rates of treatment of pharmaceuticals were the second best.

Treatment of waste sludge has become an important issue in recent years around the world. However, the trend of waste sludge treatment has shifted from volume minimization and stabilization to reuse of the sludge and recover the energy potential of it. Therefore, anaerobic treatment of sludge is gaining popularity because of byproduct methane production and high percentage of VSS reduction. Pre-treatment of sludge before anaerobic digestion in order to increase methane production, and ozone pre-treatment in this context, is one such option. Domestic sludge also contains the recently recognized, so called, emerging compounds such as Endocrine Disrupting Compounds (EDCs). Therefore treatment of EDCs in sludge is another challenge in waste sludge treatment since direct discharge of such chemicals may harm the environment by causing gender shifts within the fauna. In this context two hormones (estrone and progesterone), three pharmaceuticals (acetaminophen, carbamazepine and diltiazem) and one plasticizer (benzyl-butyl phthalate) were routinely analyzed in sludge samples which were subjected to treatment during this study. Treatment of EDCs during anaerobic digestion and the effect of ozonation both on the performance of digestion and the treatability of EDCs were investigated in this study. Four 2.5L anaerobic jars were used for anaerobic digestion connected to four 1L plastic graduated cylinders immersed in salt-water to collect the off gas. Anaerobic sludge culture of the reactor and the sludge feed to the reactors were obtained from Ankara Tatlar Wastewater Treatment Plant anaerobic digester and return activated sludge (RAS) line, respectively. One of the anaerobic digesters was used as control (no ozonation) and the others were fed with sludge samples ozonated at three different ozone doses 0.65, 1.33 and 2.65 mg ozone/g biomass. Sludge ages of the reactors were initially set to 25 days and the reactors were fed once every 2 days. The TSS, VSS, total gas volume, COD, pH, CH4 percentage and EDCs were analyzed routinely. In the reactors, operated at 25 days, because of the observation of reduction of TSS, SRT was set to infinity / thus, sludge wastage was terminated. Following the startup it was seen that at 2.65 mg ozone/g biomass dose TSS and VSS did not stay constant in the reactor and dropped sharply in the course of operation, indicating that system was not steady at this SRT. However, upon stoppage of sludge wastage from the reactors, thereby setting SRT to infinity, a steady culture could be maintained in the reactors. Both total gas production and CH4 percentage increased with the increasing doses of ozone with respect to control reactor. For 2.65 mg/g ozonated reactor total gas volume doubled the amount produced in the control reactor. All the EDCs within the scope of this study were analyzed in sludge using ultrasound-aided sequential sludge extraction method twice a week and the results showed that ozonation affected treatment of EDCs for up to 96%. The highest removal rate was obtained with natural hormones. Rates of treatment of pharmaceuticals were the second best.

Previous research indicates that pharmaceutically active compounds (PhACs) and endocrine-disrupting compounds (EDCs) are poorly removed during conventional drinking water treatment processes including coagulation; however, removal efficiency increases in the presence of natural organic matter (NOM). Therefore, this project investigates the link between various NOM types with EDC/PhAC removal. Bench-scale coagulation tests were conducted on three different source waters spiked with environmentally relevant levels (nominally 1000 ng/L) of EDCs/PhACs. Two different coagulants were used: polyaluminum chloride (PACl) and aluminum sulphate (alum). NOM was characterized using size exclusion liquid chromatography-organic carbon detection (LC-OCD). Results for Lake Ontario, Otonabee and Grand River water indicate that certain EDCs/PhACs are significantly removed during coagulation while others increase in concentration. Concurrently, particular NOM fractions (biopolymers and humic substances) are also being removed. Solvents used for EDC/PhAC spiking (acetone and acetonitrile) did not affect coagulation, but contributed to low molecular weight neutral and hydrophobic NOM fractions.

Previous research indicates that pharmaceutically active compounds (PhACs) and endocrine-disrupting compounds (EDCs) are poorly removed during conventional drinking water treatment processes including coagulation; however, removal efficiency increases in the presence of natural organic matter (NOM). Therefore, this project investigates the link between various NOM types with EDC/PhAC removal. Bench-scale coagulation tests were conducted on three different source waters spiked with environmentally relevant levels (nominally 1000 ng/L) of EDCs/PhACs. Two different coagulants were used: polyaluminum chloride (PACl) and aluminum sulphate (alum). NOM was characterized using size exclusion liquid chromatography-organic carbon detection (LC-OCD). Results for Lake Ontario, Otonabee and Grand River water indicate that certain EDCs/PhACs are significantly removed during coagulation while others increase in concentration. Concurrently, particular NOM fractions (biopolymers and humic substances) are also being removed. Solvents used for EDC/PhAC spiking (acetone and acetonitrile) did not affect coagulation, but contributed to low molecular weight neutral and hydrophobic NOM fractions.

Treatment of waste sludge has become an important issue in recent years around the world. However, the trend of waste sludge treatment has shifted from volume minimization and stabilization to reuse of the sludge and recover the energy potential of it. Therefore, anaerobic treatment of sludge is gaining popularity because of byproduct methane production and high percentage of VSS reduction. Pre-treatment of sludge before anaerobic digestion in order to increase methane production, and ozone pre-treatment in this context, is one such option. Domestic sludge also contains the recently recognized, so called, emerging compounds such as Endocrine Disrupting Compounds (EDCs). Therefore treatment of EDCs in sludge is another challenge in waste sludge treatment since direct discharge of such chemicals may harm the environment by causing gender shifts within the fauna. In this context two hormones (estrone and progesterone), three pharmaceuticals (acetaminophen, carbamazepine and diltiazem) and one plasticizer (benzyl-butyl phthalate) were routinely analyzed in sludge samples which were subjected to treatment during this study. Treatment of EDCs during anaerobic digestion and the effect of ozonation both on the performance of digestion and the treatability of EDCs were investigated in this study. Four 2.5L anaerobic jars were used for anaerobic digestion connected to four 1L plastic graduated cylinders immersed in salt-water to collect the off gas. Anaerobic sludge culture of the reactor and the sludge feed to the reactors were obtained from Ankara Tatlar Wastewater Treatment Plant anaerobic digester and return activated sludge (RAS) line, respectively. One of the anaerobic digesters was used as control (no ozonation) and the others were fed with sludge samples ozonated at three different ozone doses 0.65, 1.33 and 2.65 mg ozone/g biomass. Sludge ages of the reactors were initially set to 25 days and the reactors were fed once every 2 days. The TSS, VSS, total gas volume, COD, pH, CH4 percentage and EDCs were analyzed routinely. In the reactors, operated at 25 days, because of the observation of reduction of TSS, SRT was set to infinity / thus, sludge wastage was terminated. Following the startup it was seen that at 2.65 mg ozone/g biomass dose TSS and VSS did not stay constant in the reactor and dropped sharply in the course of operation, indicating that system was not steady at this SRT. However, upon stoppage of sludge wastage from the reactors, thereby setting SRT to infinity, a steady culture could be maintained in the reactors. Both total gas production and CH4 percentage increased with the increasing doses of ozone with respect to control reactor. For 2.65 mg/g ozonated reactor total gas volume doubled the amount produced in the control reactor. All the EDCs within the scope of this study were analyzed in sludge using ultrasound-aided sequential sludge extraction method twice a week and the results showed that ozonation affected treatment of EDCs for up to 96%. The highest removal rate was obtained with natural hormones. Rates of treatment of pharmaceuticals were the second best.

Evidence from an abundant number of studies suggests that human female reproductive functions have become impaired over the past half century and that there might be a relationship between endocrine disrupting chemicals (EDCs) and reduced fertility. It is, however, not known by what mechanisms EDCs affect different reproductive functions such as endometrial receptivity, embryo implantation and placentation. The endometrium is continuously changing its morphological and functional properties, responding to cyclic changes of oestrogen and progesterone levels during the menstrual cycle. These changes include monthly preparation for embryo implantation through changed endometrial angiogenic activity and consequent changes in endometrial vasculature. Use of primary human endometrial endothelial cells (HEECs) in this work was evaluated as a possible screening tool for effects caused by EDCs on human endometrial vasculature and subsequently on various endometrial functions. In this study HEEC and endometrial stromal cells were isolated. HEECs were grown in monocultures, and together with stromal cells in co-cultures, and exposed to endocrine active substances. These were cadmium, which has oestrogenic properties, tamoxifen, with anti-oestrogenic effects, mifepristone, which is an anti-progestin, and bisphenol A, with oestrogenic properties. The effects were evaluated by using proliferation and viability assays, migration and tube formation assays, quantitative PCR (qPCR), immunohistochemistry and western blot. Cadmium affected the expression of angiogenesis-related genes, and caused different effects in HEECs cultured alone vs. HEECs co-cultured with stromal cells. Tamoxifen altered the expression of angiogenesis-related genes and reduced HEEC migration, thus having an anti-angiogenic effect. Mifepristone caused reduced formation of tubular structures in tube-formation assays involving HEECs co-cultured with stromal cells. Bisphenol A promoted tube formation in co-cultured HEECs which was related to changes in the expression of several angiogenesis-related genes as well as up-regulated expression of VEGF-D protein. In conclusion, we showed that EDCs have the ability to induce changes in endometrial angiogenic activity in vitro and may thus disturb normal endometrial functions related to fertility and pregnancy. HEECs grown in vitro may provide valuable information on the effects of EDCs on human endometrial functions. However, this model is not suitable as a large-scale screening tool.

Endocrine disruption and high occurrences of intersex have been observed in wild fish associated with wastewater treatment plant (WWTP) effluents in the urbanized reaches of the Grand River watershed located in southern Ontario, Canada. WWTP effluent is a complex matrix with diverse aquatic environmental contaminants and stressors. This study aimed to: (1) characterize the spatio-temporal distribution and fate of antiandrogenic personal care products (triclosan, chlorophene, and dichlorophene), along with selected pharmaceuticals (carbamazepine, ibuprofen, naproxen, and venlafaxine) and the herbicide, atrazine in the Grand River watershed and (2) model the behaviour of these contaminants in the aquatic environment. Water sampling of 29 sites which covered six municipal WWTPs and ~100 km of river length was completed during summer low flows (July 2012). Monthly samples were also collected immediately upstream and downstream of a major WWTP (Kitchener) from August to November 2012. Many of the target pharmaceuticals and triclosan were detected in WWTP effluents in the Grand River watershed, especially those that did not nitrify (minimal treatment with high ammonia). Chlorophene was either undetected or was only found at trace levels in the effluents. Under low flow conditions, triclosan and several other pharmaceuticals exhibited a spatial pattern where concentrations increased directly downstream of the WWTPs, then decreased with distance downstream (dilution and/or degradation). Chlorophene, in contrast, was not found downstream of most of the WWTP outfalls but was first detected at a site 5 km upstream of a WWTP and then continued with relatively constant concentrations for approximately 29 km downstream. It was also only found during the summer sampling period. Atrazine was consistently found in all sampling locations which reflected the agricultural non-point source nature of this compound. The WASP 7.5 model (US Environmental Protection Agency) was adapted and calibrated to a reach of the Grand River associated with the Kitchener WWTP. The simulation of the fate and transport of the target compounds revealed that flow-driven transport processes (advection and dispersion) greatly influence their behaviour in the aquatic environment. However, fate mechanisms such as biodegradation and photolysis also potentially play an important role in the attenuation of most compounds. The exception was carbamazepine where it was shown to act as a conservative tracer compound for wastewater specific contaminants in the water phase. The fate model developed can be applied in the future to predict the fate of a wide variety of contaminants of emerging concern across the watershed to help define the exposure of these biologically active chemicals to sensitive ecosystems.

<p>In order to meet disinfection guidelines, wastewater utilities must achieve a high level of treatment before discharging treated water for irrigation or industrial use. However, public pressure to reduce disinfection by-products and pharmaceutically-active compounds, recently-promulgated regulations on chlorine-resistant microorganisms such as Cryptosporidium parvum, and growth in population and water demand have driven an interest in alternatives to chlorination. The WateReuse Foundation has funded WRF 02-009 (Innovative Treatment Technologies for Reclaimed Water), which is a survey of current and emerging reuse water treatment technologies. The goal of the project is to evaluate treatment technologies can provide adequate recycled water effluent without the cost of reverse osmosis (RO) or the disinfection by-products (DBPs) formed during chlorination.</p><p>The inactivation of indigenous microorganisms (total and fecal coliform bacteria, and total aerobic spores) and spiked surrogate, respiratory, and enteric viruses (MS-2 bacteriophage, adenovirus type 4, reovirus type 3, and coxsackievirus type B5) and chemical degradation by wastewater treatment technologies was evaluated on the bench-scale. These include: low- and medium-pressure UV, LPUV/H₂O₂, ozonation, O₃/H₂O₂, peracetic acid (PAA), LPUV/PAA, chlorination, chloramination, and ultrafiltration. The applicability of the candidate disinfection methods, especially emerging and comparatively untested methods such as PAA and advanced oxidation processes (AOPs), was studied through comparison of their performance and the important water matrix parameters (e.g., alkalinity, BOD, TSS, etc.).</p><p>Of the chemical disinfectants, molecular ozone and free chlorine were the most effective, with substantial coliform and virus kill at low doses. Combined chlorine in the form of monochloramine had a reduced disinfectant capacity than free chlorine, and peracetic acid (PAA) performed equally as well as free chlorine with respect to coliform bacteria in some instances but had little to no impact on spiked MS2 bacteriophage. None of the aforementioned disinfectants had an appreciable impact on indigenous aerobic spore-forming bacteria due to their physiology. UV and O₃ rapidly killed human enteric and respiratory viruses, but a consistent benefit by AOPs over their base technologies was not observed for any of their base technologies.</p><p>Low and medium-pressure UV inactivated free-floating indigenous coliform bacteria almost immediately, while slower inactivation rates at higher UV fluences illustrated the "tailing" behavior observed when bacteria are embedded in or shielded by particulate matter. Log-linear inactivation of spiked viruses and indigenous aerobic spores by UV was consistent across the utility waters. The UV-based advanced oxidation processes (UV/H₂O₂ and UV/PAA) destroyed spiked organic compounds at much higher rates than direct UV photolysis, while O₃, with or without H₂O₂ , oxidized spiked compounds and reduced estrogenicity (EEQ) at low doses. Recalcitrant chlorinated hydrocarbons such as TCEP were only moderately removed by the tested AOPs, but low doses of O₃ (3 ppm residual O₃) reduced estrogenic activity by 99%. Like other disinfection processes, AOP performance is dependant on pretreatment, especially concerning particulates.</p> / Dissertation

Alkylphenol polyethoxylates (APEOs), a class of nonionic surfactants, have been widely used for industrial, agricultural and household applications. The biodegradation metabolites of APEOs, such as nonylphenol and octylphenol, are more persistent and known to disrupt endocrine function in wildlife and human. These compounds are also recognized as endocrine disrupting chemicals (EDCs). The objectives of this study were to investigate the distribution and removal efficiencies of EDCs, including nonylphenol diethoxylates (NP2EO), nonylphenol monoethoxylates (NP1EO), nonylphenol (NP) and octylphenol (OP), of wastewater treated by the constructed wetland systems along the Dahan River and around the Dapeng Bay, respectively. In addition, the method of risk quotient was used to evaluate the potential ecological risk of APEOs to aquatic organisms in current study. The water samples collected from 32 sampling sites in the Dapeng Bay National Scenic Area including Datan, Pengcun and Linbain right bank constructed wetlands. The samples were then concentrated by solid phase extraction, and analyzed for target compounds by HPLC/fluorescence. According to the results, nonylphenol diethoxylates, nonylphenol monoethoxylates, nonylphenol and octylphenol were found approximately equal to 29.9, 47.3, 20.5 and 57.7 %, respectively of the samples from three constructed wetlands with concentrations ranged from <3.3 to 968.7, <3.3 to 226.5, <1.3 to 238.4 and <1.0 to 1458.7 ng/L, respectively. Temporal variation of APEOs showed a decreasing in the order of summer¡Öspring¡Öwinter¡Öautumn. The removal efficiencies of APEOs in these constructed wetlands showed a decreasing order of Datan wetland¡ÖPengcun wetland¡ÖLinbain right bank wetland. In addition, the samples collected from 18 sampling sites from the constructed wetlands along the riparian of Dahan River including Daniaopi, Hsin-Hai Bridge Phases I and II constructed wetlands. According to the results, nonylphenol diethoxylates, nonylphenol monoethoxylates, nonylphenol and octylphenol were found approximately equal to 91.9¡B84.8¡B17.1 and 73.7 %, respectively of samples collected from three constructed wetlands with concentrations ranged from <3.3 to 11191.5, <3.3 to 6069.0, <1.3 to 671.0 and <1.0 to 5581.9 ng/L, respectively. The removal potential of APEOs in these constructed wetlands showed a decreasing order of Hsin-Hai Bridge Phases II¡ÖDaniaopi¡ÖHsin-Hai Bridge Phases I constructed wetland. Regarding the ecological assessment in this research, the calculated risk quotients were up to 30 times higher in the constructed wetland systems of Dahan River than those in the Dapeng Bay National Scenic Area, indicating that the existing concentrations of these EDCs in wetland systems might cause potential ecological risks to aquatic organisms. Furthermore, the decreasing risk quotient from influent to effluent indicating the capabilities of treating alkylphenolic compounds in these constructed wetlands.

To date, most studies on the fate and removal of endocrine disrupting compounds (EDCs) and pharmaceutical and personal care products (PPCPs) in wastewater focus on their fate in municipal wastewater treatment plants, and mostly under aerobic condition. There are limited studies related to anaerobic condition and (to our knowledge) no study on the removal of EDCs in landfill leachate by AnMBR. Moreover, for most studies under anaerobic condition, the removal of EDCs was only reported in the liquid phase; solid phase extraction was not reported, thereby preventing mass balance in the studies. This research was conducted to investigate the potential of AnMBR for reduction of organic strength and removal of EDCs in landfill leachate. A novel lab-scale upflow anaerobic sludge blanket (UASB) reactor equipped with dual-flat sheet ultrafiltration and microfiltration membrane modules was designed and constructed to test the potential to remove EDCs and traditional landfill leachate constituents (COD, turbidity). The target EDC was 17β-estradiol (E2), a prevalent female hormone used for contraceptives and hormone replacement therapy. Due to the nature of packaging and widespread use in households, the entry of E2 into landfills is highly likely, and has been reported. The quantification of E2 from liquid phase in this project is performed by the use of solid-phase microextraction (SPME) with GC/MS. Batch assays were conducted to determine the anaerobic biodegradability of E2 as well as to measure the respective distribution coefficients of E2 to PAC, colloids and anaerobic sludge biomass. In the adsorption batch assays, it was found that the PAC has stronger adsorption potential than anaerobic sludge. The adsorption potential of E2, E1 and EE2 on sludge follows the order E2>EE2>E1 which correlates to the Kow values (4.01, 3.67, 3.1, respectively). However, all three compounds showed the same adsorption potential to the Norit 20B PAC. The biodegradability of E2 was investigated in both liquid and solid phase and under several conditions such as methanogenesis, methanogenesis with aid from PAC, and methanogenesis with additional alternative electron acceptors added (sulfate and nitrate). E2 was found to transform to E1 under all tested conditions. The compounds are present in both liquid and solid phase. E2 and E1 were not detected (< 4ng/L and <10ng/L, respectively) in the liquid phase after 25 days in most cases except the case of adding additional sulfate. The AnMBR was designed, fabricated and operated for 2 years. During the stable condition period of the AnMBR, the high removal efficiencies of COD and E2 achieved were around 92% and 98%, respectively. However, E2 was still detected in the effluent at average concentrations of 30-40 µg/L range. To expand hormone retention and removal by the AnMBR, as well as to control membrane fouling, powder activated carbon (PAC) was added to the reactor. After the PAC was added, the concentration of E2 was reduced to less than the detection limit (4ng/L) in both MF and UF effluents. The log removal of E2 in the AnMBR system increased immediately from 1.7 without PAC to 5.2 after PAC was added. This study demonstrated that the AnMBR has high potential for removal of E2, and with aid from PAC, the AnMBR can remove E2 from landfill leachate to levels below detection limit.