Biochar from co-pyrolysis of biological sludge and woody waste followed by chemical and thermal activation: end-of-waste procedure for sludge management and biochar sorption efficiency for anionic and cationic dyes.

Nine biochars were produced by co-pyrolysis of sawdust and biological sludge following the "design of experiment" approach. Two kinds of sludge (both deriving from the treatment of mixed industrial-municipal wastewater) and two types of woody waste were selected as categorical predicting variables, while contact time, pyrolysis temperature, and sludge percentage were used as quantitative variables. Biochars were analysed for their product characteristics and environmental compatibility based on the European Standards (EN 12915-1:2009) for materials intended for water treatment (i.e. ash content, water leachable polycyclic aromatic hydrocarbons (PAHs) and elements), as well as for specific surface area (SSA), using them as response variables of a multivariate partial least square multiple regression, whose results provided interesting insights on the relationships between pyrolysis conditions and biochar characteristics. Biochars produced with sludge and/or providing the highest SSA values (258-370 m2 g-1) were selected to undergo a sustainable chemical treatment using a by-product of the gasification of woody biomass, complying in all cases with European Standards and achieving therefore the end-of-waste status for sewage sludge. The biochar deriving from the highest percentage of sludge (30% by weight) and with the highest SSA (390 m2 g-1) was thermally activated achieving SSA of 460 m2 g-1 and then tested for the sorption of direct yellow 50 and methylene blue in ultrapure water and real wastewater, compared to a commercial activated carbon (AC). The biochar showed Langmuir sorption maxima (Qm) 2-9 times lower than AC, thus highlighting promising sorption performances. Qm for methylene blue in wastewater (28 mg‧g-1) was confirmed by column breakthrough experiments.

Determination of hexavalent chromium in textiles of daily use by ion chromatography and dermal risk assessment.

The determination of hexavalent chromium in textiles and clothes is challenging since during extraction, the original oxidation state should not be altered. Since, as a matter of fact, current analytical methods are focused only on total chromium determination, the purpose of this research is to develop a reliable analytical method for the determination of Cr(VI) in textiles and tissues of daily use for a reliable application of risk analysis models, which are usually based on total Cr data. After optimization, a 0.0025 M Na3PO4 extraction solution was selected for the extraction of Cr(VI) from textiles. This solution minimizes possible interconversion redox reactions and interference, and provides good extraction recoveries (88.4 ± 2.5% - 105.5 ± 0.6 %, according to Cr(VI) concentration) and quantitation limits (0.017 mg/kg), fully complying the current limits set for Cr(VI) in textiles in contact with skin, and for leachable Cr(VI). The developed method was validated investigating intra-day repeatability (n = 10) and inter-day repeatability (n = 30) which were below 12%, and matrix effect which was below 6% confirming the precision of the method and the negligibility of a matrix interference during the whole analysis. The method, which was proved to be suited also for bioaccessibility studies in saliva and sweat, was applied to the analysis of tank top, coloured paper napkin, polyamide tights, panties, highlighting Cr(VI) content in the panties only at very low concentration (0.028 mg/kg). As verified by ECHA and US EPA approaches, this amount does not pose a non-carcinogenic risk for human health. As regards carcinogenic risk, considering both adult and child exposure, the dermal contact with the panties poses an acceptable risk (R ≤ 10-6).

Innovative thermally assisted on-line solid phase extraction-reversed phase liquid chromatography applied to targeted nutrimetabolomics in human biofluids.

In this study, the use of thermal desorption in on-line solid phase extraction coupled with reversed phase liquid chromatography (on-line SPE-LC) was for the first time proposed and demonstrated for the desorption of analytes strongly retained by multiple interaction polymeric sorbents. In detail, this analytical strategy was applied to the on-line SPE-LC targeted analysis of a model set of 34 human gut metabolites characterized by heterogeneous physicochemical properties (i.e., octanol-water partition coefficient in the range -0.3 - 3.4). The novel thermally assisted on-line SPE approach was investigated in comparison to conventional room temperature desorption strategies based on the use of (i) an optimized elution gradient or (ii) organic desorption followed by post-cartridge dilution. The thermally assisted desorption strategy has been shown to be better performing and suitable for the development of a reliable and sensitive method for the analysis of the model group of analytes in urine and serum. In more detail, under the optimized experimental conditions, the proposed method provided negligible matrix effects in both biofluids for almost all target analytes. Moreover, method quantification limits were in the ranges 0.026-7.2 µg L-1 and 0.033-23 µg L-1 for urine and serum, respectively, i.e., comparable to or lower than those reported in methods previously published.

Feasibility of a Heterogeneous Nanoscale Zero-Valent Iron Fenton-like Process for the Removal of Glyphosate from Water.

Glyphosate is a widely used herbicide, and it is an important environmental pollutant that can have adverse effects on human health. Therefore, remediation and reclamation of contaminated streams and aqueous environments polluted by glyphosate is currently a worldwide priority. Here, we show that the heterogeneous nZVI-Fenton process (nZVI + H2O2; nZVI: nanoscale zero-valent iron) can achieve the effective removal of glyphosate under different operational conditions. Removal of glyphosate can also take place in the presence of excess nZVI, without H2O2, but the high amount of nZVI needed to remove glyphosate from water matrices on its own would make the process very costly. Glyphosate removal via nZVI--Fenton was investigated in the pH range of 3-6, with different H2O2 concentrations and nZVI loadings. We observed significant removal of glyphosate at pH values of 3 and 4; however, due to a loss in efficiency of Fenton systems with increasing pH values, glyphosate removal was no longer effective at pH values of 5 or 6. Glyphosate removal also occurred at pH values of 3 and 4 in tap water, despite the occurrence of several potentially interfering inorganic ions. Relatively low reagent costs, a limited increase in water conductivity (mostly due to pH adjustments before and after treatment), and low iron leaching make nZVI-Fenton treatment at pH 4 a promising technique for eliminating glyphosate from environmental aqueous matrices.

Simultaneous Determination of Steroids and NSAIDs, Using DLLME-SFO Extraction and HPLC Analysis, in Milk and Eggs Collected from Rural Roma Communities in Transylvania, Romania.

This research aims to determine five steroids and four non-steroidal anti-inflammatory drugs in milk and egg samples collected from rural Roma communities in Transylvania, Romania. Target compounds were extracted from selected matrices by protein precipitation, followed by extract purification by dispersive liquid-liquid microextraction based on solidification of floating organic droplets. The extraction procedure was optimized using a 24 full factorial experimental design. Good enrichment factors (87.64-122.07 milk; 26.97-38.72 eggs), extraction recovery (74.49-103.76% milk; 75.64-108.60% eggs), and clean-up of the sample were obtained. The method detection limits were 0.74-1.77 µg/L for milk and 2.39-6.02 µg/kg for eggs, while the method quantification limits were 2.29-5.46 µg/L for milk and 7.38-18.65 µg/kg for eggs. The steroid concentration in milk samples was

Microwave-assisted extraction and gas chromatographic determination of thirty priority micropollutants in biowaste fraction derived from municipal solid waste for material recovery in the circular-economy approach.

European and national waste directives prioritize recycling of wastes, as well as material and energy recovery from wastes themselves. Bio-waste fraction can be converted into new resources whose quality is strictly dependent upon that of waste feedstock. Methods to evaluate the contamination from organic micropollutants in bio-waste are rarely investigated. The aim of this work was to develop an innovative analytical method for the extraction and quantification of 16 polycyclic aromatic hydrocarbons (PAHs) and 14 polychlorinated biphenyls (PCBs, including dioxin-like compounds) in bio-waste. Through a full-factorial experimental design, a microwave-assisted extraction technique was optimized to extract the thirty targeted micropollutants, studying the effect of cyclohexane and dichloromethane as extraction solvents with or without acetone, and of extraction temperature. Purification of the extract was obtained by a silica-based solid-phase extraction cartridge, followed by a sulfuric acid treatment. The analysis was carried out by gas chromatography coupled with mass spectrometry. The optimized method, validated directly in the bio-waste matrix fortified with isotopically marked surrogates, is characterized by good extraction recoveries, included within 47 and 106% (relative standard deviations <10%), by satisfactory intra-day (<1.1%) and inter-day (<9.3%) precision, and by low matrix effect (<17%), despite the complexity of the matrix. The optimized procedure, applied to the analysis of PAHs and PCBs in a bio-waste sample collected from a local anaerobic digestion and composting plant, showed a total PAHs content of 562 µg/kg. As regards PCBs, the dioxin-like congener PCB 118 was the only compound quantified (25 ± 6 µg kg-1).

Biochars intended for water filtration: A comparative study with activated carbons of their physicochemical properties and removal efficiency towards neutral and anionic organic pollutants.

Seven biochars (BCs) obtained from pyrolysis or gasification of different vegetal feedstocks were thoroughly characterized in comparison with three commercial activated carbons (ACs) routinely used in drinking water treatment plants. BCs and ACs characterization included the determinations of ash, iodine and methylene blue adsorption indexes, and the release of metals and polycyclic aromatic hydrocarbons, which were performed according to international standards applied for adsorption media to be used in drinking waters. Total specific surface area, micropore and mesopore specific surface area, pH of the point of zero charge, and the release of polychlorinated biphenyls were also determined in all chars. Principal component analysis and cluster analysis were performed in order to summarize the complex set of information deriving from the aforementioned characterizations, highlighting the BC most similar (BC6 from high temperature gasification of woody biomass) and most different (BC7 from low-temperature pyrolysis of corn cob) from ACs. These BCs were studied for their adsorption in ultrapure water towards diiodoacetic acid (an emergent disinfection by-product), benzene, and 1.2-dichlorobenzene, in comparison with ACs, and results obtained were fitted by linearized Freundlich equation. Overall, BC6 showed higher sorption performances compared to BC7, even though both BCs were less performing sorbents than ACs. However, the sorption properties of BCs were maintained also in real water samples collected from drinking water treatment plants.

A Review on the Degradation of Pollutants by Fenton-Like Systems Based on Zero-Valent Iron and Persulfate: Effects of Reduction Potentials, pH, and Anions Occurring in Waste Waters.

Among the advanced oxidation processes (AOPs), the Fenton reaction has attracted much attention in recent years for the treatment of water and wastewater. This review provides insight into a particular variant of the process, where soluble Fe(II) salts are replaced by zero-valent iron (ZVI), and hydrogen peroxide (H2O2) is replaced by persulfate (S2O82-). Heterogeneous Fenton with ZVI has the advantage of minimizing a major problem found with homogeneous Fenton. Indeed, the precipitation of Fe(III) at pH > 4 interferes with the recycling of Fe species and inhibits oxidation in homogeneous Fenton; in contrast, suspended ZVI as iron source is less sensitive to the increase of pH. Moreover, persulfate favors the production of sulfate radicals (SO4•-) that are more selective towards pollutant degradation, compared to the hydroxyl radicals (•OH) produced in classic, H2O2-based Fenton. Higher selectivity means that degradation of SO4•--reactive contaminants is less affected by interfering agents typically found in wastewater; however, the ability of SO4•- to oxidize H2O/OH- to •OH makes it difficult to obtain conditions where SO4•- is the only reactive species. Research results have shown that ZVI-Fenton with persulfate works best at acidic pH, but it is often possible to get reasonable degradation at pH values that are not too far from neutrality. Moreover, inorganic ions that are very common in water and wastewater (Cl-, HCO3-, CO32-, NO3-, NO2-) can sometimes inhibit degradation by scavenging SO4•- and/or •OH, but in other cases they even enhance the process. Therefore, ZVI-Fenton with persulfate might perform unexpectedly well in some saline waters, although the possible formation of harmful by-products upon oxidation of the anions cannot be ruled out.

Characterization Techniques as Supporting Tools for the Interpretation of Biochar Adsorption Efficiency in Water Treatment: A Critical Review.

Over the past decade, biochar (BC) has received significant attention in many environmental applications, including water purification, since it is available as a low-cost by-product of the energetic valorisation of biomass. Biochar has many intrinsic characteristics, including its porous structure, which is similar to that of activated carbon (AC), which is the most widely used sorbent in water treatment. The physicochemical and performance characteristics of BCs are usually non-homogenously investigated, with several studies only evaluating limited parameters, depending on the individual perspective of the author. Within this review, we have taken an innovative approach to critically survey the methodologies that are generally used to characterize BCs and ACs to propose a comprehensive and ready-to-use database of protocols. Discussion about the parameters of chars that are usually correlated with adsorption performance in water purification is proposed, and we will also consider the physicochemical properties of pollutants (i.e., Kow). Uniquely, an adsorption efficiency index BC/AC is presented and discussed, which is accompanied by an economic perspective. According to our survey, non-homogeneous characterization approaches limit the understanding of the correlations between the pollutants to be removed and the physicochemical features of BCs. Moreover, the investigations of BC as an adsorption medium necessitate dedicated parallel studies to compare BC characteristics and performances with those of ACs.

Amino groups modified SBA-15 for dispersive-solid phase extraction in the analysis of micropollutants by QuEchERS approach.

In the analysis of contaminants in food products, sample preparation is performed by proper adsorbents, whose choice is crucial to eliminate matrix interference. In this work we modified SBA-15 adsorbents by functionalization with (3-aminopropyl)-triethoxysilane (SBA-15-APTES) and N-[3-(trimethoxysilyl)propyl]aniline (SBA-15-AN) aiming to use them for the first time in the clean-up step of a QuEChERS (quick, easy, cheap, effective, rugged and safe) extraction of micropollutants from strawberry, a sugar rich fruit. After physico-chemical characterization by nitrogen adsorption, infrared spectroscopy and thermogravimetric analysis, the adsorption capabilities of SBA-15 sorbents and possible interaction mechanisms were studied at different pH (2.1-8.5) for glucose, sucrose and fructose at concentrations characteristic of those found in strawberries. The performance of the two SBA-15 sorbents was compared with that of commercial PSA (primary secondary amine), usually proposed in QuEChERS protocols. Both SBA-15 materials exhibit up to 30% higher adsorption than PSA, suggesting their possible QuEChERS application. Synthesized SBA-15 adsorbents were hence used as innovative dispersive sorbents in the QuEChERS extractions of 13 PAHs and 14 PCBs from strawberry. For PCBs, SBA-15-AN provides better matrix removal than PSA and comparable extraction recoveries around 90%. For PAHs, the use of SBA-15-AN has the advantage of lower relative standard deviation (7%) than PSA (19%).

Optimization and validation of a method based on QuEChERS extraction and liquid chromatographic-tandem mass spectrometric analysis for the determination of perfluoroalkyl acids in strawberry and olive fruits, as model crops with different matrix characteristics.

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).

Extraction of Polycyclic Aromatic Hydrocarbons and Polychlorinated Biphenyls from Urban and Olive Mill Wastewaters Intended for Reuse in Agricultural Irrigation.

BACKGROUND: Domestic and industrial wastewater can be introduced in a reuse chain for irrigation purposes. OBJECTIVE: In this paper, we developed analytical procedures for the extraction of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) along a wastewater reuse chain for irrigation purposes. Besides urban wastewaters, olive mill wastewater (OMWW) was considered as a potential water source. Wastewaters were purified by different treatments (urban wastewater plants, pilot-activated sludge, and constructed wetland) and used for the irrigation of olive trees. Suitable extraction procedures were used to analyze treated and untreated wastewaters, soils, and postirrigation leachates. RESULTS: For wastewater and leachate samples, the optimized reverse-phase solid-phase extraction (SPE) provided recoveries up to 79%. For OMWW, the SPE procedure was preceded by a normal-phase purification stage with silica gel for the removal of polyphenols, which were as high as 8.7 g/L. After optimization, extraction recoveries in blank solutions were in the range 20-67% and moderately reduced (10-38%) in OMWW as a result of the matrix effect (ME; -10/-60%) ascribed to the very high value of chemical oxygen demand (264 g/L). LODs of the method were below 1.1 µg/L (PAHs) and 3.2 µg/L (PCBs) using GC-MS analysis. For soil samples of different compositions, microwave-assisted extraction (MAE) provided better extraction recoveries and reproducibility than the more common quick, easy, cheap, effective, rugged, and safe approach, which was affected by a high ME. The LODs of the MAE/GC-MS method were below 4.9 µg/kg (PAHs) and 12.3 µg/kg (PCBs). CONCLUSIONS: The analytical procedures developed are a valuable tool to quantify the possible propagation of residual contamination from PAHs/PCBs with irrigation along the wastewater reuse chain.

Physicochemical properties and sorption capacities of sawdust-based biochars and commercial activated carbons towards ethoxylated alkylphenols and their phenolic metabolites in effluent wastewater from a textile district.

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.

Towards the revision of the drinking water directive 98/83/EC. Development of a direct injection ion chromatographic-tandem mass spectrometric method for the monitoring of fifteen common and emerging disinfection by-products along the drinking water supply chain.

According to the recent proposal released by the European Commission for the revision of the 98/83/EC Directive, water suppliers will be requested to monitor the nine bromine- and chlorine congeners of haloacetic acids, HAAs, as well as the oxyhalides chlorite and chlorate, as disinfection by-products (DBPs) originated during the potabilization process. In this work, we propose a direct-injection method based on ion chromatography and mass spectrometric detection for the determination of the mentioned DBPs as well as bromate (already included in the 98/83/EC), implemented also for the following emerging HAAs monoiodo-, chloroiodo- and diiodo-acetic acids. The method was optimized to include the fifteen compounds in the same analytical run, tuning the chromatographic (column and gradient) and detection conditions (suppression current, transitions, RF lens settings and collision energies). To avoid matrix effect and to manage the instrumental conditions, optimization was performed directly in drinking water matrix. The method quantitation limits satisfy the new limits imposed by the future directive and range from 0.08 µg/L (monobromoacetic acid) to 0.34 µg/L (trichloroacetic acid). The performance of the method was checked along different strategic sampling points of three potabilization plants serving the city of Turin (Italy), including intermediate treatments and finished waters. Recovery was checked according to the ±30% limit of acceptability set by EPA regulations. The effect of disproportionate concentrations of chlorite and chlorate in respect to HAAs on HAA signals was studied; this aspect is underestimated in literature. The method is routinely applied by the potabilization plant of the city of Turin to confirm the effectiveness of all control measures in abstraction, treatment, distribution and storage. This study represents the first example in Italy of development and use of a cutting-edge technique for HAAs analysis along the potabilization processes.

Chromatographic determination of biogenic amines in four typical Italian cheeses: correlations with processing and nutritional characteristics through a chemometric approach.

BACKGROUND: The presence of biogenic amines (BAs) fermented food is well known. They may affect food quality, posing health risks. In this work, four typical Italian cheeses, exported worldwide, were analyzed to determine the possible presence of BAs. The cheese samples were analyzed untreated and having been subjected to common or incorrect consumer handling (domestic grating, unrefrigerated storage). RESULTS: A chromatographic-amperometric method was developed and validated. Extraction of BAs was performed by the addition of eluent, determining matrix effect and recovery of biogenic amines directly within the cheeses. Biogenic amines were present in the range of 0.019-0.044 g kg-1 , well below the current EU limit. Home-manipulation confirmed recontamination of the cheese. The contents of BAs were correlated with the main processing parameters and with the nutritional properties of the four cheeses through the multivariate statistical analysis (principal component analysis). This is believed to be the first study that presents these correlations. CONCLUSION: This study highlights correlations among BAs and carbohydrates, and anticorrelations with pH and, to a lesser extent, with moisture. Interestingly, BAs are correlated with fat content. This correlation was confirmed by a new principal component analysis performed on our data set with additional data from the literature. © 2019 Society of Chemical Industry.

Removal efficiency and mass balance of polycyclic aromatic hydrocarbons, phthalates, ethoxylated alkylphenols and alkylphenols in a mixed textile-domestic wastewater treatment plant.

In this work the occurrence and fate of polycyclic aromatic hydrocarbons (PAHs), phthalic acid esters (PAEs), mono and diethoxylate alkylphenols (AP1-2EOs) and alkylphenols (APs) have been investigated during a two-weeks period in a facility treating mixed textile-domestic wastewater (Prato, Italy). The wastewater treatment plant (WWTP) consists of primary sedimentation, activated sludge biological oxidation, secondary sedimentation, clariflocculation and ozonation. The sludge is treated within the facility by thickening, dewatering and final incineration, thus providing the almost quantitative removal of the adsorbed micropollutants. Naphthalene (50%), di(2-ethylhexyl) phthalate (74%) and branched 4-nonylphenols (59%) were the individual main representative compounds of each class in the influent wastewater, which showed concentration ranges of 5.6-66, 85-290 and 21-133µg/L for PAHs, PAEs and APs+AP1-2EOs, respectively. The WWTP efficiently removed PAHs, PAEs and APs+AP1-2EOs, providing effluent concentrations of 0.075-0.16ng/L 0.38-9.9µg/L and 0.53-1.4µg/L. All targeted priority and priority-hazardous micropollutants showed effluent concentrations in line with the European environmental quality standards (EQS), even though for di(2-ethylhexyl) phthalate and benzo(a)pyrene after correction for the dilution factor of the recipient. The WWTP performance was evaluated by mass balance, verifying its accuracy by monitoring Pb and Cd as conservative species. The biological treatment sections provided mass losses of 85.5%, 74.5% and 56.8% for APs+AP1-2EOs, PAEs and PAHs, highlighting efficient biotransformation performances of the activated sludge process. However, for the more volatile PAHs (e.g. naphthalene), a significant contribution of stripping cannot be excluded. A remarkable mass loss was also determined in the ozonation stage for PAEs (72.9%) and especially PAHs (97.0%), whereas a lower efficiency was observed for APs+AP1-2EOs (41.3%). The whole plant allowed for obtaining an almost quantitative removal (96.7-98.4%) for all targeted compounds.

Regenerable, innovative porous silicon-based polymer-derived ceramics for removal of methylene blue and rhodamine B from textile and environmental waters.

The presence of residual color in treated textile wastewater above the regulation limits is still a critical issue in many textile districts. Innovative, polymer-derived ceramics of the Si-C-O system were here synthesized in order to obtain porous nanocomposite materials where a free carbon phase is dispersed into a silicon carbide/silicon oxycarbide network. The sorbents were comprehensively characterized for the removal of two model water-soluble dyes (i.e., the cation methylene blue and the zwitterion rhodamine B). Adsorption is very rapid and controlled by intra-particle and/or film diffusion, depending on dye concentration. Among the nanocomposites studied, the SiOC aerogel (total capacity about 45 mg/g, is easily regenerated under mild treatment (250 °C, 2 h). Adsorption of dyes is not affected by the matrix composition: removals of 150 mg/L methylene blue from river water and simulated textile wastewater with high content of metal ions (2-50 mg/L) and chemical oxygen demand (800 mg/L) were higher than 92% and quantitative for a dye concentration of 1 mg/L.

Applicability of the direct injection liquid chromatographic tandem mass spectrometric analytical approach to the sub-ngL-1 determination of perfluoro-alkyl acids in waste, surface, ground and drinking water 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 100µL of centrifuged water sample, without any other sample treatment. Very good method detection limits (0.014-0.44ngL-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 20min 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| < 20%. The occurrence 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 µgL-1.

Chromium, nickel, and cobalt in cosmetic matrices: an integrated bioanalytical characterization through total content, bioaccessibility, and Cr(III)/Cr(VI) speciation.

The presence of certain metals naturally contained inside raw materials (e.g., pigments) used to produce cosmetics for make-up may represent a serious concern for the final quality and safety of the product. The knowledge of the total concentration of metals is not sufficient to predict their reactivity and their toxicological profile. For these reasons, we set up a comprehensive approach to characterize the content of Co, Cr, and Ni in two raw materials for cosmetic production, a black iron oxide and a pearly pigment, and in a finished product, pearly powder eye shadow. Namely, besides the total metal concentrations, the speciation of chromium and the bioaccessibility of the three metals were assessed. Since no standard method is so far available for hexavalent chromium extraction from cosmetic samples, three approaches were compared (EPA 3060A method, IRSA 16 method, and a Na3PO4 extraction). Results show that Na3PO4 extraction is the most selective one. Cr(VI) was undetectable in black iron oxide and present at very low concentrations (about 0.3 mg/kg) in pearly pigment and in the pearly powder eye shadow samples. The extracted Cr(VI) concentrations are not related to the total Cr content in the samples. Bioaccessibility studies were performed by in vitro extractions with synthetic lacrimal fluids and sweat. Despite the wide range of metal concentrations in the samples, the amounts of bioaccessible elements were undetectable or very low (less than 0.4 mg/kg), thus suggesting that metals in the three samples are present in inert forms. Graphical abstract The possible leaching of metals from cosmetics to biological fluids. Spectroscopic and chromatographic techniques provide complementary information for an integrated bioanalytical approach to risk characterization.

New approaches for extraction and determination of betaine from Beta vulgaris samples by hydrophilic interaction liquid chromatography-tandem mass spectrometry.

Betaine is one of most studied biologically active compounds, due its role in the main biological processes. Although it may be found in several plants and roots, such as the Beta vulgaris family, present in typical diets, just a few analytical methods have been developed for its extraction from roots. A new, quick and effective procedure for the isolation and determination of betaine from two different varieties of B. vulgaris (red and gold) is presented. For betaine extraction, an accelerated solvent extraction (ASE) was coupled with solid-phase extraction. For betaine determination, a separation method based on hydrophilic interaction chromatography coupled with tandem mass spectrometry was optimized for a sensible detection of betaine by means of experimental design. Recoveries were about 93%, with RSD <5%, for both the matrices, without evidence of interfering species. The total content of betaine in extracts of various parts of plants (juice, peel, root) have been determined, obtaining concentrations in the range 3000-4000 mg/L for the juice and in the range 2-5 mg/g for the pulp and for the peel. The B. vulgaris gold species exhibited a higher concentration of betaine, compared to the red variety. Additionally, a micro extraction by packed sorbent technique and a modified quick, easy, cheap, rugged and safe (QuEChERS) procedure, were also tested and compared. Despite the lower recoveries of the latter, with respect to the ASE/SPE procedure (75-89%, RSD <1.5%), the ease of the method, which can be applied without the SPE purification procedure, can represent a positive improvement. Graphical abstract Determination of betaine from Beta vulgaris samples.