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.

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.

Microbial electrolysis cell coupled with anaerobic granular sludge: A novel technology for real bilge water treatment.

In the current study, treatment of undiluted real bilge water (BW) and the production of methane was examined for the first time using a membraneless single chamber Microbial Electrolysis Cell (MEC) with Anaerobic Granular Sludge (AGS) for its biodegradation. Initially, Anaerobic Toxicity Assays (ATAs) were used to evaluate the effect of undiluted real BW on the methanogenic activity of AGS. According to the results, BW shown higher impact to acetoclastics compared to hydrogenotrophic methanogens which proved to be more tolerant. However, dilution of BW caused lower inhibition allowing BW biodegradation. Maximum methane production (142.2 ± 4.8 mL) was observed at 50% of BW. Operation of MEC coupled with AGS, seemed to be very promising technology for BW treatment. During 80 days of operation in increasing levels of BW, R2 (1 V) reactor resulted in better performance than AGS alone. Exposure of AGS to gradual increase of BW content revealed that CH4 production was possible and reached 51% in five days even after feeding with 90% of BW using simple commercial iron electrodes. Successful chemical oxygen demand (sCOD) removal (up to 70%) was observed after gradual biomass acclimatization. Among the different monitored volatile fatty acids (VFAs), acetic and valeric acids were the most frequently detected compounds with concentrations up to 2.79 and 1.81 g L-1, respectively. The recalcitrant nature of BW did not allow the MEC-AD (anaerobic digester) to balance the consumed energy. Microbial profile analysis confirmed the existence of several methanogenic microorganisms of which Desulfovibrio and Methanobacterium presented significantly higher abundance in the cathodes compared to anodes and AGS.

Exploring the integrity of targeted PFASs in extracted wastewater samples during transport and storage stages.

Little information exists on the effects of shipping and handling on per- and polyfluoroalkyl substances (PFASs) in environmental samples. Thus, we evaluated the integrity of dried wastewater extracts and the sensitivity of our high-resolution mass spectrometry (HRMS) instrument to perform such analyses by monitoring 13 representative PFASs in samples extracted, evaporated, and stored at room temperature up to one month. Relative to zero-day recoveries of six detected PFASs ranged between 94 and 124% (RSD <38%) for influents, between 88 and 126% (RSD <18%) for effluents after 28 days. Larger variabilities are tentatively associated with the lack of specific mass-labeled standards and the interactions between analytes and remaining matrix components over time. In a second stage, a mix of local and international dry-shipped wastewater samples were analyzed and the same PFASs were quantified. Up to six PFASs were identified, with median concentrations ranging from 1.3 (perfluoro butyl sulfonate (PFBS)) to 7.7 ng/L (perfluoro hexanoic acid (PFHxA)) and from 1.5 (PFBS) to 13.8 ng/L (PFHxA) in local influents and effluents respectively; and from 0.7 (perfluoro hexyl sulfonate (PFHxS)) to 52.8 ng/L (PFHxA) and from 0.5 (PFHxS) to 21.4 ng/L (PFHxA) in Greek influents and effluents, respectively. The importance of this study lies on the need to consider the wider recovery shifts and expanded variability ranges of PFASs derived from the transport and storage times of dried extracts, particularly when applied to HRMS and wide-scope screening approaches.

Comparing the use of a two-stage MBBR system with a methanogenic MBBR coupled with a microalgae reactor for medium-strength dairy wastewater treatment.

Two systems were compared for medium-strength dairy wastewater treatment. The first comprised a methanogenic Moving Bed Biofilm Reactor (AnMBBR) and an aerobic MBBR (AeMBBR), while the second an AnMBBR and a sequencing batch reactor (SBR) with Chlorella sorokiniana. The AnMBBR, under ambient conditions, achieves biogas production sufficient enough to attain energy autonomy. The produced energy was 0.538 kWh m-3, whereas the energy consumption 0.025 kWh m-3. Its coupling with the AeMBBR removed COD, NH4-N TKN, and PO4-P by 93 ± 4%, 97 ± 3%, 99 ± 1% and 49 ± 15%, respectively, while the use of the SBR as a second step eliminated totally COD but partially the other pollutants. The higher nitrogen removal in the first system was due to nitrification occurring in the AeMBBR. The acclimatization of microalgae to dairy wastewater enhanced their growth. Their protein content was 54.56%, while starch and lipids were 3.39% and 23.1%, respectively.

Ecotoxicity and biodegradation of the bacteriostatic 3,3',4',5-tetrachlorosalicylanilide (TSCA) compared to the structurally similar bactericide triclosan.

This article studies the ecotoxicity of 3,3',4',5-tetrachlorosalicylanilide (TCSA) using different bioassays and examines its fate in activated sludge batch experiments. Despite of the common use of TCSA as chemical uncoupler in wastewater treatment systems and as preservative in several products, limited data has been published for its ecotoxicity, while no information is available for its biodegradation. Among different bioassays, the highest toxicity of TSCA was noticed for Daphna magna (48-h LC50: 0.054 mg L-1), followed by Vibrio fischeri (15-min EC50: 0.392 mg L-1), Lemna minor, (7-d EC50: 5.74 mg L-1) and activated sludge respiration rate (3-h EC50: 31.1 mg L-1). The half-life of TSCA was equal to 7.3 h in biodegradation experiments with activated sludge, while use of mass balances showed that 90% of this compound is expected to be removed in an aerobic activated sludge system, mainly due to biodegradation. A preliminary risk assessment of TSCA using the Risk Quotient methodology showed possible ecological threat in rivers where wastewater is diluted up to 100-fold. Comparison with the structurally similar 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan, TCS) showed that both compounds have similar biodegradation potential and seem to cause analogous toxicity to Vibrio fischeri and activated sludge. Specifically, TCS was biodegraded quite rapidly by activated sludge (half-life: 6.2 h), while EC50 values equal to 0.134 mg L-1 and 39.9 mg L-1 were calculated for Vibrio fischeri, and activated sludge respiration rate. Future research should focus on monitoring of TSCA concentrations in the environment and study its effects in long-term toxicity and bioaccumulation tests.

Biodegradability assessment of food additives using OECD 301F respirometric test.

The ready biodegradability of twenty food additives, belonging to the classes of artificial sweeteners, natural sweeteners, preservatives and colorings, was investigated using activated sludge as inoculum and OECD 301F respirometric test. According to the results, saccharin, aspartame, sodium cyclamate, xylitol, erythritol, maltitol, potassium sorbate, benzoic acid and sodium ascorbate are characterized as readily biodegradable compounds, partial biodegradation (<60% during the test) was noticed for steviol, inulin, alitame, curcumin, ponceau 4R and tartrazine, while no biodegradation was observed for the other five compounds. The duration of lag phase before the start of biodegradation varied between the target compounds, while their ultimate biodegradation half-life values ranged between 0.7 ±â€¯0.1 days (benzoic acid) and 24.6 ±â€¯1.0 days (curcumin). The expected removal of target compounds due to ultimate biodegradation mechanism was estimated for a biological wastewater treatment system operated at a retention time of one day and percentages higher than 40% were calculated for sodium cyclamate, potassium sorbate and benzoic acid. Higher removal percentages are expected in full-scale Sewage Treatment Plants (STPs) due to the contribution of other mechanisms such as sorption to suspended solids, (bio)transformation and co-metabolic phenomena. Further biodegradation experiments should be conducted under different experimental conditions for the food additives that did not fulfill the requirements of the applied protocol. Future studies should also focus on the occurrence and fate of food colorants and natural sweeteners in full-scale STPs.

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.

Growth inhibition and fate of benzotriazoles in Chlorella sorokiniana cultures.

Benzotriazoles are among the most commonly found organic micropollutants in the aquatic environment. In this study, toxicity experiments were conducted in order to investigate the effects of different benzotriazoles on Chlorella sorokiniana growth. Four compounds were tested; 1H-benzotriazole (BTR), xylytriazole (XTR), 5-methyl-1H-benzotriazole (5TTR) and 5-chlorobenzotriazole (CBTR). The fate of these micropollutants was also studied under batch conditions and the effect of different mechanisms on their elimination was investigated. According to the results, the EC50 values in single-substance toxicity experiments were calculated to 8.3 mg L-1 for BTR, 22 mg L-1 for 5TTR and 38.7 mg L-1 for CBTR. A slight inhibition on microalgae growth was noted at the maximum tested concentration of XTR (77 mg L-1), while no inhibition was observed when a mixture of target BTRs was tested at 200 µg L-1. Calculation of the Risk Quotient (RQ) showed no possible ecological threat in the presence of 5TTR, XTR and CBTR, while RQ values close or higher than 1 were estimated for BTR. All target contaminants were significantly eliminated in microalgae experiments that lasted 16 days. Their removal efficiency ranged between 42.2 ±â€¯3.1% (XTR) to 97.2 ±â€¯0.9% (XTR), while their half-life values were estimated to 2.4 ±â€¯0.5 days for 5TTR, 6.5 ±â€¯0.6 days for BTR, 15.2 ±â€¯1.4 days for CBTR and 20.7 ±â€¯2.0 days for XTR. Photodegradation was the main mechanism affecting BTR, XTR and CBTR removal, while bioremoval processes enhanced 5TTR elimination. The addition of sodium acetate decreased the removal efficiency of BTRs possibly due to catabolite repression. This is the first study investigating the toxicity and fate of BTRs in microalgae cultures.

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.

Biodegradation of bilge water: Batch test under anaerobic and aerobic conditions and performance of three pilot aerobic Moving Bed Biofilm Reactors (MBBRs) at different filling fractions.

The bilge water that is stored at the bottom of the ships is saline and greasy wastewater with a high Chemical Oxygen Demand (COD) fluctuations (2-12 g COD L-1). The aim of this study was to examine at a laboratory scale the biodegradation of bilge water using first anaerobic granular sludge followed by aerobic microbial consortium (consisted of 5 strains) and vice versa and then based on this to implement a pilot scale study. Batch results showed that granular sludge and aerobic consortium can remove up to 28% of COD in 13 days and 65% of COD removal in 4 days, respectively. The post treatment of anaerobic and aerobic effluent with aerobic consortium and granular sludge resulted in further 35% and 5% COD removal, respectively. The addition of glycine betaine or nitrates to the aerobic consortium did not enhance significantly its ability to remove COD from bilge water. The aerobic microbial consortium was inoculated in 3 pilot (200 L) Moving Bed Biofilm Reactors (MBBRs) under filling fractions of 10%, 20% and 40% and treated real bilge water for 165 days under 36 h HRT. The MBBR with a filling fraction of 40% resulted in the highest COD decrease (60%) compared to the operation of the MBBRs with a filling fraction of 10% and 20%. GC-MS analysis on 165 day pointed out the main organic compounds presence in the influent and in the MBBR (10% filling fraction) effluent.

Removal mechanisms of benzotriazoles in duckweed Lemna minor wastewater treatment systems.

The fate of five benzotriazoles (1H-benzotriazole, BTR; 4-methyl-1H-benzotriazole, 4TTR; 5-methyl-1H-benzotriazole, 5TTR; xylytriazole, XTR and 5-chlorobenzotriazole, CBTR) was studied in batch and continuous-flow Lemna minor systems and the role of different mechanisms on their removal was evaluated. Single and joint toxicity experiments were initially conducted using the Organization for Economic Co-operation and Development (OECD) protocol 221 and no inhibition on specific growth rate of Lemna minor was observed for concentrations up to 200µgL-1. All tested substances were significantly removed in batch experiments with Lemna minor. Excepting 4TTR, full elimination of CBTR, XTR, 5TTR and BTR was observed up to the end of these experiments (36d), while the half-life values ranged between 1.6±0.3d (CBTR) and 25±3.6d (4-TTR). Calculation of kinetic constants for hydrolysis, photodegradation, and plant uptake revealed that for all BTRs the kinetic constants of plant uptake were by far higher comparing to those of the other mechanisms, reaching 0.394±0.161d-1 for CBTR. The operation of a continuous-flow Lemna minor system consisted of three mini ponds and a total hydraulic residence time of 8.3d showed sufficient removal for most target substances, ranging between 26% (4TTR) and 72% (CBTR). Application of a model for describing micropollutants removal in the examined system showed that plant uptake was the major mechanism governing BTRs removal in Lemna minor systems.

Fate of antimicrobials in duckweed Lemna minor wastewater treatment systems.

The fate of four antimicrobials (cefadroxil, CFD; metronidazole, METRO; trimethoprim, TRI; sulfamethoxazole, SMX) was studied in Lemna minor systems and the role of different mechanisms on their removal was evaluated. All micropollutants were significantly removed in batch experiments with active Lemna minor; the highest removal was observed for CFD (100% in 14 d), followed by METRO (96%), SMX (73%) and TRI (59%) during 24 d of the experiment. Calculation of kinetic constants for hydrolysis, photodegradation, sorption to biomass and plant uptake revealed significant differences depending on the compound and the studied mechanism. For METRO, TRI and SMX the kinetic constants of plant uptake were by far higher comparing to those of the other mechanisms. The transformation products of antimicrobials were identified using UHPLC-QToF-MS. Two were the main degradation pathways for TRI; hydroxylation takes place during both phyto- and photodegradation, while demethylation occurs only in absence of Lemna minor. The operation of a continuous-flow duckweed system showed METRO and TRI removal equal to 71±11% and 61±8%, respectively. The application of mass balance and the use of published biodegradation constants showed that plant uptake and biodegradation were the major mechanisms governing METRO removal; the most important mechanism for TRI was plant uptake.

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.

Drugs of abuse and alcohol consumption among different groups of population on the Greek Island of Lesvos through sewage-based epidemiology.

The occurrence of 22 drugs of abuse, their metabolites, and the alcohol metabolite ethyl sulphate was investigated in raw sewage samples collected during the non-touristic season from three sewage treatment plants (STPs), which serve different sizes and types of population in the Greek island of Lesvos. Using the sewage-based epidemiology approach, the consumption of these substances was estimated. Five target analytes, cocaine (COC), benzoylecgonine (BE), 3,4-methylenedioxymethamphetamine (MDMA), 11-nor-9-carboxy-delta-9-tetrahydrocannabinol (THC-COOH) and ethyl sulphate (EtS) were detected at concentrations above their limit of quantification, whereas the rest eighteen target compounds were not detected. THC-COOH was detected in most of the samples with concentrations ranging between <20 and 90ngL(-1), followed by EtS (range <1700-12,243ngL(-1)). COC, BE, and MDMA were present only in the STP that serves Mytilene (the main city of the island), at mean concentrations of 3.9ngL(-1) for COC (95% CI: 1.7-6.1), 9.4ngL(-1) for BE (95% CI: -1.6-23) and 3.2ngL(-1) for MDMA (95% CI: 1.2-5.1). Back-calculations to an amount of used substance indicated more intense use of drugs among city population than rural and University population with average values of 9.5 and 1.2mgday(-1) per 1000 inhabitants for COC (95% CI: -1.43-20.4) and MDMA (95% CI: 0.52-1.85), respectively, and 2.8gday(-1) per 1000 inhabitants for tetrahydrocannabinol (THC) (95% CI: 2.4-3.1), the active ingredient of cannabis. Alcohol consumption was observed to be higher in the city population (5.4mL pure alcohol per day per inhabitant) than in the rural population (3.4mL pure alcohol per day per inhabitant), but the difference was not statistically significant. Consumption of THC differed significantly among the three STPs.

Evaluation of polar organic micropollutants as indicators for wastewater-related coastal water quality impairment.

Results from coastal water pollution monitoring (Lesvos Island, Greece) are presented. In total, 53 samples were analyzed for 58 polar organic micropollutants such as selected herbicides, biocides, corrosion inhibitors, stimulants, artificial sweeteners, and pharmaceuticals. Main focus is the application of a proposed wastewater indicator quartet (acesulfame, caffeine, valsartan, and valsartan acid) to detect point sources and contamination hot-spots with untreated and treated wastewater. The derived conclusions are compared with the state of knowledge regarding local land use and infrastructure. The artificial sweetener acesulfame and the stimulant caffeine were used as indicators for treated and untreated wastewater, respectively. In case of a contamination with untreated wastewater the concentration ratio of the antihypertensive valsartan and its transformation product valsartan acid was used to further refine the estimation of the residence time of the contamination. The median/maximum concentrations of acesulfame and caffeine were 5.3/178 ng L(-1) and 6.1/522 ng L(-1), respectively. Their detection frequency was 100%. Highest concentrations were detected within the urban area of the capital of the island (Mytilene). The indicator quartet in the gulfs of Gera and Kalloni (two semi-enclosed embayments on the island) demonstrated different concentration patterns. A comparatively higher proportion of untreated wastewater was detected in the gulf of Gera, which is in agreement with data on the wastewater infrastructure. The indicator quality of the micropollutants to detect wastewater was compared with electrical conductivity (EC) data. Due to their anthropogenic nature and low detection limits, the micropollutants are superior to EC regarding both sensitivity and selectivity. The concentrations of atrazine, diuron, and isoproturon did not exceed the annual average of their environmental quality standards (EQS) defined by the European Commission. At two sampling locations irgarol 1051 exceeded its annual average EQS value but not the maximum allowable concentration of 16 ng L(-1).

Use of solar distillation for olive mill wastewater drying and recovery of polyphenolic compounds.

Olive mill wastewater (OMW) is characterized by its high organic load and the presence of phenolic compounds. For first time, a solar distillator was used to investigate the simultaneous solar drying of OMW and the recovery of phenolic compounds with antioxidant properties in the distillate. Two experiments were conducted and the role of thermal insulation on the performance of the distiller was studied. The use of insulation resulted to higher temperatures in the distillator (up to 84.3 °C and 78.5 °C at the air and sludge, respectively), shorter period for OMW dewatering (14 days), while it increased the performance of distillator by 26.1%. Chemical characterization of the distillate showed that pH and COD concentration gradually decreased during the experiments, whereas an opposite trend was noticed for conductivity and total phenols concentration. Almost 4% of the total phenols found initially in OMW were transferred to the distillate when an insulated solar distillator was used. Gas chromatographic analysis of collected distillates confirmed the presence of tyrosol in all samples; whereas hydroxytyrosol was found only in fresh collected distillate samples. Further experiments should be conducted to optimize the process and quantify the concentrations of recovered phenolic compounds.

Sorption and biodegradation of selected benzotriazoles and hydroxybenzothiazole in activated sludge and estimation of their fate during wastewater treatment.

Biodegradation of benzotriazole (BTR), 5-chlorobenzotriazole (CBTR), xylytriazole (XTR), 4-methyl-1H-benzotriazole (4TTR), 5-methy-1H-lbenzotriazole (5TTR) and 2-hydroxybenzothiazole (OHBTH) was studied in activated sludge batch experiments under aerobic and anoxic conditions, presence of organic substrate and different sludge residence times (SRTs). Their sludge-water distribution coefficients were also calculated in sorption experiments and ranged between 87 and 220 L kg(-1). Significant biodegradation of BTR, CBTR, XTR and OHBTH was observed in all biotic experiments. Half-life values ranged between 23 and 45 h (BTR), 18 and 47 h (CBTR), 14 and 26 h (XTR), 6.5 and 24 h (OHBTH). The addition of substrate did not suppress biodegradation kinetics; whereas in some cases accelerated biodegradation of microcontaminants. Except for CBTR, no effect of SRT on biodegradation constants was observed. Prediction of micropollutants removal in Sewage Treatment Plants (STPs) indicated that they will be partially removed, mainly due to aerobic biodegradation. Higher removal is expected at STPs operating at higher SRT and higher suspended solids concentrations.

Assessing single and joint toxicity of three phenylurea herbicides using Lemna minor and Vibrio fischeri bioassays.

Single and joint toxicity of three substituted urea herbicides, namely monolinuron [3-(4-chlorophenyl)-1-methoxy-1-methylurea], linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea] and diuron [1-(3,4 dichlorophenyl)-3,3 dimethyl urea], were studied. The duckweed Lemna minor and the luminescent bacterium Vibrio fischeri were used for the toxicity assessment and they were exposed to various concentrations of the herbicides, individually and in binary mixtures. The exposure time was 7d for the duckweed and 30 min for the bacterium. Estimation of EC50 values was performed by frond counting and reduction in light output for Lemna minor and Vibrio fischeri, respectively. Lemna minor was found to be much more sensitive than Vibrio fischeri to target compounds. The toxicity of the three herbicides applied solely was estimated to be in decreasing order: diuron (EC50=28.3 µg L(-1))≈linuron (EC50=30.5 µg L(-1))>monolinuron (EC50=300 µg L(-1)) for the duckweed and linuron (EC50=8.2 mg L(-1))>diuron (EC50=9.2 mg L(-1))>monolinuron (EC50=11.2 mg L(-1)) for the bacterium. Based on the environmental concentrations reported in the literature and EC50 values obtained from Lemna minor experiments, Risk Quotients (RQ) much higher than 1 were calculated for diuron and linuron. In Lemna minor experiments, combination of target compounds resulted to additive effects due to their same mode of phenylurea action on photosynthetic organisms. Regarding Vibrio fischeri, synergistic, additive and antagonistic effects were observed, which varied according to the concentrations of target compounds.

Investigation of photodegradation and hydrolysis of selected substituted urea and organophosphate pesticides in water.

INTRODUCTION: Photodegradation and hydrolysis of two substituted urea herbicides, monolinuron [3-(4-chlorophenyl)-1-methoxy-1-methylurea] and linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea], and one organophosphorous insecticide, phoxim [2-(diethoxyphosphinothioyloxyimino)-2-phenylacetonitrile], were studied using buffered sterilized distilled water (pH 4, 7 and 9). METHODS: Experiments were performed in the absence and presence of light (320-740 nm), while the effect of nitrates and humic acids on photodegradation was investigated for all pH values. An analytical method was developed and validated for the determination of target compounds in water samples using liquid chromatography positive ion electrospray-mass spectrometry. RESULTS: According to the results, substituted ureas neither hydrolyzed, at all tested pH values, nor photodegraded at pH 7 and 9. Slow photodegradation of the compounds was observed at pH 4. During 70 days of light exposure, initial concentrations of linuron and monolinuron were decreased by 54% and 31%, respectively, while the presence of nitrates slightly enhanced photodegradation of these compounds. On the other hand, phoxim was found to be very unstable for all the tested conditions and an increase of pH resulted to higher degradation. During hydrolysis experiments, the degradation of the compound ranged from 41% (pH 4) to 85% (pH 9) and the half-lives varied from 10 h (pH 9) to 204 h (pH 4). The presence of light enhanced phoxim degradation and as a result half-lives of 37, 22 and 9h were calculated for pH 4, 7 and 9, respectively. The addition of nitrates and humic acids did not significantly affect the photodegradation of phoxim. CONCLUSIONS: The results indicated that among the three tested pesticides, phoxim found to be the most sensitive in both photodegradation and hydrolysis.