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.

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.

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.

Treatment of real laundry wastewater using vertical flow constructed wetland planted with the ornamental climbing plant Trachelospermum jasminoides: assessing the removal of conventional pollutants and benzotriazoles.

This study investigates the effectiveness of vertical flow constructed wetlands (VFCWs) planted with a climbing ornamental plant for on-site treatment of real laundry wastewater. Specifically, the presence or absence of Trachelospermum jasminoides was evaluated for the removal performance of conventional pollutants (turbidity, TSS, COD, TP) and benzotriazoles (BTRs): 1H-benzotriazole (BTR), 5-methyl-1H-benzotriazole (5-TTR), 5-chlorobenzotriazole (CBTR), and xylytriazole (XTR). Results revealed that high removal efficiencies ranging from 92 to 98% were presented in both planted and unplanted systems for turbidity, TSS, and COD. Moreover, high removal rates were observed for CBTR and XTR, which were the only compounds found in real laundry wastewater, in both VFCW systems (planted: 100%; 94%; unplanted: 87%; 92%, respectively). The contribution of plants to the pollutant's removal was not statistically significant for all examined parameters. However, T. jasminoides demonstrated the ability to survive and grow without any visible symptoms under the harsh conditions of laundry wastewater, enabling the development of green facade. According to the findings, the application of VFCWs for on-site laundry wastewater treatment in buildings seems to be a highly promising solution, not only for primarily removing conventional pollutants but also for addressing emerging contaminants, specifically BTRs.

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.

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.

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.

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.

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.

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.

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.

Diuron biodegradation in activated sludge batch reactors under aerobic and anoxic conditions.

Diuron biodegradation was studied in activated sludge reactors and the impacts of aerobic and anoxic conditions, presence of supplemental substrate and biomass acclimatization on its removal were investigated. Diuron and three known metabolites, namely DCPMU (1-(3,4-dichlorophenyl)-3-methylurea), DCPU (1-3,4-dichlorophenylurea) and DCA (3,4-dichloroaniline), were extracted by solid-phase extraction (dissolved phase) or sonication (particulate phase) and determined using High Performance Liquid Chromatography-Diode Array Detector (HPLC-DAD). During the experiments only a minor part of these compounds was associated with the suspended solids. Under aerobic conditions, almost 60% of Diuron was biodegraded, while its major metabolite was DCA. The existence of anoxic conditions increased Diuron biodegradation to more than 95%, while the major metabolite was DCPU. Mass balance calculation showed that a significant fraction of Diuron is mineralized or biotransformed to other unknown metabolites. The presence of low concentrations of supplemental substrate did not affect Diuron biodegradation, whereas the acclimatization of biomass slightly accelerated its elimination under anoxic conditions. Calculation of half-lives showed that under aerobic conditions DCPMU, DCPU and DCA are biodegraded much faster than the parent compound. In the future, the sequential use of anoxic and aerobic conditions could provide sufficient removal of Diuron and its metabolites from runoff waters.

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.

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 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.

Occurrence and fate of endocrine disrupters in Greek sewage treatment plants.

The occurrence of five endocrine-disrupting compounds (EDCs), namely 4-n-nonylphenol (4-n-NP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), triclosan (TCS) and bisphenol A (BPA), was assessed in the raw, treated wastewater and sewage sludge of eight sewage treatment plants (STPs) in Greece. The analytes were extracted by solid-phase extraction (dissolved phase) or sonication (solid phase). Qualitative and quantitative analyses were performed by gas chromatography-mass spectrometry (GC-MS). The average concentrations in the raw and treated wastewater ranged from 0.23 (4-n-NP) to 5.76microgL(-1) (NP1EO) and from 0.15 (BPA) to 1.84microgL(-1) (NP2EO), respectively. A great part of the detected EDCs was sorbed on suspended solids. In sewage sludge, the average concentrations ranged between 0.17 (4-n-NP) and 12.3microgg(-1)dw (NP1EO). Analysis of daily mass flows in STP of Athens showed that, with the exception of 4-n-NP, all other EDCs were significantly removed (>85%) during wastewater treatment. Regarding the fate of these compounds, a significant part ranging from 45% (for TCS) to more than 70% (for NP1EO, NP2EO and BPA) was transformed by abiotic or biotic mechanisms, while the rest was accumulated in sewage sludge or disposed to the environment via the effluents. Calculation of risk quotients showed the existence of possible threat due to the presence of certain EDCs in treated wastewater and sludge.

Inhibitory effect of triclosan and nonylphenol on respiration rates and ammonia removal in activated sludge systems.

The toxic effects of triclosan (TCS) and nonylphenol (4-n-NP) on activated sludge heterotrophic and autotrophic microorganisms were evaluated. Toxicity experiments with specific oxygen uptake rate (SOUR) and ammonia uptake rate (AUR) revealed that TCS was much more toxic to heterotrophic and autotrophic microorganisms than 4-n-NP. In experiments with heterotrophic biomass, increase of sludge age (theta(c)) from 5 to 15 days resulted in a decrease of median effective concentrations (EC(50)) of TCS from 38.2 to 9.97 mg l(-1) and in an increase of EC(50) values of 4-n-NP from 441 to 649 mg l(-1). In experiments with autotrophic biomass and sludge age of 15 days, significantly lower EC(50) values were obtained for both compounds, indicating the higher sensitivity of nitrifiers to TCS and 4-n-NP. To compare toxicity of TCS and 4-n-NP towards single species and mixed wastewater cultures, experiments were performed using marine bacterium Vibrio fischeri. EC(50) values of 0.22 and 3.51 mg l(-1) were estimated for TCS and 4-n-NP, respectively, indicating the higher sensitivity of this bioassay to toxicants. According to the levels of tested compounds commonly found in influent wastewater and the results of this study, there is a possible risk for deterioration of nitrification in activated sludge systems due to the presence of TCS.

Simultaneous determination of the endocrine disrupting compounds nonylphenol, nonylphenol ethoxylates, triclosan and bisphenol A in wastewater and sewage sludge by gas chromatography-mass spectrometry.

An integrated analytical method for the simultaneous determination of 4-n-nonylphenol (4-n-NP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), bisphenol A (BPA) and triclosan (TCS) in wastewater (dissolved and particulate phase) and sewage sludge was developed based on gas chromatography-mass spectrometry. Chromatographic analysis was achieved after derivatization with bis(trimethylsilyl)trifluoroacetamide (BSTFA). Extraction from water samples was performed by solid-phase extraction (SPE). The optimization of SPE procedure included the type of sorbent and the type of the organic solvent used for the elution. Referred to solid samples, the target compounds were extracted by sonication. In this case the optimization of the extraction procedure included the variation of the amount of the extracted biomass, the duration and the temperature of sonication and the type of the extraction organic solvent. The developed extraction procedures resulted in good repeatability and reproducibility with relative standard deviations (RSDs) less than 13% for all the tested compounds for both types of samples. Satisfactory recoveries were obtained (>60%) for all the compounds in both liquid and solid samples, except for 4-n-NP, which gave recoveries up to 35% in wastewater samples and up to 63% in sludge samples. The limits of detection (LODs) of the target compounds varied from 0.03 (4-n-NP) to 0.41 microg l(-1) (NP2EO) and from 0.04 (4-n-NP) to 0.96 microg kg(-1) (NP2EO) for liquid and solid samples, respectively. The developed methods were successfully applied to the analysis of the target compounds in real samples.

Fate of Irgarol 1051, diuron and their main metabolites in two UK marine systems after restrictions in antifouling paints.

Two major antifouling biocides used worldwide, Irgarol 1051 and diuron, and their degradation products in Shoreham Harbour and Brighton Marina, UK were studied during 2003-2004. The highest concentrations of Irgarol 1051 were 136 and 102 ng L(-1) in water and 40 and 49 ng g(-1) dry weight in sediments for Shoreham Harbour and Brighton Marina, respectively. As the degradation product of Irgarol 1051, M1 was also widespread, with the highest concentration of 59 ng L(-1) in water and 23 ng g(-1) in sediments in Shoreham Harbour, and 37 ng L(-1) in water and 5.6 ng g(-1) in sediments in Brighton Marina. The target compounds showed enhanced concentrations during the boating season (May-July), when boats were being re-painted (January-February), and where the density of pleasure crafts was high. Overall, the concentration of Irgarol 1051 decreased significantly from late 2000 to early 2004, indicating the effectiveness of controlling its concentrations in the marine environment following restricted use. Diuron was only detected in 14% of water samples, and mostly absent from sediment samples.

Evaluation of single and joint toxic effects of two antifouling biocides, their main metabolites and copper using phytoplankton bioassays.

Single and joint effects of two antifouling booster biocides, irgarol 1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine) and diuron (1-(3,4 dichlorophenyl)-3,3 dimethyl urea), their metabolites, M1 (2-methylthio-4-tert-butylamino-s-triazine), DCPMU (1-(3,4-dichlorophenyl)-3 methyl urea), DCPU (1-(3,4 dichlorophenyl urea) and DCA (3,4-dichloroaniline), respectively, as well as copper were examined. Two phytoplanktonic microorganisms, the green alga Dunaliella tertiolecta and the diatom Navicula forcipata were exposed to various concentrations of the aforementioned compounds both alone and in binary mixtures during a period of 96h. Estimation of EC(50) values was performed by daily cell number counting of the tested microorganisms. The toxicity of the six compounds and the metal, applied singly, was found to be, in decreasing order, irgarol 1051>diuron>M1>DCPMU>DCA>Cu>DCPU and irgarol 1051>diuron>M1>DCA for the green alga and the diatom, respectively. Diatoms were found to be more sensitive in the presence of all the tested compounds, except diuron. Co-existence of irgarol 1051 and M1 revealed additive effects on both microorganisms. Same results were observed owing to the joint action of copper with either irgarol 1051 or M1 for almost all the examined mixtures. Combined effects of diuron with its metabolites DCPMU and DCA resulted in synergism in almost all cases, for both species of phytoplankton. On the contrary, antagonistic effects were observed owing to the joint action of copper with either diuron or one of its metabolites.