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Lay abstract In the present work, 21 bacteria associated to

Among the numerous clean-up techniques for water treatment, sorption methods are widely used for the removal of trace metals. Phragmites australis is a macrophyte commonly used in constructed wetlands for water purification, and in the last decades, its use as biosorbent has attracted increasing attention. In view of a circularly economy approach, this study investigated improvement of trace metal removal by recycling the biomass of P. australis colonizing a constructed wetland, which operates as post-treatment of effluent wastewater from an activated sludge plant serving the textile industrial district of Prato (Italy). After the annual mowing of the reed plants, the biomass was dried and blended to derive a sustainable and eco-friendly biosorbent and its sorption capacity for Fe, Cu, and Zn was investigated comparing the batch system with the easier-to-handle column technique. The possibility of regeneration and reuse of the biosorbent was also evaluated. The biomaterial showed an interesting sorption capacity for Cu, Fe, and Zn, both in batch and in column experiments, especially for Fe ions. The immobilization of the biosorbent in column filters induced some improvement in the removal efficiency, and, in addition, this operation mode has the advantage of being much more suitable for practical applications than the batch process.

The Sasso Fratino Integral Nature Reserve (Italy) aims to protect nature and territory. Since no anthropic activities are allowed, it represents a good model to study the bacterial community of a wild environment. The aim of this work was to characterise the cultivable and the total bacterial community of soil samples from the reserve in terms of taxonomy, composition, and structure. Seven soil samples were collected at different altitudes, and the chemical composition, the total and the cultivable microbiota, and the antibiotic resistance profiles of isolates were investigated. Total bacterial communities, studied through Next Generation Sequences analysis, included 390 genera. Samples differed in terms of microbial composition basing on the different altitude/vegetation of collection points. Random Amplified Polymorphic DNA Analysis (RAPD) allowed to identify 82 haplotypes out of 158 bacterial isolates. The taxonomic identification through 16S rDNA sequencing revealed that the strains were affiliated to 21 genera. Antibiotic resistance profiles of bacteria were also investigated, highlighting a high resistance against streptomycin and kanamycin. This work represents the first description of the soil bacterial community from the Natural Reserve of Sasso Fratino, and it is the first study considering the soil microbiota of an Italian integral nature reserve.

BACKGROUND Agriculture represents a productive sector typically characterized by a high water demand, whereas freshwater (FW) availability is a problem of increasing concern in the world and FW resources are becoming insufficient for sustaining agricultural irrigation. The reuse of treated wastewaters (TWWs) for crop irrigation could be an efficient tool for reducing water shortage. Hence, the present study evaluated the food quality of Fragaria x ananassa (cultivar Camarosa) fruits irrigated with four types of treated wastewaters (TWWs). Strawberries were analysed for yield, sucrose, fructose, glucose, total soluble polyphenols (TSP), total monomeric anthocyanins (TMA), and antiradical and antioxidant capacity. In addition, a targeted quantification of the most representative phenolic compounds of strawberry was performed. RESULTS TWWs complied the Italian ministerial decree 185/2003 for wastewater reuse, with very few exceptions, mainly represented by chloride concentrations (258-643 mg L-1 versus a legal threshold of 250 mg L-1 ). The reuse of TWWs reduced fruit yield (10-26%) compared to irrigation with tap water as a control. Irrigation with TWWs gave also rise to the decrease of total sugars (14-26%), TSP (2-10%) and TMA (29-49%). Individual phenolic acids, flavonols and flavanols were quite stable in response to the irrigation with TWWs, whereas anthocyanidins decreased significantly. CONCLUSION Although TWWs negatively affected fruit quality, the nutritional and nutraceutical parameters determined in the present study were in line with data previously reported for strawberries purchased in the market or cultivated in research orchards, thus suggesting that the use of TWWs does not prevent the fruit marketability. © 2020 Society of Chemical Industry.

Background: Rising number of multidrug-resistant human pathogens demands novel antibiotics: to this aim, unexplored natural sources are investigated to find new compounds. In this context, bacteria associated to medicinal plants, including Phragmites australis, might represent an important source of antimicrobial compounds. Materials & methods: In the present work, 21 bacterial endophytes isolated from P. australis roots were tested, by cross-streaking, for their inhibitory activity against 36 multidrug-resistant pathogens isolated from food, clinical patients and hospitals. Results & conclusion: Seven endophytes, belonging to Pseudomonas and Stenotrophomonas, were able to inhibit the growth of most of the target strains. In conclusion, this preliminary work could pave the way for the discovery of new antibiotics against superbugs.

In this paper, the design and start-up of a constructed wetland (CW) for the tertiary treatment of landfill leachates is presented. The flux is characterized by high salinity, high concentration of nitrogen (almost completely in the form of nitrate) and a biochemical oxygen demand (BOD)/chemical oxygen demand (COD) ratio close to zero. The CW pilot plant suffered from mechanical and hydraulic malfunctions which led to an uneven growth of plants inside the tanks. Despite this, COD has been reduced in the range of 0–30%, reduced forms of N (ammonia and nitrite) are also oxidized and removed by 50–80% and 20–26% on average. Considering the low number of plants and the loading rate, CW pilot plant allowed to remove more than 16 kg of COD, leading to a specific removal of 10 gCOD/d · m2. Moreover, bacterial communities associated to plants were isolated and analyzed in order to evaluate the influence of such communities on phytoremediation. Bulk soil registered the lowest bacterial titers, while plant compartments and rhizospheric soil showed to be more suitable for bacterial colonization. Twenty-five different bacterial genera were observed among the analyzed isolates, with the predominance of Pseudomonas genus.

In this study, we investigated the removal of Fe(III), Cr(VI), Al(III), diclofenac, and levofloxacin from treated wastewater in the presence of the free-floating plants Azolla filiculoides and Lemna minuta, to understand whether these species can be effectively used in a surface flow constructed wetland as wastewater refining treatment. Fe and Al were selected owing to their wide use as coagulant agents in wastewater treatment plants for promoting clariflocculation processes, whilst Cr was chosen due to its common use in industry. Diclofenac and levofloxacin, two molecules belonging to the most widely used pharmaceutical classes in the world, were studied as representative anti-inflammatory drugs and antibiotics, respectively. The study was performed at laboratory scale, exposing the plants separately to each individual contaminant at the concentrations of 5 mg L−1 for the metals (i.e. 2.5–5 times higher than the European limits concerning discharge into surface water), and 1 μg L−1 for the pharmaceuticals (concentration levels commonly found in wastewater). Depending on the plant species and contaminant tested, the range of different effects observed included low toxicity (i.e. Cr, Fe and diclofenac in L. minuta) and even a stimulatory effect on plant growth (i.e. for A. filiculoides with Al and for L. minuta with Al and levofloxacin). Moreover, both species proved to be very effective in the removal of Fe, Al and levofloxacin, with A. filiculoides showing the best performance (removal efficiency of 92%, 96%, and 60%, respectively), whereas for Cr and diclofenac the removal was always less than 10%. The higher removal capacity of A. filiculoides compared to L. minuta can be attributed to its superior tolerance of the contaminants, probably in turn related to the presence of nitrogen-fixing microorganism in its fronds.

A Life Cycle Assessment (LCA) was applied to compare different alternatives for sewage sludge treatment: such as land spreading, composting, incineration, landfill and wet oxidation. The LCA system boundaries include mechanical dewatering, the alternative treatment, transport, and final disposal/recovery of residues. Cases of recovered materials produced as outputs from the systems, were resolved by expanding the system boundaries to include avoided primary productions. The impact assessment was calculated using the CML-IA baseline method. Results showed that the incineration of sewage sludge with electricity production and solid residues recovery collects the lowest impact indicator values in the categories human toxicity, fresh water aquatic ecotoxicity, acidification and eutrophication, while it has the highest values for the categories global warming and ozone layer depletion. Land spreading has the lowest values for the categories abiotic depletion, fossil fuel depletion, global warming, ozone layer depletion and photochemical oxidation, while it collects the highest values for terrestrial ecotoxicity and eutrophication. Wet oxidation has just one of the best indicators (terrestrial ecotoxicity) and three of the worst ones (abiotic depletion, human toxicity and fresh water aquatic ecotoxicity). Composting process shows intermediate results. Landfill has the worst performances in global warming, photochemical oxidation and acidification. Results indicate that if the aim is to reduce the effect of the common practice of sludge land spreading on human and ecosystem toxicity, on acidification and on eutrophication, incineration with energy recovery would clearly improve the environmental performance of those indicators, but an increase in resource depletion and global warming is unavoidable. However, these conclusions are strictly linked to the effective recovery of solid residues from incineration, as the results are shown to be very sensitive with respect to this assumption. Similarly, the quality of the wet oxidation process residues plays an important role in defining the impact of this treatment.

A QuEChERS method was optimized and validated for the LC–MS/MS analysis of perfluoro-n-pentanoic acid (PFPeA), perfluoro-1-butanesulfonic acid (PFBuS), perfluoro-n-hexanoic acid (PFHxA), perfluoro-n-heptanoic acid (PFHpA), perfluoro-1-hexanesulfonic acid (PFHxS), perfluoro-n-octanoic acid (PFOA), perfluoro-n-nonanoic acid (PFNA), perfluoro-1-octanesulfonic acid (PFOS) and perfluoro-n-decanoic acid (PFDA) in freeze-dried strawberry and olive, as model fruits characterized by very different chemical compositions. The method was evaluated for apparent recovery, intra-day and inter-day precision, matrix effect and recovery. The method optimized for strawberry provided for most compounds absolute values of matrix effect (|ME%|) ≤ 11%, except for PFHxA, which showed a signal suppression of 22%. The extraction efficiency was tested at the spike levels 500–5000 pg/g d.w. for PFPeA, PFBuS, and PFHxA, and 100–1000 pg/g d.w. for the other target analytes, evidencing as a whole recoveries in the range of 65–89%. For olive fruits, due to their high fat content, an ultrasound-assisted extraction was necessary to obtain an efficient sample disgregation so as to increase the extraction yield and its precision. Moreover, a d-SPE clean-up with GCB allowed to achieve |ME%| ≤ 8% (except for PFBuS, which showed a signal enhancement of 19%) and recoveries calculated at the aforementioned spike levels were in the range 75–97%. The two methods provided very good linearity (R2 ≥ 0.9984) from 10,000 pg/g down to compound specific quantification limits, which were included in the ranges of 2.9–393 pg/g and 2.6–127 pg/g for strawberry and olive fruit, respectively. The methods were applied to the analysis of PFAAs in strawberry and olive fruits commercially available in two Italian supermarkets, as well as obtained under irrigation with various treated wastewaters (TWWs), evidencing in both cases a higher PFAAs occurrence in olives than in strawberry. However, PFAAs concentrations determined in the investigated fruit matrixes were quite low, being their sum 1.9 ng/g d.w. in the worst case (i.e. olive fruits grown under irrigation with TWWs).

Improvement of industrial productions through more environment-friendly processes is a hot topic. In particular, land and marine environment pollution is a main concern, considering that recalcitrant compounds can be spread and persist for a long time. In this context, an efficient and cost-effective treatment of wastewater derived from industrial applications is crucial. Phytodepuration has been considered as a possible solution and it is based on the use of plants and their associated microorganisms to remove and/or transform pollutants. In this work we investigated the culturable microbiota of Phragmites australis roots, sampled from the constructed wetlands (CWs) pilot plant in the G.I.D.A. SpA wastewater treatment plant (WWTP) of Calice (Prato, Tuscany, Italy) before and after the CW activation in order to check how the influx of wastewater might affect the resident bacterial community. P. australis specimens were sampled and a panel of 294 culturable bacteria were isolated and characterized. This allowed to identify the dynamics of the microbiota composition triggered by the presence of wastewater. 27 out of 37 bacterial genera detected were exclusively associated to wastewater, and Pseudomonas was constantly the most represented genus. Moreover, isolates were assayed for their resistance against eight different antibiotics and synthetic wastewater (SWW). Data obtained revealed the presence of resistant phenotypes, including multi-drug resistant bacteria, and a general trend regarding the temporal evolution of resistance patterns: indeed, a direct correlation linking the appearance of antibiotic- and SWW-resistance with the time of exposure to wastewater was observed. In particular, nine isolates showed an interesting behavior since their growth was positively affected by the highest concentrations of SWW. Noteworthy, this study is among the few investigating the P. australis microbiota prior to the plant activation.

The objective of this paper is to find the optimum solid retention time (SRT) of a wastewater treatment plant (WWTP), which minimizes operating costs, using a modeling approach with WEST software by MIKE DHI®. For the determination of the kinetic and stoichiometric parameters (used for the correct calibration of the model implemented), respirometric and kinetic batch tests were carried out. Each Oxidation ditch was modeled by a sequence of four aerated activated sludge units (ASUs) and four anoxic ASUs with recirculation. The model is able to simulate the separation efficiency of the secondary settler, which is generally quite low: in fact, the industrial origin of the wastewater induces the formation of small flocs, the dimensions of which can be further reduced by the presence of surface aerators. The nitrification/denitrification process is also accurately predicted. Using data obtained from the model, mass balances at the steady state for COD and N were made and compared to the ones obtained using measured data. After calibration and validation of the model, steady-state simulations were carried out by increasing and decreasing the SRT of the system under two different operational conditions used by the managing company and by evaluating the costs related to the water treatment line and the sludge treatment line for each scenario. It is interesting to note how the total costs are lower in summer than in winter (7.2 €cent/m3 in summer and 8.7 €cent/m3 in winter, in scenario 0). In general, the increase in the SRT led to a decrease in the total management costs. In fact, differences between scenario 0 and the scenario with the lowest total treatment costs (corresponding to an SRT of 11.4 d in winter and 10.0 d in summer) could give rise to total savings of about 44·000€/year in summer and 93·000€/year in winter.

This study focused on the Analytical Quality by Design (AQbD) optimization of the chromatographic separation and mass spectrometric detection of a wide group of structurally heterogeneous model pharmaceutical compounds (PhCs) and transformation products (TPs), chosen to cover the challenging issues of the co-presence of compounds characterized by (i) a wide range of physicochemical properties, (ii) the same mass transitions, and (iii) different ionisation modes. Italian consumption of PhCs were also considered as election criteria of target analytes. Octadecyl and pentafluorophenyl stationary phases, acetonitrile/methanol ratios and acidity of the eluents, column temperature, initial organic phase percentage, and elution gradient were investigated by AQbD, aiming at optimizing critical resolutions, sensitivities, and analysis time. Statistically significant models were obtained in most cases with fitting and cross-validation coefficients in the ranges of 0.681-0.998 and 0.514-0.967, respectively. After optimization, the analysis of target analytes was performed in a single chromatographic run, adopting a mixed acquisition mode based on scheduled acquisition windows comprising both single polarity and continuous polarity switching. For most investigated analytes the method provided detection limits in the sub-ng/L to low ng/L range, meeting for macrolides the sensitivity requested by the "Watch List" 2018/840/EU. The optimized method was applied to the direct injection analysis of PhCs and TPs in four wastewater treatment plant (WWTP) effluents and surface water (SW) samples collected in the receiving water bodies. Absolute values of matrix effect were found to be far higher than 20% for most target analytes in most samples. Seventeen PhCs and two TPs were quantified in at least one sample, at the wide concentration range of about 1-3200 ng/L. The most occurring PhCs in both WWTP effluents and SWs were levofloxacin (202-1239 and 100-830 ng/L), furosemide (865-3234 and 230-880 ng/L), ketoprofen (295-1104 and 270-490 ng/L), and ibuprofen (886-3232 and 690-1440 ng/L).

This paper presents a case study describing a full-scale membrane bioreactor (MBR) for the pretreatment of landfill leachates. The treatment train includes an aerated equalization tank, a denitrification tank, an oxidation/nitrification tank, and two ultrafiltration units. The plant has worked continuously since 2008 treating landfill leachates at a flux of 2&ndash, 11 L&middot, h&minus, 1&middot, m&minus, 2. The old train of membranes worked in these conditions for more than seven years prior to being damaged and replaced. The permeability (K) of the membrane varied between 30 and 80 L&middot, 2&middot, bar&minus, 1 during the years of operation. In 2010, after two years of operation, the oxidation/nitrification tank was changed to work in alternate cycles of aerated and anoxic conditions, in order to improve the denitrification process. The MBR, working at a mean sludge retention time of 144 days and with mixed liquor suspended solids of 17 g/L, achieved high removal rates of conventional contaminants, with more than 98% for Biochemical Oxygen Demand, 96% for ammonium, and 75% for Chemical Oxygen Demand (COD). From the COD balance, half the COD entering was determined to be biologically oxidized into carbon dioxide, while another 24% remains in the sludge. In order to obtain these results, the company used 5.2 KWh&middot, 3, while spending 0.79 &euro, &middot, 3.

A sensitive and reliable analytical method was developed for the simultaneous determination of five phthalate diesters and corresponding monoesters in human milk samples and infant formulas. The method involved a liquid-liquid extraction with a CH2Cl2/CH3OH/NaCl 30% 2/1/0.5 (v/v/v) mixture, the clean-up of the extract by size-exclusion chromatography (swelling and elution solvent: cyclohexane/ethyl acetate 9/1v/v), the derivatization of monoesters by trimethylsilyl-diazomethane and instrumental analysis by gas chromatography coupled with mass spectrometry. Recovery was in the range of 83-115% and precision was found between 9% and 21%. For phthalate diesters, method detection limits (MDLs) ranged from hundreds of ng/kg to 4.2μg/kg on a fresh weight milk (f.w.) basis, depending on blank contribution evaluated in matrix. Lower MDLs (0.03-0.8μg/kg f.w.) were achieved for corresponding monoesters. The proposed method was applied to the determination of target compounds in nine human milk samples and four infant formulas, confirming their presence in all samples. However, a generally higher contamination was assessed in artificial milk than in breast milk samples.

The applicability of a direct injection UHPLC-MS/MS method for the analysis of several perfluoroalkyl acids (PFAAs) in a wide range of water matrices was investigated. The method is based on the direct injection of 100 µL of centrifuged water sample, without any other sample treatment. Very good method detection limits (0.014–0.44 ng L−1) and excellent intra and inter-day precision (RSD% values in the range 1.8–4.4% and 2.7–5.7%, respectively) were achieved, with a total analysis time of 20 min per sample. A high number of samples – i.e. 8 drinking waters (DW), 12 ground waters (GW), 13 surface waters (SW), 8 influents and 11 effluents of wastewater treatment plants (WWTPIN and WWTPOUT) were processed and the extent of matrix effect (ME) was calculated, highlighting the strong prevalence of |ME| 50% was occasionally observed only for perfluorooctanesulphonic and perfluorodecanoic acids. Linear discriminant analysis highlighted the great contribution of the sample origin (i.e. DW, GW, SW, WWTPIN and WWTPOUT) to the ME. Partial least square regression (PLS) and leave-one-out cross-validation were performed in order to interpret and predict the signal suppression or enhancement phenomena as a function of physicochemical parameters of water samples (i.e. conductivity, hardness and chemical oxygen demand) and background chromatographic area. The PLS approach resulted only in an approximate screening, due to the low prediction power of the PLS models. However, for most analytes in most samples, the fitted and cross-validated values were such as to correctly distinguish between | ME | higher than 20% or below this limit. PFAAs in the aforementioned water samples were quantified by means of the standard addition method, highlighting their occurrence mainly in WWTP influents and effluents, at concentrations as high as one hundred of µg L−1.

Epilithic river biofilms characterize the rock surfaces along the Acquarossa river (Viterbo, Italy); they are in part red and in part black colored, maintaining a well-defined borderline. This peculiarity has raised questions about the biotic and abiotic phenomena that might avoid the mixing of the two biofilms. In this study, the structuring of bacterial communities in black and red epilithic biofilm in the Acquarossa river has been investigated with both culture dependent and independent approaches. Data obtained highlighted a (very) different taxonomic composition of black and red epilithons bacterial communities, dominated by Acinetobacter sp. and iron-oxidizing bacteria, respectively. The chemical characterization of both river water and biofilms revealed a substantial heavy metals pollution of the environment; heavy metals were also differentially accumulated in red and black epilithons. Overall, our data revealed that the structuring of red and black epilithons might be affected mainly by the antagonistic interactions exhibited by bacterial genera dominating the two biofilms. These findings suggest that biotic factors might be responsible for the structuring of natural bacterial communities, suggesting that there is a selection of populations at very small scale, and that different populations might compete for different niches.

The applicability of a direct injection UHPLC-MS/MS method for the analysis of several perfluoroalkyl acids (PFAAs) in a wide range of water matrices was investigated. The method is based on the direct injection of 100µL of centrifuged water sample, without any other sample treatment. Very good method detection limits (0.014-0.44ngL

Three biochars were produced using sawdust from waste biomass, via a simple pyrolysis thermal conversion at 450, 650, and 850 °C (BC450, BC650, and BC850), without any activation process. These materials, together with vegetal and mineral commercial activated carbons (VAC and MAC), were characterized for their elemental composition, Brunauer–Emmett–Teller surface area, t-plot microporosity and Barrett-Joyner-Halenda mesoporosity. Moreover, iodine, phenol and methylene blue porosity indexes were measured. The materials were also evaluated for their pH of the point of zero charge, as well as near-surface chemical composition and surface functionality by means of X-ray photoelectron and Fourier-transform infrared spectroscopy. Ash content, water-extractable metals and polycyclic aromatic hydrocarbons (PAHs) were also determined. BC650 showed a much higher surface area (319 m2 g−1) compared to BC450 (102 m2 g−1), as well as an increase in aromatization and the residual presence of functional polar groups. BC850 exhibited a loss of polar and aromatic groups, with the dominance of graphitic carbon and the highest value of surface area (419 m2 g−1). Biochars comply with the EN 12915-1/2009 limits for metal and PAH release in water treatment. Biochars and MAC were tested using Langmuir and Freundlich isotherms for the sorption in real effluent wastewater of a mixture of 14 branched ethoxylated 4-t-octyl and 4-nonylphenols, as well as 4-t-octyl and 4-nonylphenol, the latter representing persistent, endocrine disrupting contaminants, widespread in the effluents from wastewater treatment plants and listed as priority/priority hazardous substances in the Directive 2013/39/EU. Biochars showed a lower sorption efficiency compared to MAC. The best performance was found for BC650 towards the alkylphenols (9–13 times less efficient than the MAC). Considering the lower market price of biochar compared to MAC (estimated as at least 16 times less expensive by a small market survey), the former can be considered more competitive than the latter.

Chromium accumulation, dry weight (DW) biomass yield, water content and concentrations of some selected phenolic compounds and carbohydrates were determined in root and shoot of Nicotiana langsdorffii, either wild type (WT) or genetically modified by the insertion of GR and rolC genes, in response to the presence of Cr(VI) in the growth medium. A biomass decrease was observed for WT plants, but not for GR and rolC transformations, in response to Cr(VI) in the growth medium, highlighting a stress situation only in WT line. Shoot chromium concentrations were in all cases about 300 mg kg−1 DW. In root higher concentrations were found in rolC than in GR and WT (3843, 2600 and 2751 mg kg−1 DW, respectively). Based on the DW biomass, GR and WT accumulated higher chromium quantities than rolC, both in root (330 and 424 versus 85 μg Cr per plant) and shoot (282 and 275 versus 121 μg Cr per plant). Therefore, GR should be preferred to WT as a promising candidate for chromium phytoremediation. Metabolic shifts of sugars and phenolics were generally observed in response to either gene insertions or exposure to Cr(VI), being the latter more related to the resistance to Cr(VI) than the former.

High-performance liquid chromatography coupled with ion spray mass spectrometry in the tandem mode with both negative and positive ionization was used for investigating a variety of polyphenolic compounds in four genotypes of Fragaria vesca berries. About 60 phenolic compounds belonging to the compound classes of phenolic acids, ellagitannins, ellagic acid derivatives, flavonols, monomeric and oligomeric flavanols, dihydrochalcones and anthocyanins were reported, providing for the first time a quite complete picture of polyphenolic composition of F. vesca berries. Some of the polyphenols herein investigated, such as a tris-galloyl-hexahydroxydiphenoyl-hexose, two castalagin/vescalagin-like isomers and peonidin-malonylglucoside, were described for the first time. Principal component analysis applied on original HPLC-MS/MS data, acquired in multiple reaction monitoring mode, successfully discriminated the four investigated cultivars on the basis of their polyphenolic composition, highlighting the fundamental role of mass spectrometry for food characterization. Copyright © 2012 John Wiley & Sons, Ltd.

In this study we investigated total and hexavalent chromium removal in an h-SSF constructed wetland (CW) planted with Phragmites australis and operating as post-treatment of effluent wastewater from an activated sludge plant serving the textile industrial district of Prato (Italy). Two measurement campaigns were carried out in 2006 and 2008–2010 in which more than 950 inlet and outlet samples were analyzed. When inlet and outlet concentrations were compared one to the other, the latter were found to be significantly lower than the former (p < 0.001); during the entire period of investigation, removal of hexavalent chromium equal to about 70% was achieved. Outlet concentrations ranged between values lower than the quantification limit (0.5 μg L−1) and 4.5 μg L−1, and in all cases were therefore lower than the limit indicated for hexavalent chromium in the Italian regulation for water reuse (5 μg L−1). The comparison of the removal efficiencies achieved for hexavalent and trivalent chromium during the two campaigns suggested that the removal of the former can be sustained in the long term, while for the latter, the treatment efficiency is more sensitive to the age of the CW, being that it is it based on trivalent chromium retention in the reed bed.

Individual sugars, organic acids, total polyphenols, vitamin C and antiradical activity (as measured by DPPH method) were quantified in cultivated Fragaria vesca berries, comparing different varieties (Regina delle Valli, Alpine, Sara and Valitutto) and different environments with regard to altitude. Cultivar effect mainly influenced the concentration of total polyphenols and antiradical activity which are strongly correlated (R2 = 0.91; P = 0.001); conversely, altitude seemed to exert an influence in sugar and organic acid composition. The comparison of the general quality of the most diffused cultivar of F. vesca (Regina delle Valli and Alpine) evidenced that both cultivars have the same nutritional properties, whereas Regina delle Valli is better than Alpine from the point of view of total polyphenolic content (716 vs 471 mg catechin/100 g fresh weight) and radical scavenging activity (301 vs 219 ml DPPH solution/100 g fresh weight), thus resulting more attractive from the health protecting attributes point of view. F. vesca berries showed also a concentration of sugars, citric acid, malic acid and total polyphenols much higher than those reported in literature for Fragaria x ananassa.

For the first time QuEChERS extraction of sewage sludge was combined with the automatic solid-phase pre-concentration and purification of the extract (following indicated as SPE) and LC-MS/MS analysis, for the determination of the non-steroidal anti-inflammatory drugs acetylsalicylic acid (ASA), diclofenac (DIC), fenbufen (FEN), flurbiprofen (FLU), ketoprofen (KET), ibuprofen (IBU) and naproxen (NAP), and their metabolites salicylic acid (SAL), 4′-hydroxydiclofenac (4′-HYDIC), 1-hydroxyibuprofen (1-HYIBU), 2-hydroxyibuprofen (2-HYIBU), 3-hydroxyibuprofen (3-HYIBU) and o-desmethylnaproxen (O-DMNAP). Various commercial pellicular stationary phases (i.e. silica gel functionalized with octadecyl, biphenyl, phenylhexyl and pentafluorophenyl groups) were preliminarily investigated for the resolution of target analytes and different sorbent phases (i.e. octyl or octadecyl functionalized silica gel and a polymeric phase functionalized with N-benzylpyrrolidone groups) were tested for the SPE phase. The optimized method involves the QuEChERS extraction of 1 g of freeze-dried sludge with 15 mL of water/acetonitrile 1/2 (v/v), the SPE of the extract with the N-benzylpyrrolidone polymeric phase and the water/acetonitrile gradient elution on the pentafluorophenyl stationary phase at room temperature. Matrix effect was always suppressive and in most cases low, being it ≤20% for ASA, DIC, FLU, KET, IBU, 1-HYIBU, 2-HYIBU, 3-HYIBU, NAP and O-DMNAP, and included in the range of 35–47% for the other analytes. Recoveries were evaluated at three spiking levels, evidencing almost quantitative values for HYIBUs and O-DMNAP; for ASA, SAL and KET the recoveries were included in between 50 and 76%, whereas for the other compounds they ranged from 36% to 55%. The proposed method showed better analytical performances than those so far published, being suitable for target compound determination in real samples from tens of pg g−1 to ng g−1 of freeze-dried sludge, with a total analysis time of 30 min per sample.

Three different sorbents (i.e. endcapped octadecylsilane, octasilane and styrene-N-vinylpiperidinone co-polymer) were investigated in order to develop an on-line solid phase extraction-liquid chromatographic tandem mass spectrometric method (on-line SPE-LC-MS/MS) for the simultaneous analysis of alkylphenols polyethoxylate (AP(n)EOs, n = 1-8) and corresponding monocarboxylate (AP1ECs) and phenolic (APs) metabolites. The endcapped octadecylsilane was selected due to its full compatibility with a chromatographic approach, which allowed the elution of positively and negatively ionisable compounds in two distinct retention time windows, using a water-acetonitrile-tetrahydrofuran ternary gradient and a pellicular pentafluorophenyl column. On this SPE sorbent, the composition of the loading/clean-up solution was then optimized in order to achieve the best recoveries of target analytes. Under the best experimental conditions, the total analysis time per sample was 25 min and method detection limits (MDLs) were in the sub-nanograms per litre to nanograms per litre range (0.0081-1.0 ng L(-1)) for AP(n)EOs with n = 2-8, AP1ECs and APs, whereas for AP1EOs, an MDL of about 50 ng L(-1) was found. Using the mass-labelled compound spiking technique, the method performance was tested on inlet and outlet wastewater samples from three activated sludge treatment plants managing domestic and industrial sewages of the urban areas and the textile district of Prato and Bisenzio valley (Tuscany, Italy); in most cases, apparent recovery percentages approximately in the ranges of 50-110% and 80-120% were found for inlet and outlet samples, respectively. The on-line SPE-LC-MS/MS analysis of wastewater samples highlighted the presence of target analytes at concentrations ranging from few nanograms per litre to thousands nanograms per litre, depending on the compound and matrix analysed. AP2ECs were also tentatively identified in outlet samples.

The occurrence of pharmaceuticals and other hazardous substances in surface waters and drinking water and the long-term exposure may represent a potential risk for both the environment and human health. Many studies have evidenced that conventional technologies used for wastewater treatment do not completely remove pharmaceuticals and personal care products (PPCPs) residues, which can be detected in receiving waters at concentrations ranging from few ng L(-1) until more than μg L(-1). Nanomaterials are of fundamental importance in the current research efforts to develop more efficient water treatment and remediation systems in place of conventional technologies. This review provides a comprehensive overview of the most relevant works available in literature reporting the use of nanosorbents (nanotubes and zeolites), nanofiltration (NF) and advanced oxidation processes (AOPs) for the removal of PPCPs compounds from water and wastewater. The literature review of laboratory- and pilot-scale studies have shown that nanomaterials are promising tools in environmental cleaning processes and water purification, even if more researches are necessary.

Four different pellicular stationary phases (i.e. octadecylsilane, octasilane, Phenyl-Hexyl and pentafluorophenyl) were investigated for the chromatographic resolution of alkylphenols (APs), alkylphenols polyethoxylates (APnEOs) and alkylphenoxy carboxylates (APECs) using mixtures of water and organic solvents (i.e. methanol, acetonitrile and tetrahydrofuran) as eluents, in order to obtain their determination by a single LC-MS/MS run. In fact, alkylphenols and alkylphenoxy carboxylates must be analysed in negative ion mode, whereas alkylphenols polyethoxylates undergo ionisation only in positive ion mode, and therefore, two distinct LC-MS/MS analysis are commonly adopted. The best resolution among the aforementioned target analytes was achieved on the pentafluorophenyl column, eluting with an acidified water-acetonitrile-tetrahydrofuran mixture and using the post column addition of an ammonia solution in methanol for the detection of positively ionisable compounds. Under these optimized chromatographic conditions the investigated compounds were determined via a single chromatographic run, with only one polarity switch, in 15min, achieving the following instrumental detection limits: 600pg for AP1EOs, 0.8-14pg for AP2EOs, 10.4-150pg for APs and 4.4-4.8pg for APECs. The chromatographic method was coupled with solid-phase extraction and clean-up procedures and successfully applied to the analysis of wastewater and surface water samples, highlighting mean concentration ranging from 6ng/L for 4-t-OP1EC to 1434ng/L for 4-NP1121EC, depending on the sample analysed.

Wastewater treatment is an important link in the water cycle that allows for water sanitation and reuse, facilitates energy generation, and allows for the recovery of products from waste. The scientific community has paid significant attention to wastewater treatment, especially from a technical point of view. Extensive literature is available on new technologies, processes, and materials to improve wastewater treatment. However, scant studies have been conducted in the management field focusing on the development of a performance measurement tool that supports plant managers. The current article addresses this literature gap, developing a reporting tool that integrates technical and cost measures and implements it in a large wastewater utility. The tool successfully identifies cause and effect linkages among key plant performance drivers and supports management in finding activities with poor performance and allows them to delay non-relevant measures of control.

A fully-automated on-line solid phase extraction liquid chromatographic/electrospray ionization tandem mass spectrometric method for the analysis of estrone (E1), 17-β-estradiol (β-E2), 17-α-ethinylestradiol (EE2), 17-α-estradiol (α-E2) and estriol (E3) in surface water and wastewater was developed. The method showed a very good linearity from 250 ng/L down to compound specific quantification limits, which were included between 0.25 and 2.00 ng/L. These limits were obtained with 2.5 mL aliquots of injected sample and the total analysis time per sample was slightly less than 10 min. Under these conditions, detection limits were 0.15 ng/L for E1, 0.31 ng/L for β-E2, 0.52 ng/L for EE2, 0.59 ng/L for α-E2 and 0.95 ng/L for E3. The method reliability was tested on different kinds of real samples spiked with the estrogens, obtaining recoveries approximately included between 71 and 95%. The application to samples collected in rivers, lakes and wastewater treatment plants evidenced the presence of the investigated compounds at sub-ng/L or low ng/L concentration levels.

High-performance liquid chromatography coupled with ion spray mass spectrometry in the tandem mode with both negative and positive ionization was used for investigating a variety of polyphenolic compounds in four genotypes of Fragaria vesca berries. About 60 phenolic compounds belonging to the compound classes of phenolic acids, ellagitannins, ellagic acid derivatives, flavonols, monomeric and oligomeric flavanols, dihydrochalcones and anthocyanins were reported, providing for the first time a quite complete picture of polyphenolic composition of F. vesca berries. Some of the polyphenols herein investigated, such as a tris-galloyl-hexahydroxydiphenoyl-hexose, two castalagin/vescalagin-like isomers and peonidin-malonylglucoside, were described for the first time. Principal component analysis applied on original HPLC-MS/MS data, acquired in multiple reaction monitoring mode, successfully discriminated the four investigated cultivars on the basis of their polyphenolic composition, highlighting the fundamental role of mass spectrometry for food characterization.

In this study, during a two-year period, we investigated the fate of hexavalent and trivalent chromium in a full-scale subsurface horizontal flow constructed wetland planted with Phragmites australis. The reed bed operated as post-treatment of the effluent wastewater from an activated sludge plant serving the textile industrial district and the city of Prato (Italy). Chromium speciation was performed in influent and effluent wastewater and in water-suspended solids, at different depths and distances from the inlet; plants were also analyzed for total chromium along the same longitudinal profile. Removals of hexavalent and trivalent chromium equal to 72% and 26%, respectively were achieved. The mean hexavalent chromium outlet concentration was 1.6 ± 0.9 μg l(-1) and complied with the Italian legal limits for water reuse. Chromium in water-suspended solids was in the trivalent form, thus indicating that its removal from wastewater was obtained by the reduction of hexavalent chromium to the trivalent form, followed by accumulation of the latter inside the reed bed. Chromium in water-suspended solids was significantly affected by the distance from the inlet. Chromium concentrations in the different plant organs followed the same trend of suspended solids along the longitudinal profile and were much lower than those found in the solid material, evidencing a low metal accumulation in P. australis.

The influence of repeated applications of tartrate (TAR) and glutamate (GLU) at 50-mmol kg(-1) of soil on Cd, Cu, Pb, and Zn distribution between a contaminated soil and Paulownia tomentosa was investigated. TAR and GLU were applied by a single or a double dosage, the latter carried out with an interval between the two applications of thirty days. The comparison of the differences in mean amounts of metals accumulated in the whole plant at the end of single and double TAR and GLU application experiments indicated the positive effect of repeated GLU applications on the accumulation of Cu, Pb, and Zn by Paulownia tomentosa as compared to untreated controls. A similar effect was not observed for the TAR treatments. When soil treated with either TAR or GLU was compared with untreated controls, no significant effect on heavy-metal concentrations in the soil solution was observed 30 days after treatment, suggesting the absence of an increase of the long-term leaching risk of heavy metals in aquifers and surface waters due to the ligand application. A cost analysis of the treatment is also reported.