Study on the fate of per- and polyfluoroalkyl substances during thermophilic anaerobic digestion of sewage sludge and the role of granular activated carbon addition.

Limited information is available on the removal of per- and polyfluoroalkyl substances (PFAS) in anaerobic digestion (AD). Τhe fate of six PFAS was studied in thermophilic bioreactors in the presence of granular activated carbon (GAC) and voltage application. Reactors with GAC exhibited lower concentrations of volatile fatty acids and higher methane production compared to those with and without the application of voltage. Analysis of PFAS in dissolved and solid phase showed that their distribution was dependent on perfluorocarbon chain length and functional group. Mass balances showed that PFAS were not removed during conventional AD or after applying voltage; however, significant removal (up to 61 ± 8 %) was observed in bioreactors with GAC for perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonate (PFOS). Biomass characterization showed that in these bioreactors, the relative abundance of Acinetobacter and Pseudomonas was higher, indicating their potential role in PFAS biotransformation.

Acesulfame degradation by thermally activated persulfate: Kinetics, transformation products and estimated toxicity.

The existence of the artificial sweetener acesulfame (ACE) in quantities of significance can negatively impact water quality, and its consumption has been associated with deleterious health effects. The present investigation explores the efficacy of heat-activated sodium persulfate (SPS) for eliminating ACE. The complete degradation of 0.50 mg L-1 of ACE was achieved within 45 min under a reaction temperature of 50 °C and 100 mg L-1 of SPS. The impact of thermal decomposition on ACE at a temperature of 60 °C was negligible. This study considers several factors, such as the SPS and ACE loading, the reaction temperature, the initial pH, and the water matrix of the reactor. The results indicate that the method's efficiency is positively correlated with higher initial concentrations of SPS, whereas it is inversely associated with the initial concentration of ACE. Furthermore, higher reaction temperatures and acidic initial pH levels promote the degradation of acesulfame. At the same time, certain constituents of the water matrix, such as humic acid, chlorides, and bicarbonates, can hinder the degradation process. Additionally, the data from LC-QToF-MS analysis of the samples were used to investigate transformation through suspect and non-target screening approaches. Overall, ACE's eight transformation products (TPs) were detected, and a potential ACE decomposition pathway was proposed. The concentration of TPs followed a volcano curve, decreasing in long treatment times. The ecotoxicity of ACE and its identified TPs was predicted using the ECOSAR software. The majority of TPs exhibited not harmful values.

Combined use of strictly anaerobic MBBR and aerobic MBR for municipal wastewater treatment and removal of pharmaceuticals.

An integrated lab-scale wastewater treatment system consisting of an anaerobic Moving Bed Biofilm Reactor (AnMBBR) and an aerobic Membrane Bioreactor (AeMBR) in series was used to study the removal and fate of pharmaceuticals during wastewater treatment. Continuous-flow experiments were conducted applying different temperatures to the AnMBBR (Phase A: 35 °C; Phase B: 20 °C), while batch experiments were performed for calculating sorption and biotransformation kinetics. The total removal of major pollutants and target pharmaceuticals was not affected by the temperature of the AnMBBR. In Phase A, the average removal of dissolved chemical oxygen demand (COD), biological oxygen demand (BOD), and ammonium nitrogen (NH4-N) was 86%, 91% and 96% while in Phase B, 91%, 96% and 96%, respectively. Removal efficiencies ranging between 65% and 100% were observed for metronidazole (MTZ), trimethoprim (TMP), sulfamethoxazole (SMX), and valsartan (VAL), while slight (<30%) or no removal was observed for carbamazepine (CBZ) and diclofenac (DCF), respectively. Application of a mass balance model showed that the predominant mechanism for the removal of pharmaceuticals was biotransformation, while the role of sorption was of minor importance. The AeMBR was critical for VAL, SMX and TMP biodegradation; the elimination of MTZ was strongly enhanced by the AnMBBR. In both bioreactors, Bacteroidetes was the dominant phylum in both bioreactors over time. In the AnMBBR, Cloacibacterium and Bacteroides had a higher abundance in the biocarriers compared to the suspended biomass.

Removal of drug dexamethasone from aqueous matrices using low frequency ultrasound: Kinetics, transformation products, and effect of microplastics.

Sonochemical oxidation was employed for the degradation of the drug dexamethasone (Dex). The oxidation at 20 kHz followed pseudo-first-order kinetics and increased with applied ultrasound power density. Acoustic cavitation at 71 W/L was able to eliminate 500 µg/L of dexamethasone from ultrapure water at inherent pH in less than 60 min. The oxidation was enhanced at pH 3 and decreased at increased Dex concentration. Scavenging experiments with tert-butanol showed that hydroxyl radicals play a crucial role in decomposition, where the reaction mainly occurs on the gas-liquid interface of the formed cavities. The addition of chloride did not affect Dex removal, while in the presence of 10 mg/L of humic acid or bicarbonate, the apparent kinetic constant decreased from 0.0423 ± 0.004 min-1 to about 0.03 ± 0.002 min-1. The rate in secondary effluent was 3.3 times lower than in ultrapure water due to the complexity of the actual matrix. Six transformation products were identified via high resolution LC-MS during the sonochemical oxidation of 3 mg/L Dex in ultrapure water. The presence of polyethylene or polystyrene microplastics slightly enhanced DEX sonodegradation. The effect of ultrasound irradiation at 71 W/L for 60 min on the microplastics surfaces was inconsiderable.

Heat-activated persulfate for the degradation of micropollutants in water: A comprehensive review and future perspectives.

This work is a critical review of the most important studies that have dealt with heat-activated persulfate to degrade persistent micropollutants in the last six years. The effect of the different operating parameters is discussed, wherein in all cases, the efficiency was favored at higher temperatures and oxidant concentrations. Particular emphasis was given to the effect of the aqueous matrix. Since heat activation is a homogeneous process based on the production of free radicals, in most of the studies presented, the removal of pollutants decreases as the complexity of the aqueous matrix increases except in cases where secondary oxidative species are produced that are selective with specific pollutants. It has also been observed that the change in toxicity usually follows the removal of the parent compound despite the formation of several by-products. Nowadays, combining different processes for the simultaneous activation of persulfate seems to be gaining ground. A hybrid process is an interesting strategy to reduce costs and increase efficiency, especially in real wastewater. In this light, the most interesting studies of hybrid systems for the destruction of micropollutants in recent years based on thermally activated persulfate are also summarized. Finally, some steps are proposed for future research towards the industrial application, including the study of chemical mixtures, the integrated toxicity assessment, the examination of simultaneous disinfection and decomposition of pollutants into real wastewater, the estimation of the required costs, and energy the combination of processes and their coupling with renewable sources, and the design of pilot plants and the scale-up of the hybrid processes.

Thermally activated persulfate oxidation of ampicillin: Kinetics, transformation products and ecotoxicity.

The heat-activated persulfate system showed encouraging results for the destruction of the widely used antibiotic Ampicillin (AMP). AMP removal follows exponential decay, and the observed kinetic constant was enhanced with persulfate (PS) dosage at the range 50-500 mg L-1 and temperature (40-60 °C), while AMP thermolysis at 60 °C was almost negligible. The apparent activation energy was estimated to 124.7 kJ mol-1. Alkaline conditions, water matrix constituents like bicarbonates, humic acid, and real water matrices retarded AMP oxidation. Experiments performed with tert-butanol and methanol as scavengers demonstrated the contribution of sulfate radicals as the dominant reactive species. Seven transformation products (TPs) of AMP have been identified from AMP destruction. An EC50 value equal to 187 mg L-1 was calculated for 72 h of exposure of the microalgae Chlorella sorokiniana to AMP. According to the ecotoxicity experiments that conducted after treatment of AMP with PS for different reaction times, no important inhibition of microalgae was noticed for contact time of 72 h and 10 d. These results indicate the formation of no toxic AMP by-products for the applied experimental conditions.

Sorption of two common antihypertensive drugs onto polystyrene microplastics in water matrices.

Recent studies have shown the widespread occurrence of microplastics in multiple environmental compartments. When discharged into the aquatic environment, microplastics interact with other chemicals acting as vectors of organic and inorganic micropollutants. In the present study, we examined the sorption of two commonly used antihypertensive drugs, valsartan (VAL) and losartan (LOS), onto polystyrene (PS) microplastics and we studied the effects of water matrix, solution's pH, salinity, and microplastics' aging on their sorption. According to the results, the sorption of VAL and LOS onto PS is a slow process that reaches equilibrium after 12 days. The sorption of both target micropollutants was pH-dependent and significantly decreased under alkaline conditions. The removal of VAL was enhanced in the presence of 100 mM of Ca2+ while no statistical significant effects were observed when Na+ was added. The increase of salinity either did not affect or decreased the removal of LOS. Lower sorption of both drugs was observed when aged PS was used despite that the specific surface area for aged PS was 39% higher than pristine. Calculation of the sorption distribution coefficient (Kd) for different water matrices showed that the increase of matrix complexity inhibited target compounds' removal and the sorption rate decreased from bottled water > river water ≈ treated wastewater for the two compounds. For VAL, the Kd values ranged between 795 ± 63 L/kg (bottled water) and 384 ± 88 L/kg (river water), while for LOS between 4453 ± 417 L/kg (bottled water) and 3078 ± 716 L/kg (treated wastewater). Both VAL and LOS sorption onto PS microplastics can be described by hydrophobic and electrostatic interactions. The current results indicate that PS particles could affect the transportation of antihypertensive drugs in the aquatic environment causing potential adverse effects on the environment and public health.

Exposure to phthalates from personal care products: Urinary levels and predictors of exposure.

Phthalates are a large group of chemicals used in many everyday consumer products such as food packaging, household cleaners, cosmetics, fragrances and personal care products (PCPs). A number of diseases such as obesity, hypertension, as well as reproductive system effects and endocrine disorders have been linked to phthalate exposure through the use of PCPs, due to their frequent use and high phthalate content. In this study we review available literature on phthalates and their metabolites in urine and report the various determinants of exposure through the use of PCPs in infants, toddlers, children and adults. The range of creatinine-adjusted concentrations for each phthalate was 1.5-14956.1 µg/g for MEP, 0.4-94.5 µg/g for MEHP, 0.39-425.9 µg/g for MEHHP, 0.5-481.3 µg/g for MEOHP, 0.1-755.1 µg/g for MBzP, and 0.3-401.4 µg/g for MiBP. Time of sampling, frequency of use, race and age are critical factors that influence phthalate concentrations. Using PCPs 48 h before urine collection, using a combination of PCPs (i.e., particularly leave-on versus rinse-off products), being younger (i.e., children compared to their mothers), and being a woman of colour (i.e., Mexican-American and black versus white) leads to higher phthalate levels in urine. The most striking association between any phthalate and PCPs was observed between MEP and perfumes or fragrance-containing products such as shampoos, body lotions and hair products. Future studies should focus on different types and brands of PCPs (i.e., branded versus generic), explore possible ethnic/racial differences and the applicability of non-invasive matrices such as nails and hair for phthalate biomonitoring, as well as intervention studies that explore behavioural changes.

Removal of drug losartan in environmental aquatic matrices by heat-activated persulfate: Kinetics, transformation products and synergistic effects.

In this study, the oxidative degradation of losartan (LOS), a widely administered medicine for high blood pressure by heat-activated persulfate was investigated. Increased temperature and persulfate concentration, as well as acidic conditions enhance the degradation efficiency of LOS, whose rate follows pseudo-first order kinetics. From the respective apparent rate constants in the range 40-60 °C, an apparent activation energy of 112.70 kJ/mol was computed. Radical scavenging tests demonstrated that both HO• and [Formula: see text] contribute towards LOS degradation. LOS degradation was suppressed in real water matrices including bottled water (BW) and secondary wastewater effluent (WW), while other experiments indicated that the presence of bicarbonates and humic acid negatively affected its oxidation. Instead, the addition of chloride ions at 250 mg/L resulted in a positive effect on LOS removal. The combination of heat-activated PS with low-frequency ultrasound exhibited a synergistic effect, with the ratio S being 2.29 in BW and 1.52 in WW. Five transformation products of LOS were identified through HRMS suspect and non-target screening approaches, among which two are reported for the first time. Using the in-house risk assessment program, ToxTrAMs was revealed that most of the identified TPs present higher toxicity than LOS against Daphnia magna.

Solar light induced photocatalytic removal of sulfamethoxazole from water and wastewater using BiOCl photocatalyst.

The photocatalytic activity of bismuth oxychloride (BiOCl) toward sulfamethoxazole (SMX) elimination was investigated. BiOCl was synthesized according to a simple method using thiourea. Its physicochemical characteristics were determined by nitrogen physisorption, X-Ray diffraction, diffuse reflectance spectroscopy, scanning electron microscopy and transmission electron microscopy. Simulated solar irradiation and 1 g/L BiOCl, could effectively remove 0.5 mg/L SMX in less than 90 min. An increase in SMX concentration from 0.25 mg/L to 4 mg/L decreased the observed kinetic constant. Concerning the pH effect, it was found that under alkaline conditions SMX removal was slightly hindered. The water matrix's influence on SMX removal was explored, carrying out experiments in real water matrices, (bottled water (BW) and secondary effluent (WW)). Interestingly SMX removal was not practically altered in WW secondary effluent, but it was slightly hindered in BW bottled water. Experiments, performed in synthetic matrices, revealed that the presence of bicarbonates and chlorides slightly slowed down degradation kinetics, while humic acid enhanced SMX removal at concentrations up to 10 mg/L. Finally, an enhancement on SMX degradation was observed in the presence of persulfate. Quenching experiments of potential reactive species revealed that SMX degradation takes place mainly through reaction with hydroxyl radicals and photogenerated electrons.

Determinants of flame retardants in non-occupationally exposed individuals - A review.

Flame retardants (FRs) constitute a large group of different substances, some of which have been phased out of the market due to health concerns, while others are still used in many common consumer products to prevent fire hazards. This review addressed the determinants of FRs in non-occupationally exposed individuals based on surveys and questionnaire data. For this literature review, three databases (Scopus, Pubmed and Web of Knowledge) were searched by applying suitable terms, inclusion and exclusion criteria, producing a final selection of 78 articles for review. Based on these surveys there is epidemiological evidence for a significant association (p < 0.05) among human exposure and demographic factors, as well as a significant correlation between exposure to FRs and behavioural and environmental factors. Age, gender, housing characteristics, electrical and electronic equipment and mouthing behaviour (in children) play a leading role in human exposure to FRs as published studies demonstrated. However, the methodological differences among studies such as population size, questionnaire design and statistical analysis did not reveal a complete pattern of human exposure routes. Risk perception and communication are also discussed based on limited available data. Knowledge gaps and future perspectives relating to standardized protocols, elucidation of contamination sources, and risk response of health information from different target groups were also identified.

Sonochemical degradation of trimethoprim in water matrices: Effect of operating conditions, identification of transformation products and toxicity assessment.

The sonochemical degradation of trimethoprim (TMP), a widely used antibiotic, in various water matrices was investigated. The effect of several parameters, such as initial TMP concentration (0.5-3 mg/L), actual power density (20-60 W/L), initial solution pH (3-10), inorganic ions, humic acid and water matrix on degradation kinetics was examined. The pseudo-first order degradation rate of TMP was found to increase with increasing power density and decreasing pH, water complexity (ultrapure water > bottled water > secondary wastewater) and initial TMP concentration. TMP degradation is accompanied by the formation of several transformation products (TPs) as evidenced by LC-QToF-MS analysis. Nine such TPs were successfully identified and their time-trend profiles during degradation were followed. An in silico toxicity evaluation was performed showing that several TPs could potentially be more toxic than the parent compound towards Daphnia magna, Pimephales promelas and Pseudokirchneriella subcapitata.

Degradation of methylparaben by sonocatalysis using a Co-Fe magnetic carbon xerogel.

The degradation of methylparaben (MP) through 20 kHz ultrasound coupled with a bimetallic Co-Fe carbon xerogel (CX/CoFe) was investigated in this work. Experiments were performed at actual power densities of 25 and 52 W/L, catalyst loadings of 12.5 and 25 mg/L, MP concentrations between 1 and 4.2 mg/L and initial pH values between 3 and 10 in ultrapure water (UPW). Matrix effects were studied in bottled water (BW) and secondary treated wastewater (WW), as well as in UPW spiked with bicarbonate, chloride or humic acid. The pseudo-first order kinetics of MP degradation increase with power and catalyst loading and decrease with MP concentration and matrix complexity; moreover, the reaction is also favored at near-neutral conditions and in the presence of dissolved oxygen. The contribution of the catalyst is synergistic to the sonochemical degradation of MP and the extent of synergy is quantified to be >45%. This effect was ascribed to the ability of CX/CoFe to catalyze the dissociation of hydrogen peroxide, formed through water sonolysis, to hydroxyl radicals. Experiments in UPW spiked with an excess of tert-butanol (radical scavenger), sodium dodecyl sulfate or sodium acetate (surfactants) led to substantially decreased rates (i.e. by about 8 times), thus implying that the liquid bulk and the gas-liquid interface are major reaction sites. The stability of CX/CoFe was shown by performing reusability cycles employing magnetic separation of the catalyst after the treatment stage. It was found that the CX/CoFe catalyst can be reused in up to four successive cycles without noteworthy variation of the overall performance of the sonocatalytic process.

The physicochemical properties and antioxidant capacities of commercial and homemade Greek vinegars.

BACKGROUND: Due to its high content of antioxidant compounds, vinegar can be considered an excellent source of health promoting compounds. The aim of this study was to compare the physicochemical composition and antioxidant capacity of eighteen vinegars made from red and white wine, apple, rose petals, and balsamic acid. METHODS: Eight randomly selected commercial vinegars from the Greek market and ten homemade vinegars were used. Their quality characteristics, color profile, polyphenol content and antioxidant capacity were determined. RESULTS: The results showed that there is a high diversity of values among the examined vinegar samples indicating that the raw material and the applied production methods can affect their composition. Red wine vinegars and red balsamic vinegars exhibited the highest levels of total phenols, followed by fruit vinegars, white wine vinegars and white balsamic vinegars. The antioxidant capacity was strongly affected by the total phenolic content, followed by the total flavonoid content and less so by the color density. CONCLUSIONS: Our findings could provide important information to consumers about the randomly selected vinegars from the Greek market and could be used for the development and optimization of homemade and commercial vinegars.

Review on fresh and dried figs: Chemical analysis and occurrence of phytochemical compounds, antioxidant capacity and health effects.

Fig fruit (Ficus carica L.) is one of the most important agricultural products of the tropic and subtropics areas. In the Middle East and the Mediterranean region, the fig is included in diet since the ancient years and it is considered as the symbol of longevity. This review presents the main phytochemical compounds found in fresh and dried figs of different varieties, describes the analytical methods used for their determination and discuss the antioxidant capacity and the potential effects of figs in human health. Phenolic acids and flavonoids are the major types of phytochemical compounds that have been found in fresh and dried figs. Their levels are strongly influenced by various factors such as the color, the part of fruit, the maturity and the drying process. Gallic acid, chlorogenic acid, rutin, quercetin-3-O-rutinoside and epicatechin are the most predominant phenolic acids and flavonoids in dried and fresh fig varieties. Extracts of dark-colored varieties contain higher amount of phenolic compounds than the light-colored varieties. Fruit skin contributes most to the amount of phenolic compounds compared to the fruit pulp. The ripening stage affects the concentrations of phenolic compounds in figs, the maximum have been found in ripe fruit. On the other hand, contradictory results have been reported in the literature regarding the effect of air- and sun- drying on the total content of phytochemical compounds, as well as on the concentrations of individual phenolic compounds and carotenoids in figs. The antioxidant capacity of figs is highly correlated with their amount of phenolic compounds. The leaves, roots, fruit and latex of the plant are known for their health properties including acetyl cholinesterase inhibition, antifungal, anti-helminthic and anticarcinogenic activities. Future efforts should be focused on the application of fig extracts as functional ingredients of food products, on clinical trials in order to confirm the beneficial effect of plant extracts in human health and, on the valorization of the waste material produced during figs' processing.

Review on the occurrence and fate of microplastics in Sewage Treatment Plants.

Microplastics are plastic fragments lower than 5 mm that are detected in the environment causing various effects on organisms. Several research articles have recognized Sewage Treatment Plants as important sources of polyethylene and polypropylene beads, polyester, polyamide and other types of microplastics. For their determination, techniques such as visual identification using microscope, Fourier-transform infrared and RAMAN spectroscopy are used, while chemical oxidation, enzymatic maceration and density separation are applied as pretreatment methods for the removal of the inorganic and organic content. Microplastics' concentrations range up to 3160 particles L-1, 125 particles L-1 and 170.9 × 103 particles Kg-1 TS dw in raw, treated wastewater and sludge, respectively. Their removal during wastewater treatment ranges between 72% and 99.4%; the main processes that contribute to their removal are primary and secondary treatment, while the effect of tertiary treatment depends on the applied technology. Entrapment in suspended solids and accumulation to sludge are the major mechanisms governing their fate. A standardized protocol for samples' collection and pretreatment as well as microplastics' isolation and characterization is needed; future reseach should investigate the possible chemical and physical changes of microplastics during treatment, and their role as carriers for the transfer of emerging micropollutants.

Using mechanisms of hydrolysis and sorption to reduce siloxanes occurrence in biogas of anaerobic sludge digesters.

Hydrolysis of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6) and dodecamethylcyclohexasilane (D6_silane) and their sorption to digested sludge was studied in batch experiments. Hydrolysis was affected by the type of the compound and the applied temperature, while the relevant half-life values ranged between 0.07±0.01d (D3, 55°C) and 48.4±17.1d (D6_silane, 4°C). D5 showed the greatest affinity for sorption to digested sludge (logKd: 3.84±3.42), the lowest LogKd value was found for D3 (1.46±0.95). Prediction of investigated compounds' fate in a single-stage anaerobic digestion system indicated that volatilization seems to be the major fate in both mesophilic and thermophilic conditions. The addition of a pre-digester with 3d retention time would significantly decrease the expected concentrations of all siloxanes in biogas, enhancing their removal through hydrolysis and sorption to sludge.

Review on the occurrence, fate and removal of perfluorinated compounds during wastewater treatment.

Perfluorinated compounds (PFCs) consist of a fully fluorinated hydrophobic alkyl chain attached to a hydrophilic end group. Due to their wide use in several industrial and household applications, they have been detected in numerous Sewage Treatment Plants (STPs) during the last ten years. The present review reports the occurrence of 22 PFCs (C4-C14, C16, C18 carboxylates; C4-C8 and C10 sulfonates; 3 sulfonamides) in municipal or/and industrial wastewater, originating from 24 monitoring studies. PFCs levels in sewage sludge have also been reported using data from 12 studies. Most of the above monitoring data originate from the USA, North Europe and Asia and concern perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), while limited information is available from Mediterranean area, Canada and Australia. PFCs concentrations range up to some hundreds ng/L and some thousands ng/g dry weight in raw wastewater and sludge, respectively. They are not significantly removed during secondary biological treatment, while their concentrations in treated wastewater are often higher compared to raw sewage. Their biodegradation during wastewater treatment does not seem possible; whereas some recent studies have noted the potential transformation of precursor compounds to PFCs during biological wastewater treatment. PFCs sorption onto sludge has been studied in depth and seems to be an important mechanism governing their removal in STPs. Concerning tertiary treatment technologies, significant PFCs removal has been observed using activated carbon, nanofiltration, reverse osmosis or applying advanced oxidation and reduction processes. Most of these studies have been conducted using pure water, while in many cases the experiments have been performed under extreme laboratory conditions (high concentrations, high radiation source, temperature or pressure). Future efforts should be focused on better understanding of biotransformation processes occurred in aerobic and anaerobic bioreactors and result to PFCs formation and on the application of advanced treatment technologies under conditions commonly found in STPs.

Sorption of Perfluorinated Compounds onto different types of sewage sludge and assessment of its importance during wastewater treatment.

The distribution coefficient (Kd) and the organic carbon distribution coefficient (KOC) were determined for four Perfluorinated Compounds (PFCs) to three different types of sludge taken from a conventional Sewage Treatment Plant (STP). Batch experiments were performed in six different environmental relevant concentrations (200ngL(-1)to 5µgL(-1)) containing 1gL(-1) sludge. Kd values ranged from 330 to 6015, 329 to 17432 and 162 to 11770Lkg(-1) for primary, secondary and digested sludge, respectively. The effects of solution's pH, ionic strength and cation types on PFCs sorption were also evaluated. Sorption capacities of PFCs significantly decreased with increased pH values from 6 to 8. Furthermore, the divalent cation (Ca(2+)) enhanced PFCs sorption to a higher degree in comparison with the monovalent cation (Na(+)) at the same ionic strength. The obtained Kd values were applied to estimate the sorbed fractions of each PFC in different stages of a typical STP and to calculate their removal through treated wastewater and sludge. In primary settling tank, the predicted sorbed fractions ranged from 3% for Perfluorooctanoic Acid (PFOA) to 55% for Perfluoroundecanoic acid (PFUdA), while in activated sludge tank and anaerobic digester sorption was more than 50% for all target compounds. Almost 86% of initial PFOA load is expected to be detected in treated wastewater; while Perfluorodecanoic acid (PFDA), PFUdA and Perfluorooctanesulfonate (PFOS) can be significantly removed (>49%) via sorption to primary and excess secondary sludge. In anaerobic digester, the major part (>76%) of target PFCs is expected to be sorbed to sludge, while almost 3% of initial PFOA load will be detected in sludge leachates.

Contribution of primary and secondary treatment on the removal of benzothiazoles, benzotriazoles, endocrine disruptors, pharmaceuticals and perfluorinated compounds in a sewage treatment plant.

The occurrence and fate of 36 emerging contaminants, belonging to five different classes, (benzotriazoles, BTRs; benzothiazoles, BTHs; perfluorinated compounds, PFCs; non-steroidal anti-inflammatory drugs, NSAIDs and endocrine disruptors, EDCs) were investigated in raw, treated wastewater (both particulate and dissolved phases), and in sludge from a sewage treatment plant (STP) in Athens, Greece. The average concentrations of BTRs, BTHs, NSAIDs and EDCs in raw wastewater ranged between 11 ng L(-1) and 7.27 µg L(-1), while PFCs did not exceed 100 ng L(-1). In dewatered sludge, the average concentrations ranged between 0.8 ng g(-1) dw (perfluorohexanoic acid, PFHxA) and 3895 ng g(-1) dw (nonylphenol, NP). The distribution of emerging contaminants between particulate and dissolved phase was different among the compounds. BTRs and BTHs showed lower solid-liquid distribution coefficients (Kd) than all other compounds. For 9 over the 27 compounds detected in influents, the removal efficiency was higher than 70%, while the others either were removed to a lesser extent or detected at higher concentrations in effluents. Based on this, advanced treatment processes should be applied in the future for achieving adequate emerging contaminants removal in STPs. Regarding removal mechanisms, almost 60% of BTRs and 30 to 75% of BTHs were removed in bioreactors, while the contribution of primary and secondary clarifiers was of minor importance. Sorption to primary sludge was a significant mechanism affecting EDCs fate in STP.