A new supported catalyst composed of a nanostructured TiO2 film deposited on a stainless steel mesh (nanoTiO2-SS) using the Metal Organic Chemical Vapour Deposition (MOCVD) technique was evaluated for the photocatalytic degradation of a mixture of contaminants of emerging concern. Results showed that under the tested oxidative conditions tested, the nanoTiO2-SS catalyst demonstrated an efficiency in degrading the target contaminants higher than that observed under direct photolysis and photocatalysis using the conventional TiO2 Degussa P25 catalyst at the same amount of TiO2 participating to the photocatalysis. Specifically, the rate of removal of warfarin and trimethoprim obtained with the new catalyst was found twice the one observed by using TiO2 Degussa P25 and approximately 1.6 times faster for metoprolol, carbamazepine and gemfibrozil. An evaluation of the electrical energy per order magnitude of removal (EE/O) confirmed the enhanced performance of the new catalyst (24.3-31.8 kWh m-3 rather than 32.8-39.3 kWh m-3 for conventional TiO2) and that the performance is compound-dependent. Toxicity testing revealed that some assays are suitable for the investigation of bioactivity of treated waters containing contaminants of emerging concern at µg L-1 level. Specifically, the AMES Fluctuation Test, Fish Embryo Acute Toxicity Test and Green alga Selenastrum capricornutum test provided valuable results for an environmental impact assessment. On the other hand, the Daphnia magna and Vibrio fischeri acute toxicity tests were not sensitive enough to detect bioactivity in the samples analysed without prior pre-concentration.

Emerging water pollutants (e.g., antibiotics, household chemicals) and pathogens (e.g. antibiotic-resistant bacteria, viruses) are only partially removed by conventional wastewater treatment plants. Thus, both groups of contaminants are continuously discharged into European rivers used as drinking water supplies. This de facto potable water reuse is frequently happening worldwide. There are concerns that emerging water pollutants and pathogens adversely affect aquatic life as well as human health, in particular in European areas with water scarcity problems. Under the umbrella of the European research initiative "Water JPI (Joint Programming Initiative ,,Water Challenges for a Changing World")" the project FRAME is funded for 3-years (2015-18). Leading European researches from four countries (Germany, Italy, France and Norway) are closely working together to develop new strategies to minimize the impacts of a broad range of chemical and biological contaminants when reusing treated municipal wastewater via subsurface treatment to augment drinking water resources. The project's main aim is to provide sufficient quantities of safe drinking water, while preserving ecosystems and human health. FRAME is addressing important aspects in the context of producing high quality water from recycled water including: a) removal efficiencies of emerging contaminants by various treatment processes, b) detection and removal of transformation products formed by microbial and chemical reactions of the emerging chemicals, c) inactivation of viruses and other pathogens, d) removal efficiencies of antibiotic resistant bacteria, e) use of bioassays and biomarkers to detect effects caused by specific pollutants and mixtures of pollutants, f) quantifying the reduction of environmental and human health risks, g) costs, non-monetary benefits and potential drawbacks of various treatment strategies. FRAME is testing several treatment combinations including ozonation and advanced oxidation processes coupled with a new process of sequential biologically active filtration, which are presented in the present communication. Modelling transport and fate of emerging contaminants and their transformation products through various treatment combinations will guide in assessing the efficiency of various mitigation strategies. The FRAME concept will influence European and national regulation for Indirect Potable Reuse and will be primarily validated at water reclamation facilities in Braunschweig, Germany.

Amorphous titanium hydroxide and boron-doped (B-doped) sodium titanates hydrates were synthetized and used as adsorbents for the removal of Pb(2+) from water. The use of sodium borohydride (NaBH4) and titanium(IV) isopropoxide (TTIP) as precursors permits a very easy synthesis of B-doped adsorbents at 298K. The new adsorbent materials were first chemically characterized (XRD, XPS, SEM, DRIFT and elemental analysis) and then tested in Pb(2+) adsorption batch experiments, in order to define kinetics and equilibrium studies. The nature of interaction between such sorbent materials and Pb(2+) was also well defined: besides a pure adsorption due to hydroxyl interaction functionalities, there is also an ionic exchange between Pb(2+) and sodium ions even working at pH 4.4. Langmuir model presented the best fitting with a maximum adsorption capacity up to 385mg/g. The effect of solution pH and common ions (i.e. Na(+), Ca(2+) and Mg(2+)) onto Pb(2+) sorption were also investigated. Finally, recovery was positively conducted using EDTA. Very efficient adsorption (>99.9%) was verified even using tap water spiked with traces of Pb(2+) (50ppb).

In recent years, the identification and monitoring of polluted sites have become very important due tothe widespread of contamination phenomena. The environmental assessment of contaminated sites iscomplex and difficult for the variety of the pollutants and for the physical and chemical heterogeneity ofpolluted sites. Some studies promote an integrated approach, which combines geophysical investigationwith geochemical analysis carried out on subsoil samples to quantitatively estimate the extent and thelevel of the contamination. In this work, a contaminated site located close to Taranto city, in the southof Apulia Region (Italy), has been investigated by chemical and geophysical surveys in order tocharacterize and evaluate the pollution which is occurring since years. Soil chemical analyses of texture,electrical conductivity, pH, organic carbon content, nitrogen, available phosphorous and carbonatecontent have been carried out to characterize soil properties of this site. Analytical investigations ofpollutants have been performed using Gas Chromatography/Mass Spectrometry (GC/MS) andInductively Coupled Plasma Mass Spectrometry (ICP-MS) to identify organic or inorganic compounds,respectively. Geophysical survey has been carried out to assess the geological features of the test siteand support the results of the physical and chemical soil analysis. Particularly, an Electrical ResistivityTomography (ERT) profile has been performed to visualize geo-lithological layers and hydrogeologicalproperties for evaluating the vulnerability of the area. Moreover six high resolution ERT and InducedPolarization (IP) profiles have been conducted close to the soil sampling points to image electricalstructures in the upper part of the soil, severely contaminated by inorganic and organic pollutants.Preliminary results highlight that this integrated approach can efficiently support soil contaminationassessment.

A promising membrane configuration based on immobilized TiO2 on poly(vinylidene fluoride) (PVDF) dual layer hollow fibre membranes was prepared and successfully employed for the photocatalytic degradation of eight pharmaceuticals. Experiments were carried out in a flow reactor of 0.5 L equipped with a lamp emitting at 254 nm, treating groundwater and secondary wastewater effluent. The efficiency of the new catalyst to phototransform target micropollutants was demonstrated, being dependent on the selected compound. Only the application of photocatalysis using the supported catalyst allowed to increase the phototransformation rate of trimethoprim, metoprolol and carbamazepine treating secondary wastewater effluent (1.4-2.2 times faster than photolysis). The determination of electrical energy per order of magnitude of transformation (EEO) confirmed the lowest energy requirements to transform selected pharmaceuticals in secondary effluent employing the supported catalyst (33-58 kW h m-3 compared to 49-79 kW h m-3 applying only photolysis). The detection and identification of transformation products formed during the investigated treatments was performed by UPLC-QTOF/MS/MS. 156 transformation products were detected showing two different types of time profiles, namely a bell-shape trend or a constant increase along reaction time thus accumulating in the reaction mixture. The chemical structure for 19 out of 156 detected compounds was proposed as derived from parent compounds spiked in the secondary effluent. ? 2018 Elsevier B.V.

The biodegradability of different wastewater samples originated from the industrial production of threepharmaceuticals (naproxen, acyclovir, and nalidixic acid) was performed through the standard Zahn-Wellens test. Moreover, the wastewater composition before and during the test was evaluated in termsof parent compounds and main metabolites by LC/MS, and the biodegradability of the parent compoundswas also assessed by performing extra Zahn-Wellens tests on synthetic solutions. The results, besidesshowing the relatively good biodegradability of acyclovir and naproxen, evidenced the masking role ofthe organic matrices, especially in the case of nalidixic acid. The latter compound showed to berecalcitrant and persistent, despite the apparently good performance of the Zahn-Wellens test. Deeperevaluation evidenced that the biodegradation of high concentrations of organic solvents and other biodegradablecompound tended to ''hide" the lack of removal of the target compound.

The occurrence of pharmaceuticals in the environmenthas been a topic of increasing concern. Pharmaceuticals are notcompletely mineralized in the human body and are released on thesewage systems as the pharmaceutical itself and as their "biologicallyactive" metabolites through excretion, as well as by improperelimination and disposal. Conventional wastewater treatment plants(WWTPs) are not designed to remove these emerging pollutants andthey are thus released into the environment. The antiepileptic drugcarbamazepine (CBZ) and the non-steroidal anti-inflammatorydiclofenac (DCF) are two widely used pharmaceuticals, frequentlydetected in water bodies, including rivers and groundwater, inconcentrations ranging from ng L 1 to mg L 1. These two compoundswere classified as medium to high-risk pollutants in WWTP effluentsand surface waters. Also, CBZ has been suggested as a molecularmarker of wastewater contamination in surface water andgroundwater and the European Union included DCF in the watch listof substances Directive to be monitored. In the present study,biodegradation of CBZ and DCF by the bacterial strain Labrysportucalensis F11, a strain able to degrade other pharmaceuticalcompounds, was assessed; tests were performed with F11 as single carbon and energy source, as well as in presence of 5.9mM of sodiumacetate. In assays supplemented with 2.0 and 4.0 ?M of CBZ, thecompound was no longer detected in the bulk medium after 24hr and5days, respectively. Complete degradation was achieved in 21 daysfor 11.0 ?M and in 23 days for 21.0 ?M. For the highestconcentration tested (43.0 ?M), 95% of degradation was achieved in30days. Supplementation with acetate increased the degradation rateof CBZ, for all tested concentrations. In the case of DCF, whensupplemented as a single carbon source, approximately 70% of DCF(1.7, 3.3, 8.4, 17.5 and 34.0 ?M) was degraded in 30days. Completedegradation was achieved in the presence of acetate for all testedconcentrations, at higher degradation rates. The detection ofintermediates produced during DCF biodegradation was performedby UPLC-QTOF/MS/MS, which allowed the identification of a rangeof metabolites. Stoichiometric liberation of chorine occurred and nometabolites were detected at the end of the biodegradation assayssuggesting a complete mineralization of DCF. Strain Labrysportucalensis F11 proved to be able to degrade these two top priorityenvironmental contaminants and may be potentially useful forbiotechnological applications/environment remediation.

Diclofenac (DCF) is a widely used non-steroidal anti-inflammatory pharmaceutical which is detected in the environment at concentrations which can pose a threat to living organisms. In this study, biodegradation of DCF was assessed using the bacterial strain Labrys portucalensis F11. Biotransformation of 70% of DCF (1.7-34 mu M), supplied as the sole carbon source, was achieved in 30 days. Complete degradation was reached via co-metabolism with acetate, over a period of 6 days for 1.7 mu M and 25 days for 34 mu M of DCF. The detection and identification of biodegradation intermediates was performed by UPLC-QTOF/MS/MS. The chemical structure of 12 metabolites is proposed. DCF degradation by strain F11 proceeds mainly by hydroxylation reactions; the formation of benzoquinone imine species seems to be a central step in the degradation pathway. Moreover, this is the first report that identified conjugated metabolites, resulting from sulfation reactions of DCF by bacteria. Stoichiometric liberation of chlorine and no detection of metabolites at the end of the experiments are strong indications of complete degradation of DCF by strain F11. To the best of our knowledge this is the first report that points to complete degradation of DCF by a single bacterial strain isolated from the environment.

The degradation of two of the most frequently used UV-filters was investigated through microcosm studies. Marinesediments sampled fromtwo sites in Italy (La Spezia harbour and Sarno river estuary, S1 and S2 respectively)were used to set up aerobic and anaerobic sets of reactors. The sediments were spiked with a methanol solutionof 3-(4-methylbenzylidene)camphor (4-MBC) and 2-ethylhexyl 4-(dimethylamino)benzoate (EH-DPAB), atconcentrations of either 25 or 50 mg kg-1 each. Methanol (6.3 g/L) also served as an organic amendment andgrowth substrate for improving microbial activity.Monitoring of the biotic and abiotic degradation of the selectedcontaminants over 16 months revealed that 4-MBC biodegradationwas very slow and incomplete,whereas over90% of EH-DPAB was degraded both in the aerobic and the anaerobic reactors by the natural microbial communitiesof both sediments. Repeated spikes of EH-DPAB were followed by complete decay, characterised by firstorderkinetics. The calculated kinetic rate constants under aerobic and anaerobic conditions were similar. In reactorsinoculated with the S1 sediment the degradation rate constants progressively increased after each spike,up to the value of 0.039 d-1. For the S2 sediment the rate constant was around 0.020 d-1 throughout the durationof the experiment. Mass spectrometry analysis of sediment extracts allowed detection of potential transformationproducts of EH-DPAB and 4-MBC. Moreover, the natural microbial community of the sediments wasstudied using the CAtalyzed Reporter Deposition Fluorescence In Situ Hybridization (CARD-FISH) both in the initialsediments and after degradation under aerobic and anaerobic conditions.

Alternative approaches for obtaining biodiesel from municipal sludge have been successfully investigated.In order to avoid the expensive conventional preliminary step of sludge drying, dewatered sludge(TSS: 15 wt%) was used as starting material. The best performance in terms of yield of fatty acid methylesters (18 wt%) with the lowest energy demand (17 MJ kg1FAME) was obtained by a new two-step approachbased on hexane extraction carried out directly on dewatered acidified (H2SO4) sludge followed by methanolysisof extracted lipids. It was found that sulphuric acid plays a key role in the whole process not onlyfor the transesterification of glycerides but also for the production of new free fatty acids from soaps andtheir esterification with methanol. In addition to biodiesel production, the investigated process allowsvalorization of primary sludge as it turns it into a valuable source of chemicals, namely sterols(2.5 wt%), aliphatic alcohols (0.8 wt%) and waxes (2.3 wt%).

The disposal of municipal sludge represents a relevant environmental problem in the field of wastewater treatment. As amatter of fact, 80 g of solids are produced per equivalent habitant per day. In detail, 60% comes from the primary treatmentand 40% from the secondary one. The sludge collected from these two different steps is made of two very different kind ofbiomasses: the primary sludge, is basically constituted by a large organic component (cellulose, lipids and proteins) and aminor inert one, while the secondary sludge is made of the biomass produced during the demolition of the soluble BOD.Such differences are going to open new distinguished uses for the two kinds of sludge [1]. Actually the production ofsecondary sludge can be drastically reduced by a new technology whose acronym is SBBGR[2] thus limiting the problem tothe disposal of primary sludge. In the last years, there have been some examples of sludge valorisation, in particular of itslipid fraction, to afford Fatty Acids Methyl Esters (FAMEs, namely biodiesel). The common approach used consists intoworking directly on a dry sludge with methanol and sulphuric acid as catalyst obtaining 11-14% of FAMEs from primarysludge and only 2% from secondary sludge [3]. Such an approach requires a high energy demand to obtain the dry sludge asstarting raw material for the alcoholysis process, from the dewatered sludge, the real product obtained from the sludgetreatment in a wastewater plant.In this work we present an inedited approach in which the starting raw material is the dewatered sludge (TSS = 20%)coming from the municipal wastewater treatment plant of Bari West (a Soutern Italy town). Two different methods havebeen used and compared: 1) the direct alcohlolysis of the dewatered sludge and 2) the preliminary extraction with hexanewith the subsequent alcoholysis of the oily residue. In both cases the energy demand per kilo of the final product result to belower than the energy required with the common approach.From a chemical point of view, a detailed analysis of the starting system has been carried out evidencing that together withthe glycerides, also free fatty acids (FFAs) and soaps are present in the sludge. For this reason, the trans-esterification ofglycerides is not the only reaction involved in the production of FAMEs, but direct esterification of FFAs and the splittingof soaps into the relevant FFAs are also involved in the whole process. Sulphuric acid plays a key role in the overall processas catalyst not only for the trans-esterification of glycerides (as already mentioned) [2] but even for the direct esterificationof FFAs in addition to work as strong acid for producing new FFAs from the soaps.The best results in term of yields of FAMEs (14% of the dry solids) have been obtained with the approach of hexaneextraction operated directly on the dewatered sludge, with a subsequent methanolysis catalysed by sulphuric acid at 5%w.Wi

A very detailed study was carried out on separation of lipids from wet sewage scum taken from several wastewater treatment plants (WWTPs). A solvent-less separation of lipids was optimized by simply heating sewage scum at 353 K and centrifuging the heated mass at 4000 rpm per 1 min [1]. Recoverability of 93-99% of total oils was determined. Extracted lipids have a very similar composition in terms of free fatty acids (FFAs), calcium soaps (32-40%wt) and glycerides (mono-, di- and tri-glycerides were practically absents), as well as fatty acid profiles in all of samples studied. Since mainly composed of FFAs, once separated, lipids were converted into biodiesel through a direct esterification process.Reaction conditions were optimised using the desirability function applied on the response surface methodology analysis of a Box-Behnken factorial design of experiments. By carrying out the reaction at 72°C for 120 min and using AlCl3·6H2O as a catalyst (1.5% mol of Al respect to fatty acids), almost 94% of the starting acids were converted into methyl esters [2]. At the end of the reaction, a biphasic system was obtained in which the upper methanolic phase, which contained most of the starting catalyst, was separated from the heaviest phase, mainly composed of fatty acid methyl esters. Such a distribution not only allowed the biodiesel to be easily separated, but also catalysts were efficiently recovered and reused for at least four times, determining a total TON greater than 200,without revealing any loss of its activity [3].This efficient separation between biofuel produced and unreacted methanol allow a three sequential batch reactors to be run, in which methanol and catalysts were charged in counter current respect to starting feedstock. In this way, the complete conversion (>99%) of starting FFAs into FAMEs was perfectly matched with using the minimum amount of reactants under very mild conditions (345 K, 2 h). The overall convenience of the process was completed by the anaerobic digestion of fibrous residues obtained from centrifugation of starting sewage scum: the final biogas resulted largely enough to sustain the overall heat of process [4].

The biodegradation potential of marine sediments towards two selected UV-filters was tested through a laboratory investigation. Sediments collected from two locations in Italy were spiked with 3-(4-methylbenzylidene)camphor (4-MBC) and 2-ethylhexyl 4-(dimethylamino)benzoate (EH-DPAB), and used to set up eight microcosms that were operated under either aerobic or anaerobic conditions. UV-filters concentration in the sediment was monitored over 360 days. Results showed that native microbial communities of both sediments were able to perform the complete removal of EH-DPAB, whereas 4-MBC was scarcely affected by biodegradation. Degradation kinetics of EH-DPAB was first-order, with kinetic rate constants around 0.02 d-1 for both sediments under both aerobic and anaerobic conditions. Microbiological characterisation of microcosms showed that the composition and structure of the sediment microbial communities changed after the different treatments with respect to the native microbial population.

Three different chemical oxidation processes were investigated in terms of their capability to degrade organic chemical components of real mature landfill-leachate in combination with biological treatment run in a Sequencing Batch Biofilter Granular Reactor (SBBGR). H2O2, H2O2 + UV and O3 were integrated with SBBGR and respective effluents were analyzed and compared with the effluent obtained from biological SBBGR treatment alone. In agreement with their respective oxidative power, conventional bulk parameters (residual COD, TOC, Ntot, TSS) determined from the resulting effluents evidenced the following efficacy ranking for degradation: SBBGR/O3 > SBBGR/UV + H2O2 > SBBGR/H2O2 > SBBGR. A more detailed characterization of the organic compounds was subsequently carried out for the four treated streams. For this, effluents were first subjected to a sample preparation step, allowing for a classification in terms of acidic, basic, strongly acidic and strongly basic compounds, and finally to analysis by liquid chromatography/high resolution mass spectrometry (LC/HR-MS). This classification, combined with further data post-processing (non-target screening, Venn Diagram, tri-dimensional plot and Principal Component Analysis), evidenced that the SBBGR/H2O2 process is comparable to the pure biological oxidation. In contrast, SBBGR/O3 and SBBGR/UV + H2O2 not only resulted in a very different residual composition as compared to SBBGR and SBBGR/H2O2, but also differ significantly from each other. In fact, and despite of the SBBGR/O3 being the most efficient process, this treatment remained chemically more similar to SBBGR/H2O2 than to SBBGR/UV + H2O2. This finding may be attributable to different mechanism of degradation involved with the use of UV radiation. Apart from these treatment differences, a series of recalcitrant compounds was determined in all of the four treatments and partly identified as hetero-poly-aromatic species (humic acids-like species). ? 2018 Elsevier B.V.

The application of a biological treatment together with a chemical oxidation process was investigated. Inparticular, the effectiveness of the biological treatment followed by a UV/H2O2-based advanced oxidationprocess (AOP) used as an end treatment was compared with that in which the same AOP was integratedwith biological degradation for treating a medium age sanitary landfill leachate.The results show that better performance with removal efficiencies higher than 80% for all investigatingparameters was obtained when AOP was integrated with the biological treatment, thus allowing thedischarge limits to be met. This was due to the biological removal of the biodegradable compounds producedby UV/H2O2 treatment. Instead, UV/H2O2-based AOP biodegradability enhancement gave noadvantage when it was used as an end treatment. Finally, the results show that H2O2 alone (i.e., withoutUV power) was quite ineffective either as a mineralizing or as a biodegradability enhancing agent andthat the only reactive species was essentially the hydroxyl free radical OH.

Urban wastewater treatment plants (WWTPs) are among the main anthropogenic sources for the release of contaminants of emerging concern (CECs) into the environment, which can result in toxic and adverse effects on aquatic organisms and consequently on humans. Unfortunately, WWTPs are not designed to remove CECs and secondary (e.g., conventional activated sludge process, CAS) and tertiary (such as filtration and disinfection) treatments are not effective in the removal of most CECs entering WWTP. Accordingly, several advanced treatment methods have been investigated for the removal of CECs from wastewater, including consolidated (namely, activated carbon (AC) adsorption, ozonation and membranes) and new (such as advanced oxidation processes (AOPs)) processes/technologies. This review paper gathers the efforts of a group of international experts, members of the NEREUS COST Action ES1403 who for three years have been constructively discussing the state of the art and the best available technologies for the advanced treatment of urban wastewater. In particular, this work critically reviews the papers available in scientific literature on consolidated (ozonation, AC and membranes) and new advanced treatment methods (mainly AOPs) to analyse: (i) their efficiency in the removal of CECs from wastewater, (ii) advantages and drawbacks, (iii) possible obstacles to the application of AOPs, (iv) technological limitations and mid to long-term perspectives for the application of heterogeneous processes, and (v) a technical and economic comparison among the different processes/technologies. ? 2018 Elsevier B.V.

Fenton oxidation of the nonionic surfactant Brij 35 was enhanced by the effect of 1,4-hydroquinone adsorbed on granular activated carbon (GAC). The procedure allowed 90%-94% surfactant removal after 24 h at pH= 2.7-3.0, using 97mg g- 1 of hydroquinone adsorbed on GAC and concentrations of surfactant, H2O2, and iron (either Fe2 + or Fe3 + ) of, respectively, 1300, 450, and 9mg L- 1. In the absence of carbon and hydroquinone, and with the same concentration of H2O2, conventional Fenton process required 300mg L- 1 of Fe(II) to obtain 85% removal of Brij 35. Quinone-loaded carbon was effectively recycled until surfactant removal decreased to 50%-60%. Only 3% of hydroquinone was desorbed from GAC to the aqueous solution, and about 40% of the dissolved fraction was degraded to low-molecular-weight organic acids. This is the first description of a Fenton process performingthe recycling of a redox-active organic compound adsorbed on GAC, with the aim of decreasing the amount of iron salt utilized in the conventional Fenton reaction.

Batch and column tests were conducted to compare the efficiencies of three Fenton-like systems in the degradation of chlorobenzene. In the investigated systems, iron powder was the source of Fe2+ ions, and either Fe 3+ or Cu2+ were added in order to enhance the degradation process. Optimum pH and concentrations of Fe 3+ , Cu2+ and hydrogen peroxide were assessed by treating synthetic chlorobenzene solutions both in batch and in column mode, thus achieving the minimum residual concentration of chlorobenzene. Optimum conditions assessed by means of column tests were then applied to column treatment of real chlorobenzene-contaminated groundwater. Results showed that,when the TOC content of water was above 12 mg L-1, the performance of the Fe0/H2O2 system was enhanced by the addition of Fe3+, leading to 10-2 ?g L-1 of residual chlorobenzene.

A robust analytical method is presented for the direct determination of polychlorinated biphenyls in soil samples by thermal desorption/gas chromatography/mass spectrometry. The method is simple to perform (thermal desorption and analysis are performed in-line employing a limited amount of sample, 2mg) and eliminates the need for any solvent and time-consuming extraction. The analytical procedure was optimized using a soil sample spiked with Aroclor 1254 and Aroclor 1260 and validated with a certified industrial soil sample for which the concentration of thirteen PCB congeners are known. Limits of detection were sensitive to matrix effects and varied substantially among analytes. The matrix effect resulted in a reduction of the limits of detection by 1.5-10 times. However, it was found that the matrix effect is not due to ion suppression but to the increase of the noise of selected ion monitoring (SIM) traces, indicating that no limitation exists with using a single surrogate standard. By employing a 13C-labelled PCB internal standard, limits of detection in the range of 0.8 to 10 mu gg(-1) of soil were obtained. The obtained experimental results demonstrated that the proposed analytical method can be conveniently applied for screening a large number of heavily contaminated soil samples thus avoiding the employment of harmful solvents and time-consuming extraction procedures.

The enhanced removal of organic compounds from a pharmaceutical wastewater resulting from the productionof an anti-viral drug (acyclovir) was obtained by employing a membrane bioreactor (MBR) and anozonation system. An integrated MBR-ozonation system was set-up by placing the ozonation reactor inthe recirculation stream of the MBR effluent. A conventional treatment set-up (ozonation as polishingstep after MBR) was also used as a reference. The biological treatment alone reached an average CODremoval of 99%, which remained unvaried when the ozonation step was introduced. An acyclovir removalof 99% was also obtained with the MBR step and the ozonation allowed to further remove 99% of theresidual concentration in the MBR effluent. For several of the 28 organics identified in the wastewaterthe efficiency of the MBR treatment improved from 20% to 60% as soon as the ozonation was placed inthe recirculation stream. The benefit of the integrated system, with respect to the conventional treatmentset-up was evident for the removal of a specific ozonation by-product. The latter was efficiently removedin the integrated system, being its abundance in the final effluent 20-fold lower than what obtained whenozonation was used as a polishing step. In addition, if the conventional treatment configuration isemployed, the same performance of the integrated system in terms of by-product removal can only beobtained when the ozonation is operated for longer than 60 min. This demonstrates the effectivenessof the integrated system compared to the conventional polishing configuration.

Wastes produced by oil/water separation at the wastewater treatment plant of Bari West (Southern Italy) were taken, characterized and converted. About 12% of this material was composed of greases, mainly made of free fatty acids (50%) and soaps (34%), and was easily separable by the aqueous phase through a hot centrifugation. After chemical activation of this fatty fraction, a direct esterification was carried out under very mild conditions (320 K and atmospheric pressure), converting more than 90% of the original free fatty acids into the respective methyl esters in less than 4 h, by using AlCl3 center dot 6H(2)O. The activation energy correlated to the use of this catalyst was also calculated (Ea(est) = 43.9 kJ mol (1)). The very low cost of the biodiesel produced (0.45 (SIC) L (1)) and the associated relevant specific energy (5.02 MJ kg(FAMEs)(-1)) make such a process a really sustainable and effective example of valorization of a waste. (C) 2013 Elsevier Ltd. All rights reserved.

A very efficient separation of lipids from wet sewage scum was optimised and positively tested on samples taken from several wastewater treatment plants (WWTPs). By simply heating sewage scum at 353 K and centrifuging the heated mass at 4000 rpm per 1 min, a recoverability of 93-99% of total oils was always obtained. This procedure resulted to be effective on samples with very different starting water contents. In all cases, extracted lipids have a very similar composition in terms of free fatty acids (FFAs), calcium soaps (32-40%wt) and glycerides (mono-, di- and tri-glycerides were practically absents), as well as fatty acid profiles. Once separated, lipids were converted into biodiesel through a direct esterification process carried out by adopting three sequential batch reactors, in which methanol and catalysts were charged in counter current. In this way, the complete conversion (>99%) of starting FFAs into FAMEs was perfectly matched with using the minimum amount of reactants under very mild conditions (345 K, 2 h). The overall convenience of the process was completed by the anaerobic digestion of fibrous residues obtained from centrifugation of starting sewage scum: the final biogas resulted largely enough to sustain the heat of process. (C) 2015 Elsevier Ltd. All rights reserved.

There is a substantial lack of information on most priority pollutants, related contamination trends, and (eco)toxicological risks for the major Italian watercourse, the River Po. Targeting substances of various uses and origins, this study provides the first systematic data for the River Po on a wide set of priority and emerging chemicals, all characterized by endocrine-active potentials. Flame retardants, natural and synthetic hormones, surfactants, personal care products, legacy pollutants, and other chemicals have been investigated in sediments from the River Po and its tributary, the River Lambro, as well as in four fish species from the final section of the main river. With few exceptions, all chemicals investigated could be tracked in the sediments of the main Italian river for tens or hundreds of kilometres downstream from the Lambro tributary. Nevertheless, the results indicate that most of these contaminants, i.e., TBBPA, TCBPA, TBBPA-bis, DBDPE, HBCD, BPA, OP, TCS, TCC, AHTN, HHCB, and DDT, individually pose a negligible risk to the River Po. In contrast, PBDE, PCB, natural and synthetic estrogens, and to a much lower extent NP, were found at levels of concern either to aquatic life or human health. Adverse biological effects and prohibition of fish consumption deserve research attention and management initiatives, also considering the transport of contaminated sediments to transitional and coastal environments of the Italian river.

Electrochemical TiO2 photocatalysis is an innovative and rather unknown method of advanced oxidation processes (AOP) for water treatment. The photoactive coating is grown directly on titanium wire meshes. It shows good mechanical adhesion to the substrate and good electrical conductivity. During the wastewater treatment step aimed at removing organic pollutants, an electrical bias can be effectively applied to the catalyst through the wire mesh, leading to a synergistic effect with UV light and a faster degradation kinetics with respect to either photocatalytic or the electrochemical process.Photoactive TiO2 coatings are obtained by a number of techniques including sol-gel, CVD, RF Magnetron Sputtering, Plasma Spray, Electron Beam Evaporation, Anodic Oxidation [1] and Plasma Electrolytic Oxidation (PEO) [2]. In the present study, the catalyst was obtained by Plasma Electrolytic Oxidation.Various studies over recent years have proved the increasing occurrence in effluent of wastewater treatment plants (WWTP) of several contaminants of emerging concern (CECs), which are not completely removed by the common technologies employed in conventional WWTP. CECs found at highest levels (ng/L to ?g/L) are pharmaceuticals, artificial sweeteners, pesticides, flame-retardants, plasticizers and perfluoroalkyl substances.In the present study, the effectiveness of the aforementioned UV-based AOP for CECs removal was explored by investigating the decontamination of aqueous solutions containing the pharmaceutical drug carbamazepine, which is one of the main CEC in municipal wastewaters. The process was carried out in a laboratory-scale tubular photocatalytic reactor working in semi-batch mode under electrical polarization of the catalyst. The UV source consisted of a 30 W UV-C lamp emitting at 254 nm.

The large estuary that the River Po forms at its confluence into the Adriatic Sea comprises a multitude of transitional environments, including coastal lagoons. This complex system receives the nutrients transported by the River Po but also its load of chemical contaminants, which may pose a substantial (eco)toxicological risk. Despite the high ecological and economic importance of these vulnerable environments, there is a substantial lack of information on this risk. In light of the recent amendments of the European Water Framework Directive (2013/39/EU), the present study investigated the sediment contamination of six coastal lagoons of the Po delta and its effects on Manila clams (Ruditapes philippinarum), exposed in situ for 3 months. Sediment contamination and clam bioaccumulation of a wide range of chemicals, i.e. trace metals (Cd, Cr, Ni, Hg, Pb, As), polybrominated diphenyl ethers (PBDEs), alkylphenols (APs), organochlorine compounds (PCBs, DDTs), polycyclic aromatic hydrocarbons (PAHs) and organotins (TPhT, TBT), suggested a southward increase related to the riverine transports. Where the River Po influence was more direct, the concentrations of contaminants were higher, with nonylphenol and BDE-209 exceeding sediment quality guidelines. Biometric indicators suggested the influence of contamination on organism health; an inverse relationship between PBDEs in sediments and clam condition index has been found, as well as different biota-sediment accumulation factors (BSAFs) in the lagoons.

Enhanced performance of biological processes for xenobiotic removal in municipal and industrial wastewater treatment plants can be achieved by adopting the following general strategies based on different principles of operation: increase of the biomass concentration (i.e., using biofilm, immobilized cell, and granular sludge reactors); dynamic operating conditions able to modify the biocenosis composition and to induce alternative metabolic pathways required by xenobiotic biodegradation; two-phase systems, which optimize the substrate delivery to the microorganisms on the basis of their metabolic demand; and combined treatment processes utilizing synergistic physical/chemical methods. In this chapter, the three following strategies for enhancing the biological process are presented and discussed: Addition of adsorption or absorption media Advanced oxidation processes: UV and UV/H2O2 Bioreactors operated with attached and granular biomass The proposed alternatives have been chosen as representative examples of promising technological solutions still under investigation. For each alternative a short presentation including the principle of operation, the realized applications and potentialities, as well as a case study is reported. ? 2016 Springer International Publishing Switzerland.

Fat, oil and grease (FOG) recovered by the oil/water separator of a wastewater treatment plant (WWTP) were sampled, characterized, activated and converted into biofuel. Free acids (50-55%) and fatty soaps (26-32%) not only composed the main components, but they were also easily separable from the starting waste. The respective free fatty acid profiles were gas-chromatographically evaluated, interestingly verifying that free acids had a different profile (mainly oleic acid) with respect to the soapy fraction (saturated fatty acids were dominant). The inorganic composition was also determined for soaps, confirming that calcium is the most commonly present metal. The chemical activation of this fatty waste was made possible by converting the starting soaps into the respective free fatty acids by using formic acid as activator, coproducing the relevant formates. The activated fatty matter was then converted into biofuel through direct esterification under very mild conditions (345 K, atmospheric pressure) and obtaining thermodynamic conversion in less than 2 h. The process was easily scaled up, isolating at the end pure biodiesel (purity>96%) through distillation under vacuum, providing a final product conformed to commercial purposes.

Semiconductor/metal nanocomposites based on anatase TiO2 nanoparticles and Au nanorods (TiO2/AuNRs) were prepared by means of a co-precipitation method and subsequently calcinated at increasing temperature (from 250° to 650°C) obtaining up to 20 grams of catalysts. The structure and the morphology of the obtained nanocomposite material were comprehensively characterized by means of electron microscopy (SEM and TEM) and X-ray diffraction techniques. The photocatalytic performance of the TiO2/AuNRs nanocomposites was investigated as a function of the calcination temperature in experiment of degradation of water pollutants under both UV and UV-Vis irradiation, Photocatalytic experiments under UV irradiation were performed by monitoring spectrophotometrically the decolouration of a target compound (methylene blue, MB) in aqueous solution. UV-Visible light irradiation was, instead, used for testing the photocatalytic removal of an antibiotic molecule, Nalidixic acid, by monitoring the degradation process by HPLC-MS analysis. Interestingly, TiO2/AuNRs calcined at 450°C was up to 2.5 and 3.2 times faster than TiO2P25 Evonik, that is a commercially available reference material, in the photocatalytic degradation of the Methylene Blue and the Nalidixic Acid, under UV and visible light, respectively. The same nanocomposite material showed a photocatalytic degradation rate for the two target compounds up to 13 times faster than the bare TiO2-based catalysts.The obtained results are explained on the basis of the structure and morphology of the nanocomposites, that could be tuned according to the preparative conditions. The role played by the plasmonic domain in the heterostructured materials, either under UV and UV-Visible illumination, is also highlighted and discussed.The overall results indicate that the high photoactivity of TiO2/AuNRs in the visible range can be profitably exploited in photocatalytic applications, thanks also to the scalability of the proposed synthetic route, thus ultimately envisaging potential innovative solution for environmental remediation.

Heavy fluctuations in wastewater composition, such as those typical of tourist areas, can lead to a deteri-orationintreatmentplantperformanceifnoactionistakeninadvance.Mathematicalmodelling,appliedto treatment plant performance prediction, can provide valuable information to address the stress issue.The present study shows that the evolutionary polynomial regression methodology (EPR) is able to pre-dicttheperformancesofanattachedgranularbiomasssystemsothatitispossibletomakethenecessaryoperatingchangesinadvance,avoidingdeteriorationinthequalityoftheeffluentdischarged.ThepresentpapershowstheresultsofEPRapplicationtogrossparametersofagranularattachedbiomassreactor.Foreach parameter, a model capable of predicting the effluent value was assessed, based on the knowledgeoftheinfluentcharacteristics.Coefficientsofdeterminationvalues(CoD)obtainedduringthemodelsval-idation phase, can be said to be more than satisfactory, varying between 84.2% and 94.6%. Moreover, theapplied tests showed typical behaviours commonly found when observed and predicted values are quitesimilar. This paper reports the first application attempt for modelling this kind of emerging treatmentsystem and gross parameters.

The Artificial Neural Networks by Multi-objectiveGenetic Algorithms (ANN-MOGA) model has been appliedto gross parameters data of a Sequencing Batch BiofilterGranular Reactor (SBBGR) with the aim of providing an effectivetool for predicting the fluctuations coming from touristicpressure. Six independent multivariate models, whichwere able to predict the dynamics of raw chemical oxygendemand (COD), soluble chemical oxygen demand (CODsol),total suspended solid (TSS), total nitrogen (TN), ammoniacalnitrogen (N-NH4+) and total phosphorus (Ptot), were developed.The ANN-MOGA software application has shown to besuitable for addressing the SBBGR reactor modelling. The R2found are very good, with values equal to 0.94, 0.92, 0.88,0.88, 0.98 and 0.91 for COD, CODsol, N-NH4+, TN, Ptot andTSS, respectively. A comparison was made between SBBGRand traditional activated sludge treatment plant modelling.The results showed the better performance of the ANNMOGAapplication with respect to a wide selection of scientificliterature cases.

RATIONALE The balance of organic nitrogen and sulfur during ozonation of organic pollutants often shows a lack of complete mineralization. It follows that polar and ionic by-products are likely to be present that are difficult to identify by liquid chromatography/mass spectrometry (LC/MS). METHODS The structural elucidation of low molecular weight organic acids arising from Uniblu-OH ozonation has been investigated by ion chromatography/electrospray tandem mass spectrometry (IC/ESI-MS/MS) employing a quadrupole time-of-flight mass spectrometer. Unequivocal elemental composition of the by-products was determined by a combination of mass accuracy and high spectral accuracy. RESULTS The employed identification strategy was demonstrated to be a powerful method of unequivocally assigning a single chemical composition to each identified compound. The exact mass measurements of [MH] ions allowed the elemental formulae and related structures of eighteen by-products to be determined confidently. The main degradation pathways were found to be decarboxylation and oxidation. The experimental procedure allowed the identification of both nitrogen- and sulfur-containing organic acid by-products arising from Uniblu-OH ozonation. CONCLUSIONS The obtained results are of environmental relevance for the balance of organic nitrogen and sulfur during the ozonation of organic pollutants due to the lack of complete mineralization of the compounds containing these atoms. Copyright (c) 2012 John Wiley & Sons, Ltd.

Various studies over recent years have proved the increasing occurrence in effluent of wastewater treatment plants (WWTP)of several contaminants of emerging concern (CECs), which are not completely removed by the common technologies employed in conventional WWTP. CECs found at highest levels (ng L-1 to µg L-1) are pharmaceuticals, artificial sweeteners, pesticides, flame-retardants, plasticizers and perfluoroalkyl substances [1,2].The main objective of this study was to investigate an electrochemical treatment based on a boron-doped diamond (BDD) electrode, as an advanced oxidation process (AOP) for the removal of several CECs from effluent of WWTP with enhanced performance in terms of efficiency and applicability [3]. Electrochemical treatments were performed with a CONDIAPUREÒ system using a DIACHEMÒ electrode stack in a flow through cell (CONDIAS GmbH, Germany), in both synthetic water and real secondary effluent. The electrode stack was composed by two BDD cathodes and one BDD anode and in situ oxidation was performed with four anode/cathode pairs applying a total current of 0.4 A. A total of 10 L of solution with the target organic pollutants was circulated through the reactor at a flow rate of 18.5 L/min.The removal of a mixture of CECs (iopromide, carbamazepine, diclofenac, erythromycin, benzotriazol, sulfamethoxazole, caffeine, gabapentin, metoprolol, phenythoin, primidone, venlafaxine, TCEP) by the investigated electrochemical system was primarily assessed in synthetic model water spiked with the target contaminants at concentration in the range of 2-5 µg L-1. Removal below limit of quantification (LOQ) was achieved for all tested compounds after 200 min of treatment. Decay follows pseudo first order kinetics and kinetic constants (k) of 0.07 min-1 for sulfamethoxazole and diclofenac and in the range 0.03-0.01 min-1 for the other CECs were obtained, being TCEP the pollutant with slowest kinetics. Afterwards, the secondary effluent of the municipal WWTP Garching (Germany) was employed as a real water matrix which revealed the occurrence of several CECs (including the mixture of selected compounds listed above) at concentration levels between 20 ng L-1 and 20 µg L-1. The electrochemical treatment of the effluent was performed under the same conditions employed with the spiked synthetic water. Results demonstrated removal below LOQ for all the target CECs after 300 min with lower degradation rates than in the spiked synthetic water solution (k <= 0.01 min-1). The detection of transformation products of investigated CECs was performed by UPLC-QTOF/MS/MS, by employing a non-target analysis approach which was based on accurate MS and MS/MS data and open source databases and software.

The electrochemical degradation of six of the most widely used iodinated contrast media was investigated. Batch experiments were performed under constant current conditions using two DSA (R) electrodes (titanium coated with a proprietary and patented mixed metal oxide solution of precious metals such as iridium, ruthenium, platinum, rhodium and tantalum). The degradation removal never fell below 85% (at a current density of 64 mA/cm(2) with a reaction time of 150 min) when perchlorate was used as the supporting electrolyte; however, when sulphate was used, the degradation performance was above 80% (at a current density of 64 mA/cm(2) with a reaction time of 150 min) for all of the compounds studied. Three main degradation pathways were identified, namely, the reductive de-iodination of the aromatic ring, the reduction of alkyl aromatic amides to simple amides and the de-acylation of N-aromatic amides to produce aromatic amines. However, as amidotrizoate is an aromatic carboxylate, this is added via the decarboxylation reaction. The investigation did not reveal toxicity except for the lower current density used, which has shown a modest toxicity, most likely for some reaction intermediates that are not further degraded. In order to obtain total removal of the contrast media, it was necessary to employ a current intensity between 118 and 182 mA/cm(2) with energy consumption higher than 370 kWh/m(3). Overall, the electrochemical degradation was revealed to be a reliable process for the treatment of iodinated contrast media that can be found in contaminated waters such as hospital wastewater or pharmaceutical waste-contaminated streams. (C) 2014 Elsevier B.V. All rights reserved.

Raw leachate and a biological effluent coming from the same raw leachate that has been biologically treatedin a new type of biological reactor, were electrochemically treated. A batch-type electrolytic cell usingtwo patented DSA electrodes was employed. Raw leachate, treated for 240 min at a current density of200 mA/cm2, falls within the sewer discharge limits set by Italian legislation for the COD. Instead, effluentobtained through combined biological and electro-oxidation treatment (by using 83 mA/cm2 and133 mA/cm2) has a COD such that could be discharged into the sewer and, after applying a current densityequal to 200 mA/cm2 after 240 min, has a COD value such that can even discharged into receivingwater bodies. The electrochemical oxidation carried out is only effective on nitrogen ammonia throughindirect electro-oxidation; it is not effective on other nitrogen-containing species. In any case, whereammonia is present (i.e., in the raw leachate), 82% is removed by the end of the test (i.e., after240 min of electrolysis) at 200 mA/cm2. Also, for the raw leachate, chloramine formation is most markedat low current densities. Nevertheless, the toxicity does not appear to be affected; in fact, decreaseregardless of the applied current density.

There is a need for a reliable sustainable option to effectively manage the landfill leachate generation. This study presents a simple procedure for the revegetation of the walls of closed landfills, employing the leachate as a fertirrigant. The native plants Lepidium sativum, Lactuca sativa, and Atriplex halimus, which suit the local climate, were chosen for this study in Southern Italy. The methodology was structured into three phases (i) early stage toxicity assessment phase (apical root length and germination tests), (ii) adult plant resistance assessment phase, and (iii) soil properties verification phase. The rationale of the proposed approach was first to look at the distinctive qualities and the potential toxicity in landfill leachates for fertigation purposes. Afterwards, through specific tests, the plants used were ranked in terms of resistance to the aqueous solution that contained leachate. Finally, after long-term irrigation, any possible worsening of soil properties was evaluated. The results demonstrated the real possibility of using blended leachate as a fertigant for the revegetation of the walls of closed landfills. In particular, the plants maintained good health when leachate was blended at concentrations of lower than 25 and 5 %, respectively for A. halimus and Lepidium sativum. Irrigation tests showed good resistance of the plants, even at dosages of 112 and 133.5 mm m(-2), at maximum concentrations of 25 and 5 %, respectively, for A. halimus and Lepidium sativum. The analysis of the total chlorophyll content and of aerial parts dried weight confirmed the results reported above.

Sono riportati i risultati dell'attività sui fanghi urbani condotta dall'Irsa nell'ambito del progetto europeo FP6 Neptune, terminato il 31 marzo 2010 dopo 3,5 anni di attività. L'obiettivo è stato di verificare se la gestione dei fanghi urbani possa essere facilitata mediante la separazione dei fanghi primari da quelli secondari, destinando in agricoltura il fango secondario (biologico) e a processi termici distruttivi on-site o off-site il fango primario. Questo approccio, già oggetto di uno studio teorico [1], si basa sulle evidenze che le caratteristiche chimiche e tecnologiche del fango primario e secondario sono differenti (contaminanti, nutrienti, ispessibilità, digeribilità, disidratabilità)[2]. Il fango secondario, normalmente esente da contaminazione organica, ma ricco di azoto e fosforo può essere destinato all'uso agricolo dopo trattamenti specifici di stabilizzazione effettiva e di riduzione del volume. I risultati relativi alla caratterizzazione di fango primario e secondario campionati su tre impianti dell'area di Roma, la valutazione dell'inceneribilità di fanghi dei suddetti impianti nonché le valutazioni energetiche di differenti schemi di trattamento confermano che la separazione dei fanghi può essere una valida alternativa di gestione per i grandi impianti di depurazione.

A regression tree model has been used to make predictions of six gross parameters (COD, CODsol, N-NH4 +, TN, Ptot and TSS) of an innovative SBBGR reactor. R2 values ranging from 0.94 to 0.97 were found forammonia and total phosphorus, respectively. This application showed its usefulness as a decision support system for wastewater treatment plants in tourist areas which typically operate under high stressconditions due to the sharp fluctuations of wastewater flow and composition. A forecast of the bioreactor's performance would help the plant manager to put in place the required practices and procedures.The regression tree model could be part of the automation and control system of the SBBGR plant, allowing the change of operating conditions to be carried out automatically and in an effective way to face thetouristic stress issue.

Recent studies showed that endocrine active compounds (EDs) capable to induce fish gonadal histopathologies, plasma vitellogenin and thyroid disruption, are transported by the River Lambro to the River Po, potentially affecting the fish community of the main Italian river. To assess whether fish relative abundance, composition and health were impaired by the River Lambro, a 3-year survey was undertaken in the main river. Results showed that the tributary supports in the River Po a denser fish community (+43 %), with a higher total biomass (+35 %). The survey also showed niche- and sensitivity-dependent effects, so that three benthopelagic species (bleak, topmouth gudgeon, and bitterling) were, for example, more abundant downstream from the tributary (up to 3.4×), but their sizes were significantly smaller. The present fish community was then compared with that described 30 years before in the same area of the Po River. This comparison highlighted that some fish species have disappeared and many have severely declined. To better evaluate this contrast, a sediment core of the Lambro tributary was analysed for the time trends of natural estrogens (E1, E2, E3), bisphenol A and alkylphenols. The results showed that during the last 50 years the River Lambro has been exposed to high estrogenic activities (16.1 ± 9.3 ng E2 equivalents/g), which inevitably affected also the River Po. In addition, at the time of the previous survey, six species of the main river had skewed sex ratios toward all-female populations, providing evidence that EDs and particularly (xeno)estrogens were already affecting the long-term viability of fish populations. Estrogens thus can be ascribed among the causal factors of fish qualitative and quantitative decline of the River Po, although long-term effects have been likely mitigated by nonconfinement of fish populations and nutrient enrichment.

Nanocrystalline titania (TiO2) synthesized via sol-gel, by using an alkoxide precursor were deposited ontocommercially available silica and alumina fibers, namely E-Glass and Nextel 650, respectively. Differentprocessing conditions and material preparation parameters, such as amount of TiO2, film composition andannealing temperature were tested in order to obtain nanocrystalline TiO2 with different morphologicaland structural characteristics. The materials were characterized by scanning electron microscopy (SEM),X-ray diffraction (XRD), and the Brunauer, Emmett, and Teller (BET) surface area measurements. Thephotocatalytic activity of the obtained coated fibers was investigated by monitoring the degradationof a model molecule, an azo dye (Methyl Red), under UV irradiation in aqueous solution. The detectedphotocatalytic performance of the sol-gel derived nanocrystalline TiO2 was explained on the basis ofmechanism associated to the photocatalytic decomposition of organic molecules using semiconductoroxides and accounted for the structural and morphological characteristics of the TiO2 based coating. Thematerials with the most suited characteristics for photocatalysis were used to scale up the depositiononto a larger sample of fiber and then tested in a photocatalytic reactor. A commercially available TiO2standard material (TiO2 P25 Degussa) was used as reference, in order to ultimately assess the viability ofthe coating process for real application.

Analysis of 11 polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A bis 2,3-dibromopropylether (TBBPA-bis), tetrachlorobisphenol A (TCBPA), tetrabromobisphenol A (TBBPA)and hexabromocyclododecanes (HBCDs) was optimized by ultrahigh pressure liquid chromatography/tandem mass spectrometry (UPLC-MS/MS) operating in negative ion (NI) mode. Electrosprayionization (ESI), atmospheric pressure photoionization (APPI) and atmospheric pressure chemicalionization (APCI) sources were tested and for PBDEs APCI gave higher sensitivity than APPI whilefor TBBPA-bis APCI and APPI showed similar performance. ESI was the best option for TCBPA, TBBPAand HBCDs. Detection limits were between 20 and 59 fg for the compounds analyzed by ESI, 0.10and 0.72 pg for PBDEs and 6 pg for TBBPA-bis. The matrix effect of sewage sludge extract was alsotested showing negligible ion suppression for APCI and an increase of the background level of allinvestigated pollutants leading to a worsening of the limits of quantification by a factor between 1.2 and3.3. The UPLC-APCI/MS/MS method for PBDEs, after pressurized liquid extraction (PLE), was validatedby comparison with the concentration values from the NIST 1944 standard reference material. Theadvantages of the methods include low detection limits, PBDE congeners specificity using selectedmultiple reaction monitoring (MRM) transitions, and the absence of thermal degradation of higher PBDEcongeners, especially BDE-209. The methods were applied for the determination of the above reportedflame retardants in sewage sludge in order to get more information about the degradation on PBDEs(in particular BDE-209) during municipal wastewater treatments.

An analytical set-up was optimized aimed at detecting a wide range of non target compounds in terms of polarities, namely from low/medium polar to very polar/ionic. Such an analytical strategy was applied for monitoring both the influent and the effluents of the step included in a pilot-scale experimental set-ups for wastewater reuse. The set-ups include sequential biofiltration with intermediate aeration at different empty bed contact time (EBCT) or with an intermediate ozonation. The non target screening was finalized to better tailor the wastewater reuse procedure.The comparison of the different treatment steps was performed based on (i) comparing the removal efficiency of suspect CECs identified in the samples, (ii) number of overall trends (compounds whose peak area along the treatment steps decreases, increases or remains steady) and (iii) by a multivariate analysis employing the principal component analysis (PCA).The investigation performed was able to assess the behavior of compounds detected as suspect (e.g. metformin) along the experimental set-up based on multiple treatment barriers. In addition, non target screening allowed to compare the effluents in terms of the four classes of compounds and to obtain relevant results to be conveniently used for the assessment strategies of the experimental wastewater reuse set-ups.

The photochemical degradation of two azo and two anthraquinonic dyes was performed using potassiumperoxymonosulphate (Oxone) activated by UV radiation. The fast decolourization of all dyes wasobserved within 6 min of UV irradiation, with corresponding dye decays higher than 80%. The kinetic rateconstants of the dyes' decay were determined, along with the energetic efficiency of the photochemicaltreatment, taking into account the influence of a few anions commonly present in real wastewaters (i.e.,chloride, nitrate, carbonate/bicarbonate and phosphate ions). Chloride and carbonate/bicarbonate ionsenhanced dye degradation, whereas phosphate ions exerted an inhibitory effect, and nitrates did nothave a predictable influence. The dye decolourization was not associated with efficient mineralization, assuggested by the lack of a significant total organic carbon (TOC) decrease, as well as by the lowconcentrations of a few detected low molecular weight by-products, including nitrate ions, formaldehydeand organic acids. High molecular weight by-products were also detected by mass spectrometry analysis.The investigated process may be proposed as a convenient pre-treatment to help dye degradation inwastewater during combined treatment methods.

A 2-year sampling campaign was conducted inthree wastewater treatment plants of various sizes in theRome area to assess the occurrence of nutrients andmicropollutants among primary, secondary and digestedsludge. The primary purpose was to evaluate the quality ofdifferent sludge types and their suitability for agricultural use.Primary sludgewas consistently more polluted than secondaryin terms of organic micropollutants, whereas heavy metalspartitioned equally among the sludge types. In digestedsludge, the heavy metal concentrations were always belowlimit values proposed for agricultural utilisation. In contrast,organic micropollutants concentrated during anaerobic digestionand affected the quality of the digested sludge. Secondarysludge resulted less polluted and richer in nitrogen and phosphorus(up to three times) than primary sludge and is hencemore suitable for agricultural use. Separate processing ofprimary and secondary sludge might therefore be an innovativeoption for sludge management that could maximise thepossibilities of agricultural use of secondary sludge and limitdisposal problems only to primary sludge. In fact, primarysludge could be easily treated and disposed of by conventionalprocesses including thickening, anaerobic digestion, centrifugationand incineration, whereas the difficult digestibility ofsecondary sludge could be improved by disintegration pretreatmentbefore stabilisation.

Diclofenac (DCF) is one of the most detected pharmaceuticals in environmental water matrices and is known to be recalcitrant to conventional wastewater treatment plants. In this study, degradation of DCF was performed in water by photolysis and photocatalysis using a new synthetized photocatalyst based on hydroxyapatite and TiO2 (HApTi). A degradation of 95% of the target compound was achieved in 24 h by a photocatalytic treatment employing the HApTi catalyst in comparison to only 60% removal by the photolytic process. The investigation of photo-transformation products was performed by means of UPLC-QTOF/MS/MS, and for 14 detected compounds in samples collected during treatment with HApTi, the chemical structure was proposed. The determination of transformation product (TP) toxicity was performed by using different assays: Daphnia magna acute toxicity test, Toxi-ChromoTest, and Lactuca sativa and Solanum lycopersicum germination inhibition test. Overall, the toxicity of the samples obtained from the photocatalytic experiment with HApTi decreased at the end of the treatment, showing the potential applicability of the catalyst for the removal of diclofenac and the detoxification of water matrices.

The photocatalytic properties of anatase TiO2nanorods(NRs) and noble metal
semiconductor nanocomposites (TiO2NRs/Ag)prepared by colloidal chemistry routes and immobilized onto suitablesubstrates were investigated. Photocatalytic experiments were performedunder UV irradiation in order to test the degradation of a target compound(the azo dye, methyl red) in aqueous solution using TiO2P25 Degussa as areference material. Absorbance spectroscopy and liquid chromatography/mass spectrometry (LC/MS) measurements pointed out that, according topH conditions, TiO2NRs and TiO2NRs/Ag presented a photoactivity up to1.3 and 2 times higher than TiO2P25 Degussa, respectively. Notably, theTiO2NRs/Ag-based catalysts demonstrated a photocatalytic activity 2-foldhigher than bare TiO2NRs. Remarkably, only a negligible dependence on pH conditions was detected for the nanocompositecatalyst, whereas both TiO2NRs and TiO2P25 Degussa showed much higher photoactivity at acidic pH. In all the investigated cases,the identified byproducts pointed out the occurrence of the same reaction mechanism, basically relying on the hydroxyl radicalattaching on the benzene ring and on the homolytic rupture of the nitrogen
carbon bond of the dimethyl-amino moiety.

An innovative pilot plant based on UVB and TiO2 (Anatase) allowed for photocatalytic degradation of organic micro-pollutants. The catalyst was immobilized onto a channel through which the solution containing a target molecule (methylene blue, MB) was re-circulated. Due to the cationic nature of the MB substrate, the adsorption reaction onto the catalyst surface provided a significant contribution to the overall degradation mechanism due to the negatively charged surface at neutral pH (TiO2 pHzpc=6.8). The influence of the initial MB concentration was investigated in the range 0.3-2.0mg/L with the Langmuir-Hinshelwood (LH) model showing good data correlations at concentrations up to 0.7 mg/L, whereas at higher concentrations a pure zero-order (catalytic) kinetic trend was observed. Flow rate of the re-circulating solution sensibly influenced kinetics after the larger volumes of liquid exposed to UVB=TiO2 and to the better oxygen saturation in the liquid phase. UV-vis and HPLC-MS=MS experimental determinations allowed for identification of MB residual concentration and by-products.

Two different nanosized TiO2-based catalysts supported onto glass with tailored photocatalytic propertiesupon irradiation by UV light were successfully employed for the degradation of nalidixid acid, awidely diffused antibacterial agent of environmental relevance known to be non-biodegradable. Anataserod-like TiO2 nanocrystals (TiO2NRs) and a semiconductor oxide-noble metal nanocomposite TiO2 NRs/Ag nanoparticles (NPs), synthesized by colloidal chemistry routes, were cast onto glass slide andemployed as photocatalysts. A commercially available catalyst (TiO2 P25), also immobilized onto a glassslide, was used as a reference material. It was found that both TiO2 NRs/Ag NPs composite and TiO2 NRsdemonstrated a photocatalytic efficiency significantly higher than the reference TiO2 P25. Specifically,TiO2 NRs/Ag NPs showed a photoactivity in nalidixic acid degradation 14 times higher than TiO2 P25and 4 times higher than bare TiO2 NRs in the first 60 min of reaction. Several by-products were identifiedby HPLC-MS along the nalidixic acid degradation, thus getting useful insight on the degradation pathway.All the identified by-products resulted completely removed after 6 h of reaction

Phytoremediation comprises a set of technologies (e.g. plant assisted bioremediation,phytoextraction, phytostabilisation) based on some specific plant capabilities directlyor indirectly promoting contaminant removal. Bioremediation of contaminated sites isin line with environmental sustainability and with so called Green Remediation. Itmeans "the practice of considering all environmental effects of remedy implementationand incorporating options to maximize the net environmental benefit of cleanup actions".Phytoremediation or more properly plant assisted bioremediation provides arelatively low cost, environment friendly treatment for many multi contaminated areas.In this work, the results of the first 14th months of poplarassisted bioremediationof a historically PCB contaminated area in Southern Italy is reported. The Monviso clone was selected forits tested capability to promote hexachlorocyclohexane degradation in another CNR field study. The areainvestigated has been used for several decades as an unsupervised waste disposal tip and it is contaminatedas well as PCBs by heavy metals. Six hundred poplar cuttings (Monviso clone) were planted in anarea of 785 m2 previously fertilized with compost. After 14 months, of plant cuttings, soils, roots andleaves of selected target trees were analysed in order to identify PCBs and heavy metals contamination(HM). Chemical investigations were conducted before and after poplar planting using GC-MS and ICP-MSinstruments, respectively. At the same time, the abundance, cell viability and dehydro-genase activity(DHA) of the autochthonous microbial community were assessed to investigate micro-organisms' role inthe reclamation processes. The comparison of the initial chemical analysis of the contaminated area withthose performed 14 months after the poplar cutting planting, makes it possible to show:- a general decrease in most of PCB congeners in all soil samples analysed and in no case was the legallimit (60 ppb) exceeded. Trace concentrations of PCBs were found in roots and leaves (their amountwas always below the legal limits).- HMs, which were initially found as widespread contaminants and at concentrations generally higherthan the legal limits, had by 14 months after the poplar-cuttings planting drastically, decreased at allthe sampling points. Zn, Cd, Se and Sn were detected in leaf and root samples of the target tree investigated.The HM plant bioconcentration factor (BAF, considering roots and leaves) and translocationfactor (TF) suggest that poplars are also able to partially phytoextract and phyto-stabilise HMs.Microbial results show a significant improvement in microbial activity. In fact microbial DHA increasedin all samples analysed 14 months after the poplar-cuttings planting, although it maintained differentvalues at the different sampling points. Overall experimental results suggest an improvement insoil quality in terms of decreasing of P

Plant-based clean up technologies are gaining popularity as sustainable solutions to contaminated soil remediation. In particular, plant-assisted bioremediation or phyto-assisted bioremediaton exploits the synergistic action between plant root system and natural microorganisms (bacteria and fungi) to remove, convert or contain toxic substances in soil and water. It relies on the use of a selected appropriate plant for stimulating in the rhizosphere (e.g. through root exudates production, oxygen transport) the biodegradation activity of natural soil microorganisms. In this context, a poplar-assisted bioremediation strategy has been applying for three years to a multi-contaminated (PCBs and heavy metals) area in Southern Italy using a specific poplar clone (Monviso). It was chosen thanks to its capabilities previous tested for promoting hexachlorocyclohexane degradation. At selected times (0, 420, 900 days) PCB and heavy metal (HMs: V, Cr, Sn, Pb) concentrations were assessed on soil samples at different depths and distance from tree trunks inside some contaminated plots. Similarly, microbial analyses were performed on soil samples to assess total microbial abundance, cell viability, dehydrogenase activity and the phylogenetic composition of the autochthonous microbial community. Three years after the poplar planting a significant decrease in PCB and HMs concentrations was observed. Currently, the values of all PCBs detected are under the Italian legislation limits in the plots investigated. The microbiological analysis show an overall improvement in soil quality in terms of an increase in microbial abundance, cell viability and organic carbon content in the rhizosphere soil samples. Moreover, the phylogenetic analysis of the microbial community showed a higher percentage of Bacteria in the rhizosphere than in the bulk soil. In particular, a significant increase in Actinobacteria and Alpha-Gamma-Proteobacteria, which include several speciesable to degrade PCBs, was observed. Overall results show that the poplar-assisted bioremediation strategy was able to promote both the persistent organic contaminant degradation and the phytostabilization of the inorganic ones.

A plant-assisted bioremediation strategy was applied in an area located in Southern Italy, close to the city of Taranto, historically contaminated by polychlorinated biphenyls (PCBs) and heavy metals. A specific poplar clone (Monviso) was selected for its ability to promote organic pollutant degradation in the rhizosphere, as demonstrated elsewhere. Chemical and microbiological analyses were performed at the time of poplar planting in selected plots at different distances from the trunk (0.25-1m) and at different soil depths (0-20 and 20-40cm), at day 420. A significant decrease in PCB congeners and a reduction in all heavy metals was observed where the poplar trees were present. No evidence of PCB and heavy metal reduction was observed in the non poplar-vegetated soil. Microbial analyses (dehydrogenase activity, cell viability, microbial abundance) of the autochthonous microbial community showed an improvement in soil quality. In particular, microbial activity generally increased in the poplar-rhizosphere and a positive effect was observed in some cases at up to 1m distance from the trunk and up to 40cm depth. The Monviso clone was effective in promoting both a general decrease in contaminant occurrence and an increase in microbial activity in the chronically polluted area a little more than one year after planting.

Plant-assisted bioremediation, the use of plants to promote the extraction, the sequester or detoxification of pollutants through biological processes is a green, effective, in situ, non intrusive, low cost, aesthetically pleasing and, socially accepted technology to remediate contaminated soil. Potential for plant-assisted bioremediation depends upon the interactions among, soil, contaminants, microorganisms (bacteria and microfungi) and plants occurring in the rhizosphere where, the release of root exudates and oxygen with circadian rhythm can stimulate the biodegradation activity of natural soil microorganisms. This technology has been applying for three years to a multi-contaminated (PCBs and heavy metals) area in Southern Italy using as plant a selected poplar clone (Monviso).

The European Union (EU) Project Routes aimed to discover new routes in sludge stabilization treatments leading to high-quality digested sludge, suitable for land application. In order to investigate the impact of different enhanced sludge stabilization processes such as (a) thermophilic digestion integrated with thermal hydrolysis pretreatment (TT), (b) sonication before mesophilic/thermophilic digestion (UMT), and (c) sequential anaerobic/aerobic digestion (AA) on digested sludge quality, a broad class of conventional and emerging organic micropollutants as well as ecotoxicity was analyzed, extending the assessment beyond the parameters typically considered (i.e., stability index and heavy metals). The stability index was improved by adding aerobic posttreatment or by operating dual-stage process but not by pretreatment integration. Filterability was worsened by thermophilic digestion, either alone (TT) or coupled with mesophilic digestion (UMT). The concentrations of heavy metals, present in ranking order Zn > Cu > Pb > Cr ~ Ni > Cd > Hg, were always below the current legal requirements for use on land and were not removed during the processes. Removals of conventional and emerging organic pollutants were greatly enhanced by performing double-stage digestion (UMT and AA treatment) compared to a single-stage process as TT; the same trend was found as regards toxicity reduction. Overall, all the digested sludges exhibited toxicity to the soil bacterium Arthrobacter globiformis at concentrations about factor 100 higher than the usual application rate of sludge to soil in Europe. For earthworms, a safety margin of factor 30 was generally achieved for all the digested samples. © 2014 Springer-Verlag Berlin Heidelberg.

tHomogeneous aluminium species, obtained by dissolving AlCl3·6H2O into methanol, were characterisedand tested as catalysts into the direct esterification of free fatty acids with methanol. The nature andthe role of this catalyst was further investigated through ESI-MS and FTIR spectroscopy, by revealingan immediate exchange reaction between methanol and the water molecules originally bounded to thealuminium, producing a final mixed methanol-aquo-complex whose reactivity was found to be compa-rable to that of a methanolic solution of hydrogen chloride. Reaction conditions were optimised using thedesirability function applied on the response surface methodology analysis of a Box-Behnken factorialdesign of experiments. By carrying out the reaction at 72oC for 120 min and using a catalyst amount of1.5% (mol of Al respect to fatty acids), almost 94% of the starting acids were converted. At the end of thereaction, a biphasic system was obtained in which the upper methanolic phase, which contained mostof the starting catalyst, was separated from the heaviest phase, mainly composed of fatty acid methylesters. Such a distribution not only allowed the biodiesel to be easily separated, but also the catalystswere efficiently recovered and reused for at least four times, determining a total TON greater than 200,without revealing any loss of its activity.

Chemical-biological degradation of a widely spread antibacterial (nalidixic acid) was successfully obtained by an integrated membrane bioreactor (MBR)-ozonation process. The composition of the treated solution simulated the wastewater from the production of the target pharmaceutical, featuring high salinity and a relevant concentration of sodium acetate. Aim of treatment integration was to exploit the synergistic effects of chemical oxidation and bioprocesses, by adopting the latter to remove most of the COD and the ozonation biodegradable products. Integration was achieved by placing ozonation in the recirculation stream of the bioreactor effluent. The recirculation flow rate was three-fold the MBR feed. and the performance of the integrated system was compared to the standard polishing configuration (single ozonation step after the MBR). Results showed that the introduction of the ozonation step did not cause relevant drawbacks to both biological and filtration processes. nalidixic acid passed undegraded through the MBR and was completely removed in the ozonation step. Complete degradation of most of the detected ozonation products was better achieved with the integrated MBR-ozonation process than using the sequential treatment configuration, i.e. ozone polishing after MBR, given the same ozone dosage.

Various studies over recent years have proved the increasing occurrence in effluent of wastewater treatment plants (WWTP)of several contaminants of emerging concern (CECs), which are not completely removed by the common technologies employed in conventional WWTP. CECs found at highest levels (ng L-1 to ?g L-1) are pharmaceuticals, artificial sweeteners, pesticides, flame-retardants, plasticizers and perfluoroalkyl substances (1,2).The main objective of this study was to investigate an electrochemical treatment based on a boron-doped diamond (BDD) electrode, as an advanced oxidation process (AOP) for the removal of several CECs from effluent of WWTP with enhanced performance in terms of efficiency and applicability (3).Electrochemical treatments were performed with a CONDIAPURE? system using a DIACHEM? electrode stack in a flow through cell (CONDIAS GmbH, Germany), in both synthetic water and real secondary effluent. The electrode stack was composed by two BDD cathodes and one BDD anode and in situ oxidation was performed with four anode/cathode pairs applying a total current of 0.4 A. A total of 10 L of solution with the target organic pollutants was circulated through the reactor at a flow rate of 18.5 L/min.The removal of a mixture of CECs (iopromide, carbamazepine, diclofenac, erythromycin, benzotriazol, sulfamethoxazole, caffeine, gabapentin, metoprolol, phenythoin, primidone, venlafaxine, TCEP) by the investigated electrochemical system was primarily assessed in synthetic model water spiked with the target contaminants at concentration in the range of 2-5 ?g L-1. Removal below limit of quantification (LOQ) was achieved for all tested compounds after 200 min of treatment. Decay follows pseudo first order kinetics and kinetic constants (k) of 0.07 min-1 for sulfamethoxazole and diclofenac and in the range 0.03-0.01 min-1 for the other CECs were obtained, being TCEP the pollutant with slowest kinetics.Afterwards, the secondary effluent of the municipal WWTP Garching (Germany) was employed as a real water matrix which revealed the occurrence of several CECs (including the mixture of selected compounds listed above) at concentration levels between 20 ng L-1 and 20 ?g L-1. The electrochemical treatment of the effluent was performed under the same conditions employed with the spiked synthetic water. Results demonstrated removal below LOQ for all the target CECs after 300 min with lower degradation rates than in the spiked synthetic water solution (k <= 0.01 min-1).The detection of transformation products of investigated CECs was performed by UPLC-QTOF/MS/MS, by employing a non-target analysis approach which was based on accurate MS and MS/MS data and open source databases and software.

The treatment of a pharmaceutical wastewater resulting from the production of an antibacterial drug (nalidixic acid) was investigated employing a membrane bioreactor (MBR) integrated with either ozonation or UV/H2O2 process. This was achieved by placing chemical oxidation in the recirculation stream of the MBR. A conventional configuration with chemical oxidation as polishing for the MER effluent was also tested as a reference. The synergistic effect of MBR when integrated with chemical oxidation was assessed by monitoring (i) the main wastewater characteristics, (ii) the concentration of nalidixic acid, (iii) the 48 organics identified in the raw wastewater and (iv) the 55 degradation products identified during wastewater treatment. Results showed that MBR integration with ozonation or UV/H2O2 did not cause relevant drawbacks to both biological and filtration processes, with COD removal rates in the range 85-95%. Nalidixic acid passed undegraded through the MBR and was completely removed in the chemical oxidation step. Although the polishing configuration appeared to give better performances than the integrated system in removing 15 out of 48 secondary organics while similar removals were obtained for 19 other compounds. The benefit of the integrated system was however evident for the removal of the degradation products. Indeed, the integrated system allowed higher removals for 34 out of 55 degradation products while for only 4 compounds the polishing configuration gave better performance. Overall, results showed the effectiveness of the integrated treatment with both ozone and UV/H2O2.

The possibility of reusing leachate substances for agronomical purposes might be of interest, especially in arid areas when used in addition to the leachate water content. This study presents a simple procedure for the revegetation of the walls of closed landfills, reusing the leachate as a fertigant. The results demonstrated the real possibility of employing blended leachate as a fertigant for the revegetation of the walls of closed landfills. The native plants Lepidium sativum, Lactuca sativa and Atriplex halimus, which suit the local climate, were chosen for this study in Southern Italy. The methodology was structured into three phases: (i) early-stage toxicity assessment phase (apical root length and germination tests), (ii) adult plant resistance assessment phase and (iii) soil properties verification phase. The rationale of the proposed approach was first to look at the distinctive qualities and the potential toxicity in landfill leachates for fertigation purposes. Afterwards, through specific tests, the plants used were ranked in terms of resistance to the aqueous solution that contained leachate. Finally, after long-term irrigation, any possible worsening of soil properties was evaluated. In particular, the plants maintained good health when leachate was blended at concentrations of lower than 25% and 5%, respectively, for Atriplex halimus and Lepidium sativum. Irrigation tests showed good resistance of the plants, even at dosages of 112 and 133.5 mm/m2, at maximum concentrations of 25% and 5%, respectively, for Atriplex halimus and Lepidium sativum. The analysis of the total chlorophyll content and of aerial parts dried weight confirmed the results reported above. ? 2016 Springer International Publishing Switzerland.

Epidemiological studies show that exposure to specific persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF), polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) is strongly associated with negative interferences on endocrine systems and on alterations of reproductive physiology. Therefore, the determination of these compounds in the environment is of great importance from the ecotoxicological point of view. Accurate determination of PCDD/F, PBDE and PCB in complex matrices is a challenge because of their low expected concentrations in the range of ppb to sub-ppb. For the complexity of environmental matrices, analytical determinations often require long time periods of analysis and several stages of extraction/preconcentration, purification, etc in order to eliminate interferences. These procedures do not fit in extensive environmental monitoring programs, where it is necessary to analyze a large number of samples at a time not excessively long. In this paper, the official EPA methods (1,2) for chlorinated pollutant analysis has been evaluated and modified to provide a faster and more reliable alternative analytical method for simultaneous determination of interest compounds in soil and sediments with a single extraction.Accelerated solvent extraction (ASE) has been used for simultaneous extraction of organic compounds. The most favorable extraction conditions proved to be n-hexane as the extraction solvent, temperature of 120 °C, pressure of 1500 psi and three static cycles in each case. Purification of the extract was accomplished by automated Power-PrepTM/Sample Clean-up system. The analyses were then performed by using gas chromatography coupled to triple quadrupole mass spectrometry. Utilizing triple quadruple mass spectrometry under positive EI with multiple reaction monitoring (MRM) mode, greatly enhances the sensitivity and selectivity of detection, compared to selective ion monitoring (SIM) mode. The GC-QqQ(MS/MS) sensitivity, lower than that of GC-HRMS, is good enough (LODs in the down to low pg levels) to detect the normal concentrations of these compounds in environmental samples. The obtained analytical results demonstrate excellent recoveries for the various congeners, comparable to those of official methods and detection limits useful for the analysis of real matrices. The determination of these compounds in soils and sediments and the evaluation of the distribution of various congeners (fingerprint method) has allowed to obtain information on the origin of the contamination.

Present technologies for wastewater treatment do not sufficiently address the increasing pollution situation of receiving water bodies, especially with the growing use of personal care products and pharmaceuticals (PPCP) in the private household and health sector. The relevance of addressing this problem of organic pollutants was taken into account by the Directive 2013/39/EU that introduced (i) the quality evaluation of aquatic compartments, (ii) the polluter pays principle, (iii) the need for innovative and affordable wastewater treatment technologies, and (iv) the identification of pollution causes including a list of principal compounds to be monitored. In addition, a watch list of 10 other substances was recently defined by Decision 2015/495 on March 20, 2015. This list contains, among several recalcitrant chemicals, the painkiller diclofenac and the hormones 17 beta-estradiol and 17 alpha-ethinylestradiol. Although some modern approaches for their removal exist, such as advanced oxidation processes (AOPs), retrofitting most wastewater treatment plants with AOPs will not be acceptable as consistent investment at reasonable operational cost. Additionally, by-product and transformation product formation has to be considered. The same is true for membrane-based technologies (nanofiltration, reversed osmosis) despite of the incredible progress that has been made during recent years, because these systems lead to higher operation costs (mainly due to higher energy consumption) so that the majority of communities will not easily accept them. Advanced technologies in wastewater treatment like membrane bioreactors (MBR) that integrate biological degradation of organic matter with membrane filtration have proven a more complete elimination of emerging pollutants in a rather cost- and labor-intensive technology. Still, most of the presently applied methods are incapable of removing critical compounds completely. In this opinion paper, the state of the art of European WWTPs is reflected, and capacities of single methods are described. Furthermore, the need for analytical standards, risk assessment, and economic planning is stressed. The survey results in the conclusion that combinations of different conventional and advanced technologies including biological and plant-based strategies seem to be most promising to solve the burning problem of polluting our environment with hazardous emerging xenobiotics.

Fat, oil and grease produced by oil/water separation at the wastewater treatment plant of Bari West (Southern Italy) were taken, characterized and converted. After chemical activation of this fatty fraction, with the aim of converting the starting calcium soaps into the respective free fatty acids, a direct esterification was carried out under very mild conditions. Working at 345 K under atmospheric pressure, the thermodynamic conversion (more than 90%) of the free fatty acids into the respective methyl esters was obtained in less than 2 h, by using AlCl3·6H2O as catalyst. Fundamental parameters, such as kinetic and equilibrium constants at different temperatures and activation energy correlated to the use of this catalyst, were also calculated. The biodiesel was purified with a distillation under vacuum, providing a final product conformed to the EN14214 requirements. The convenience of the overall process in terms of costs (0.45 EUR L-1) and specific thermal energy supply (5.02 MJ KgFAMEs-1) make such a process a really sustainable and effective example of valorization of a waste.

The Water Framework Directive, recently amended with new priority substances (2013/39/EU), is meant to regulate the health status of European aquatic environments, including transitional waters. Despite the ecological and economic importance of transitional water bodies and, in particular, of coastal lagoons, a relevant example of this type of environments, little is known about their contamination by priority substances, particularly by endocrine disrupting chemicals (EDCs). In this study, a wide array of priority substances, all with recognised disrupting properties, was investigated in the Sacca di Goro Lagoon (Adriatic Sea, Italy), which receives freshwater from the Po River after draining the most urbanised and industrialised Italian regions. Flame retardants, alkylphenols, bisphenol A, natural and synthetic steroids, personal care products and legacy pollutants were investigated both in sediments and in the clam Ruditapes philippinarum collected from three sites in the lagoon. Sediments showed that most of the chemicals analysed could reach the lagoon ecosystem but their concentrations were below existing quality guidelines. Clams essentially reflected this condition although some concern was raised by polybrominated diphenyl ethers (PBDEs): the limit for the sum of six congeners set for biota in the European Directive (2013/39/EU) to protect human health was exceeded 4-5 times. No significant biota-sediment accumulation factors (BSAFs) were calculated. Nonylphenol, tonalide, PBDE, polychlorinated biphenyls and bisphenol A were the most abundant chemicals in clam tissues.

An on-line solid phase extraction coupled with high-performance liquid chromatography in tandem with mass spectrometry (on-line SPE/HPLC/MS-MS) method for the determination of five microcystins and nodularin in surface waters at submicrogram per liter concentrations has been optimized. Maximum recoveries were achieved by carefully optimizing the extraction sample volume, loading solvent, wash solvent, and pH of the sample. The developed method was also validated according to both UNI EN ISO IEC 17025 and UNICHIM guidelines. Specifically, ten analytical runs were performed at three different concentration levels using a reference mix solution containing the six analytes. The method was applied for monitoring the concentrations of microcystins and nodularin in real surface water during a sampling campaign of 9 months in which the ELISA method was used as standard official method. The results of the two methods were compared showing good agreement when the highest concentration values of MCs were found. [Figure not available: see fulltext.]