Microplastic in marine environment: reworking and optimisation of two analytical protocols for the extraction of microplastics from sediments and oysters.

Marine sediments and sessile biota (i.e. oysters) are nowadays recognised to be affected by microplastic (MP) pollution. NOAA proposes two distinct MP extraction protocols for sandy and bed sediments, which, however, were already demonstrated to suffer from many limitations. Conversely, to what concern oysters, works already published are usually time consuming, requiring a KOH 24-48 h oxidation step. The aim of this study is to show how iterative adaptation of the NOAA protocol allows to extract MPs, included PET, from marine sediments, regardless their characteristics. The method tested on PE-LD/PET/PA/PE-HD is based on density separation and oxidation treatments which were both carefully tuned, obtaining final recoveries higher than 85% for all the micropolymers (100% for PE and PA). Furthermore, a new protocol for the extraction of MPs from oysters was assessed, highlighting its efficacy (recoveries higher than 84% for all the plastics) and time-saving peculiarity. Finally, both protocols were successfully applied in the MPs extraction from real samples from Atlantic Ocean.•The extraction of PE-LD/PET/PA/PE-HD was optimised in sediments (regardless their characteristics) and oysters.•For sediments, density separation and oxidation procedures were carefully optimised.•For oysters, oxidation times were reduced from 24 to 48 h to 1 h.

Innovative combination of QuEChERS extraction with on-line solid-phase extract purification and pre-concentration, followed by liquid chromatography-tandem mass spectrometry for the determination of non-steroidal anti-inflammatory drugs and their metabolites in sewage sludge.

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.

Adsorption of bentazone herbicide onto mesoporous silica: application to environmental water purification.

Within the last few years, the presence of bentazone herbicide has been observed in many water resources. For the first time, removal of bentazone using mesoporous silica was investigated revealing reversible adsorption. The adsorption isotherm was well described using the Freundlich model. The affinity towards bentazone is strongly affected by pH in the range of 2-7, decreasing with the increase of the pH, becoming negligible at the neutrality. Regeneration of the adsorbent was possible, and a recovery as high as 70 % was obtained using CH3OH-NaOH solution. Furthermore, appreciable recovery (47 %) was also obtained using water. Applications on the purification of lake water and wastewaters, both characterized by a significant organic carbon load, spiked with 2 mg L(-1) bentazone were tested, observing removal yields in the range of 61-73 %. Taking advantage of the fast adsorption kinetics observed, an in-flow purification treatment was set-up, with quantitative removal of bentazone from polluted water.

Simple SPE-HPLC determination of some common drugs and herbicides of environmental concern by pulsed amperometry.

In this work the electrochemical behavior of substances of environmental concern [bentazone, atrazine, carbamazepine, phenytoin and its metabolite 5-(4-hydroxyphenyl)-5-phenylhydantoin, HPPH] on a glassy carbon working electrode (Ag/AgCl reference electrode) was studied with the aim to develop a HPLC method coupled with amperometric detection. Constant potential (DC), pulsed amperometric detection modes were studied. For the pulsed mode, several waveforms were set and investigated. Detection conditions were optimized as a function of eluent pH. In order to reduce the limits of detection and to analyze natural water samples, a SPE protocol was optimized to be coupled to the developed procedure. For this aim, five sorbents of different physico-chemical characteristics were tested optimizing a recovery procedure for each of the cartridge evaluated. At the optimized SPE conditions, recoveries were included in the range (R=90.2-100.5% for all the analytes, with excellent reproducibility (<%, n=3). The method detection limits obtained by pulsed amperometry after the SPE protocol (preconcentration factor 100) were 113 ng L(-1) (0.47 nmol L(-1)), 67 ng L(-1) (0.25 nmol L(-1)), 234 ng L(-1) (1.1 nmol L(-1)), for bentazone, HPPH and carbamazepine, respectively. Robustness of the method was assessed for each analyte at a concentration level corresponding to about three times the limit of detection, through the evaluation of intra-day (n=13) and inter-day tests (4 days, n=52). Finally the method was successfully applied for the analysis of a river sample (Po River, Turin, Italy).

Fast low-pressure microwave assisted extraction and gas chromatographic determination of polychlorinated biphenyls in soil samples.

A new technology equipment for low-pressure microwave assisted extraction (usually employed for organic chemistry reactions), recently launched in the market, is used for the first time in environmental analysis for the extraction of commercial technical Aroclor mixtures from soil. Certified reference materials of Aroclor 1260, Aroclor 1254 and Aroclor 1242 in transformer oils were used to contaminate the soil samples and to optimize the extraction method as well as the subsequent gas chromatographic electron capture detection (GC-ECD) analytical method. The study was performed optimizing the extraction, the purification and the gas chromatographic separation conditions to enhance the resolution of difficult pairs of congeners (C28/31 and C141/179). After optimization, the recovery yields were included within the range 79-84%. The detection limits, evaluated for two different commercial polychlorinated biphenyl (PCB) mixtures (Aroclor 1260 and Aroclor 1242) were 0.056 ± 0.001 mg/kg and 0.290 ± 0.006 mg/kg, respectively. The method, validated with certified soil samples, was used to analyze a soil sample after an event of failure of a pole-mounted transformer which caused the dumping of PCB contaminated oil in soil. Moreover, the method provides simple sample handling, fast extraction with reduced amount of sample and solvents than usually required, and simple purification step involving the use of solvent (cyclohexane) volumes as low as 5 mL. Reliability and reproducibility of extraction conditions are ensured by direct and continuous monitoring of temperature and pressure conditions.