Wastewater and seawater monitoring in Antarctica: Passive sampling as a powerful strategy to evaluate emerging pollution.

The Ross Sea, among the least human-impacted marine environments worldwide, recently became the first marine protected area in Antarctica. To assess the impact of the Italian research station Mario Zucchelli (MZS) on the surrounding waters, passive sampling - as well as spot sampling for comparison - took place in the effluent of the wastewater treatment plant (WWTP) and the receiving surface marine waters. Polar Organic Chemical Integrative Samplers (POCIS) were deployed for six consecutive 2-week periods from November to February in a reservoir collecting the wastewater effluent. Passive samplers were also deployed at shallow depth offshore from the wastewater effluent outlet from MZS for two separate 3-week periods (November 2021 and January 2022). Grab water samples were collected alongside each POCIS deployment, for comparison with passive sampling results. POCIS, used for the first time in Antarctica, demonstrated to be advantageous to estimate time-averaged concentrations in waters and the results were comparable to those obtained by repeated spot samplings. Among the 23 studied ECs - including drugs, UV-filters, perfluorinated substances, caffeine - 15 were detected in both grab and passive sampling in the WWTP effluent and followed similar concentration profiles in both types of sampling. High concentrations of caffeine, naproxen and ketoprofen in the dozens of µg L-1 were detected. Other compounds, including drugs and several UV filters, were detected down to sub- µg L-1 concentrations. In marine waters close to the effluent output, only traces of a drug (4.8 ng L-1) and two UV filters (up to 0.04 µg L-1) were quantified.

Polar licit and illicit ingredients in dietary supplements: chemometric optimization of extraction and HILIC-MS/MS analysis.

Many dietary supplements claim the ability to enhance sports performance and to improve the fitness of the consumers. Occasionally, along with legal ingredients, illicit compounds may be added without being labelled, leading to unintended doping. Hence, the aim of this study was to develop an analytical method to determine a set of 12 polar (logDpH=7 from -2.0 to +0.3) compounds including diuretics, stimulants, ß2-agonists, methylxanthines, and sweeteners. Hydrophilic interaction liquid chromatography was chosen as separation strategy, coupled with tandem mass spectrometry. The instrumental method was optimized using a two-step design of experiments (DoE). Firstly, a Plackett-Burman (PB) DoE was performed to identify the more influencing variables affecting peak areas and chromatographic resolution among temperature, water percentage in the mobile phase, and flow rate, as well as type and concentration of buffers. Secondly, a D-optimal DoE was set, considering only the most significant variables from the PB-DoE results, achieving a deeper understanding of the retention mechanism. Sample processing by salt-assisted liquid-liquid extraction was studied through DoE as well, and the whole method showed recoveries in the range 40-107% and procedural precision ≤11% for all analytes. Finally, it was applied to real samples, in which the four methylxanthines and two artificial sweeteners were detected and quantified in the range of 0.02-192 mg g-1. These values were compared to the quantities declared on the DS labels, when possible. Furthermore, a sequence of MS/MS scans allowed detection of a signal in one of the samples, structurally similar to the ß2-agonist clenbuterol.

Determination of polycyclic aromatic hydrocarbons in bud-derived supplements by magnetic molecular imprinted microparticles and GC-MS: D-optimal design for a fast method optimization.

Within the world of natural food supplements, organic extracts deriving from young plant meristematic tissue (bud-derivatives) are becoming attractive, thanks to their richness in bioactive molecules. This natural source is scarce, but every year, tons of plant material, including buds, come from city pruning. If this sustainable source is rather promising from a circular economy point of view, the safety of the obtained supplements must be assessed. In fact, anthropic microcontaminants, such as polycyclic aromatic hydrocarbons (PAHs), could adsorb onto the urban buds, leading to a possible contamination of the bud-derivatives. In this study, we developed a magnetic dispersive solid phase extraction (m-dSPE) based on molecularly imprinted microparticles, combined with GC-MS, to quantify the 16 priority PAHs in such extracts. The D-optimal experimental design was implemented to maximize analytes' recovery with the smallest set of experiments. The optimized method was characterized by great selectivity thanks to the molecular imprinted polymer and ease of use provided by m-dSPE. Moreover, it complies with green principles, thanks to the minimum consumption of organic solvent (1.5 mL of acetone per sample). The recoveries ranged from 76 to 100% and procedural precision was below 10% for most PAHs. Despite the matrix complexity, low quantification limits (0.7-12.6 µg kg-1) were reached. This guaranteed the PAHs' quantitation at levels below those indicated as safe by a European Community regulation on food supplements. None of the analyzed samples, coming from different anthropically impacted areas, showed concerning PAHs levels.

Solvent-Free Determination of Selected Polycyclic Aromatic Hydrocarbons in Plant Material Used for Food Supplements Preparation: Optimization of a Solid Phase Microextraction Method.

The exploitation of waste and by-products in various applications is becoming a cornerstone of the circular economy. A range of biomasses can be employed to produce food supplements. An example is a particular extract obtained from plant buds (rich in bioactive molecules), which can be easily retrieved from cities' pruning. In order to safely use this material, its possible contamination by organic pollutants needs to be estimated. A green and simple method to detect priority polycyclic aromatic hydrocarbons (PAHs) in bud samples by head space solid phase microextraction coupled to GC-MS was developed. This strategy, optimized through experimental design and response surface methodology, requires a minimal sample pre-treatment and negligible solvent consumption. The final method was found to be accurate and sensitive for PAHs with mass up to 228 Da. For these analytes, satisfactory figures of merit were achieved, with detection limits in the range 1-4 ng g-1, good inter-day precision (relative standard deviation in the range 4-11%), and satisfactory accuracy (88-105%), along with specificity guaranteed by the selected ion monitoring detection. The method was applied to bud samples coming from differently polluted areas, thus helping in estimating the safety of their use for the production of food supplements.

Using integrative samplers to estimate the removal of pharmaceuticals and personal care products in a WWTP and by soil aquifer treatment enhanced with a reactive barrier.

The need and availability of freshwater is a major environmental issue, aggravated by climate change. It is necessary to find alternative sources of freshwater. Wastewater could represent a valid option but requires extensive treatment to remove wastewater-borne contaminants, such as contaminants of emerging concern (CECs). It is urgent to develop not only sustainable and effective wastewater treatment techniques, but also water quality assessment methods. In this study, we used polar organic chemical integrative samplers (POCIS) to investigate the presence and abatement of contaminants in an urban wastewater treatment plant (WWTP) and in soil aquifer treatment (SAT) systems (a conventional one and one enhanced with a reactive barrier). This approach allowed us to overcome inter-day and intraday variability of the wastewater composition. Passive sampler extracts were analyzed to investigate contamination from 56 pharmaceuticals and personal care products (PPCPs). Data from the POCIS were used to estimate PPCPs' removal efficiency along the WWTP and the SAT systems. A total of 31 compounds, out of the 56 investigated, were detected in the WWTP influent. Removal rates along WWTP were highly variable (16-100 %), with benzophenone-3, benzophenone-1, parabens, ciprofloxacin, ibuprofen, and acetaminophen as the most effectively removed chemicals. The two SAT systems yielded much higher elimination rates than those achieved through the primary and secondary treatments together. The SAT system that integrated a reactive barrier, based on sustainable materials to promote enhanced elimination of CECs, was significantly more efficient than the conventional one. The removal of the recalcitrant carbamazepine and its epoxy- metabolite was especially remarkable in this SAT, with removal rates between 69-81 % and 63-70 %, respectively.

A Review on Polyethersulfone Membranes in Polar Organic Chemical Integrative Samplers: Preparation, Characterization and Innovation.

The membranes in polar organic chemical integrative samplers (POCIS) enclose the receiving sorbent and protect it from coming into direct contact with the environmental matrix. They have a crucial role in extending the kinetic regime of contaminant uptake, by slowing down their diffusion between the water phase and the receiving phase. The drive to improve passive sampling requires membranes with better design and enhanced performances. In this review, the preparation of standard polyethersulfone (PES) membranes for POCIS is presented, as well as methods to evaluate their composition, morphology, structure, and performance. Generally, only supplier-related morphological and structural data are provided, such as membrane type, thickness, surface area, and pore diameter. The issues related to the use of PES membranes in POCIS applications are exposed. Finally, alternative membranes to PES in POCIS are also discussed, although no better membrane has yet been developed. This review highlights the urge for more membrane characterization details and a better comprehension of the mechanisms which underlay their behavior and performance, to improve membrane selection and optimize passive sampler development.

An optimized processing method for polar organic chemical integrative samplers deployed in seawater: Toward a maximization of the analysis accuracy for trace emerging contaminants.

Passive sampling of emerging contaminants (ECs) in seawater represents a challenge in environmental monitoring. A specific protocol for Polar Organic Chemical Integrative Sampler (POCIS) processing may be necessary when dealing with marine applications, due to the peculiarity of the considered matrix. Herein, both the instrumental LC-MS/MS analysis and the sampler processing for the determination of 22 ECs in seawater were carefully optimized. The study entailed a test simulating POCIS sorbent exposure to seawater as well as the processing of replicated field POCIS with different elution solvents. The final method involved washing the sorbent with water, to eliminate most salts, and a two-step elution, by using methanol and a small volume of a dichloromethane-isopropanol mixture. With this protocol, recoveries between 58 and 137% (average 106%) were obtained for most analytes, including non-steroidal anti-inflammatory drugs, UV-filters, perfluorinated substances and caffeine. Still, the protocol was not suitable for very hydrophilic compounds (recovery under 20% for artificial sweeteners and the pharmaceutical salbutamol), which also showed remarkable ion suppression (matrix effects in the range 4-46%). For all other chemicals, the matrix effects were in the range 67-103% (average 86%), indicating satisfactory accuracy. Also, the overall method showed high sensitivity (detection limits in the range 0.04-9 ng g-1 of POCIS sorbent) and excellent specificity, thanks to the monitoring of two "precursor ion-product ion" MS transitions for identity confirmation. The method was applied to samplers deployed in the Ligurian coast (Italy), detecting caffeine, bisphenol A, ketoprofen and two UV-filters as the most concentrated in the POCIS sorbent.

The study of polar emerging contaminants in seawater by passive sampling: A review.

Emerging Contaminants (ECs) in marine waters include different classes of compounds, such as pharmaceuticals and personal care products, showing "emerging concern" related to the environment and human health. Their measurement in seawater is challenging mainly due to the low concentration levels and the possible matrix interferences. Mass spectrometry combined with chromatographic techniques represents the method of choice to study seawater ECs, due to its sensitivity and versatility. Nevertheless, these instrumental techniques have to be preceded by suitable sample collection and pre-treatment: passive sampling represents a powerful approach in this regard. The present review compiles the existing occurrence studies on passive sampling coupled to mass spectrometry for the monitoring of polar ECs in seawater and discusses the availability of calibration data that enabled quantitative estimations. A vast majority of the published studies carried out during the last two decades describe the use of integrative samplers, while applications of equilibrium samplers represent approximately 10%. The polar Chemcatcher was the first applied to marine waters, while the more sensitive Polar Organic Chemical Integrative Sampler rapidly became the most widely employed passive sampler. The organic Diffusive Gradients in Thin film technology is a recently introduced and promising device, due to its more reliable sampling rates. The best passive sampler selection for the monitoring of ECs in the marine environment as well as future research and development needs in this area are further discussed. On the instrumental side, combining passive sampling with high resolution mass spectrometry to better assess polar ECs is strongly advocated, despite the current challenges associated.

Unravelling the role of membrane pore size in polar organic chemical integrative samplers (POCIS) to broaden the polarity range of sampled analytes.

Polar organic chemical integrative samplers (POCIS) are widely used in their standard configuration for sampling contaminants in water bodies. A wider polyethersulfone (PES) membrane pore size was employed in POCIS exposed in a static calibration experiment to investigate the uptake of 21 emerging contaminants ranging from hydrophilic (perfluoroalkyl compounds, xanthines, an artificial sweetener) to more hydrophobic compounds (pharmaceuticals, oestrogens, UV filters). Compared to standard POCIS with 0.1-µm pore size PES membranes, the POCIS with 5-µm pore size PES membranes did not increase sampling rates for compounds of relatively low and mid-hydrophobicity. However, the uptake of more hydrophobic and anionic compounds, which either poorly diffuse through or are retained within the standard 0.1-µm PES membrane, showed a marked increase. This led to the first ever recorded sampling rates for triclosan (0.249 L day-1) and two UV filters (0.075-0.123 L day-1). Based on these results, more attention should be placed on the choice of the appropriate membrane for each POCIS application. The most suitable configuration depends on the studied compound physico-chemical characteristics-such as the polarity and the compound membrane-to-sorbent partitioning coefficient-but also on the site conditions (deployment time, fouling, flow variations, et.).

Development of an Accurate Mass Retention Time Database for Untargeted Metabolomic Analysis and Its Application to Plasma and Urine Pediatric Samples.

Liquid-chromatography coupled to high resolution mass spectrometry (LC-HRMS) is currently the method of choice for untargeted metabolomic analysis. The availability of established protocols to achieve a high confidence identification of metabolites is crucial. The aim of this work is to describe the workflow that we have applied to build an Accurate Mass Retention Time (AMRT) database using a commercial metabolite library of standards. LC-HRMS analysis was carried out using a Vanquish Horizon UHPLC system coupled to a Q-Exactive Plus Hybrid Quadrupole-Orbitrap Mass Spectrometer (Thermo Fisher Scientific, Milan, Italy). The fragmentation spectra, obtained with 12 collision energies, were acquired for each metabolite, in both polarities, through flow injection analysis. Several chromatographic conditions were tested to obtain a protocol that yielded stable retention times. The adopted chromatographic protocol included a gradient separation using a reversed phase (Waters Acquity BEH C18) and a HILIC (Waters Acquity BEH Amide) column. An AMRT database of 518 compounds was obtained and tested on real plasma and urine samples analyzed in data-dependent acquisition mode. Our AMRT library allowed a level 1 identification, according to the Metabolomics Standards Initiative, of 132 and 124 metabolites in human pediatric plasma and urine samples, respectively. This library represents a starting point for future metabolomic studies in pediatric settings.

An innovative sampling approach combined with liquid chromatography-tandem mass spectrometry for the analysis of emerging pollutants in drinking water.

In this work, an innovative sampling and preconcentration method followed by analysis with liquid chromatography coupled to tandem mass spectrometry with electrospray ionization (LC-ESI-MS/MS) was developed for the determination of different emerging pollutants (five anti-inflammatory drugs and one antibacterial agent) in water matrices. Thin-film microextraction blades, consisting of stainless steel blades with a coating made of divinylbenzene, have been employed. The blades, fixed onto a stainless steel support, were mounted on a laboratory stirrer with adjustable speed, immersed in water samples and eluted with methanol. The analytical procedure was developed, carefully optimizing stirring speed and extraction time. A good reproducibility among the blades was observed; quantitation limits at the ng L-1 level were achieved. Calibration curves were constructed by applying the whole procedure to tap water samples, free from analytes, spiked with standards in the concentration range 0.01-2 µg L-1 ; good linearity was obtained, with R2 between 0.9984 and 0.9991. The optimized method was applied to tap and surface waters; two anti-inflammatory drugs were detected at the ng L-1 level in surface water. In one sample, diclofenac and naproxen were measured at 26 ± 5 and 15 ± 1 ng L-1 , respectively; only diclofenac was quantified in the other sample at 14 ± 3 ng L-1 .

The experimental design approach to the optimization of a simple quick easy cheap effective rugged and safe method for the analysis of phytoestrogens in complex soy-based food.

The present paper deals with the multivariate optimization of an extraction-purification strategy for the determination of phytoestrogens (daidzein, genistein, coumestrol, formononetin, and biochanin A) in soy-based meat substitutes by high performance liquid chromatography with tandem mass spectrometry. For a reliable quantitation of these new concerning compounds in such a complex matrix, recovery and matrix effect must be carefully evaluated. Therefore, two sequential experimental designs were used to optimize the sample-pretreatment of soy-based burgers: the chosen technique was the quick, easy, cheap, effective, rugged and safe methodology, which does not require any particular facility or instrumentation. Thanks to the first screening design (Plackett-Burman), the significant factors influencing the studied responses were identified and further investigated through a response surface design (Box-Behnken). The optimal values of the variables (volume of extraction solvent mix/sample mass ratio and two clean-up sorbents) led to quantitative recoveries (97-104%) and low ion suppression (matrix effect 60-93%) for all analytes. This optimized method was characterized by low detection limits (0.2-1.5 ng/g) and excellent intraday precision (RSD 2-4%). It was applied to the determination of the considered compounds in several soy-burgers from the Italian market, detecting low ng/g levels (up to 40 ng/g) of coumestrol, formononetin, and biochanin A, and high concentrations (7.9-78 µg/g) of genistein and daidzein.

Phytoestrogens in soy-based meat substitutes: Comparison of different extraction methods for the subsequent analysis by liquid chromatography-tandem mass spectrometry.

This paper presents the development of an efficient extraction procedure followed by a high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for the determination of five phytoestrogens (genistein, daidzein, formononetin, biochanin A, and coumestrol) in soy-based meat substitutes. Phytoestrogens are considered endocrine disrupting compounds, and their quantification is important in soy-based products, whose diffusion is increasing nowadays. The HPLC-MS/MS method, with electrospray ionization (ESI) source, was optimized to obtain high specificity and sensitivity, as well as rapidity of the analysis. Three extraction techniques were applied to soy burgers and compared: ultrasound assisted extraction, ultrasound assisted extraction followed by solid phase extraction and the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) methodology. Both ultrasound assisted extraction and QuEChERS proved to be suitable for the determination of phytoestrogens, showing high recoveries, in the range of 86% to 99% and 75% to 105%, respectively. Matrix effect was evaluated, and ion suppression was observed for coumestrol and formononetin, demonstrating the importance of matrix effect assessment when complex samples are analyzed by HPLC-ESI-MS. The complete analytical protocols provided limits of detection and quantitation in soy-burgers at the ng g-1 level for all the considered phytoestrogens. Some soy burger samples were analyzed by both ultrasound assisted extraction and QuEChERS followed by HPLC-MS/MS. High concentration levels of daidzein and genistein (2-59 µg g-1 and 2-72 µg g-1 , respectively) were found; formononetin was in the range of 5 to 26 ng g-1 , while biochanin A and coumestrol were under the limit of quantitation in all samples. The results obtained with the two different sample treatment were in good agreement, proving the precision and accuracy of the described techniques.

Untargeted approach for the evaluation of anthropic impact on the sheltered marine area of Portofino (Italy).

Seawater passive sampling with Polar Organic Chemical Integrative Samplers (POCIS) combined with Gaschromatography-Mass Spectrometry analysis were employed as a tool for screening unknown contaminants in a complex Ligurian marine coastal area. The untargeted approach allowed recognizing different classes of compounds, mainly hydrocarbons from C20 to C30. Besides, two chemicals, deriving from anthropic activities, N-butylbenzenesulfonamide (NBBS) and diphenyl sulfone (DPS), were identified and quantified in all samples. Both analytes showed decreasing concentrations from the more confined site to the outer one. The oceanographic characterization of the area performed with multiparametric probes provided useful information, in agreement with chemical analyses. The presence of NBBS and DPS in the site presenting lower continental inputs demonstrated the usefulness of the integrative sampling approach for temporal and spatial monitoring, especially for low level and/or short-term pollution events that traditional monitoring can fail to detect.

Marine environment pollution: The contribution of mass spectrometry to the study of seawater.

The study of marine pollution has been traditionally addressed to persistent chemicals, generally known as priority pollutants; a current trend in environmental analysis is a shift toward "emerging pollutants," defined as newly identified or previously unrecognized contaminants. The present review is focused on the peculiar contribution of mass spectrometry (MS) to the study of pollutants in the seawater compartment. The work is organized in five paragraphs where the most relevant groups of pollutants, both "classical" and "emerging," are presented and discussed, highlighting the relative data obtained by the means of different MS techniques. The hyphenation of MS and separative techniques, together with the development of different ion sources, makes MS and tandem MS the analytical tool of choice for the determination of trace organic contaminants in seawater. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 37:492-512, 2018.

3,3'-dichlorobiphenyl (non-Aroclor PCB-11) as a marker of non-legacy PCB contamination in marine species: comparison between Antarctic and Mediterranean bivalves.

In this study the accumulation of the 3,3'-dichlorobiphenyl (PCB-11) in monitoring organisms from the Antarctic and Mediterranean coastal environments has been investigated. This lesser-known PCB congener, unrelated to the industrial use of commercial mixtures, continues to be generated and released into the environment mainly as an unintentional by-product of pigment manufacturing. Specimens of the filter-feeders Adamussium colbecki from Terra Nova Bay and of Mytilus galloprovincialis and Ruditapes philippinarum from the north-western Adriatic coasts were collected and analyzed for PCB-11 by Gas Chromatography coupled both to Low-Resolution and High-Resolution Mass Spectrometry (LRMS, HRMS). In order to assess the influence of PCB-11 with respect to the legacy contamination, 126 PCB congeners related to the Aroclor commercial mixtures were simultaneously analyzed. PCB-11 was detected in all the samples, regardless of the species and of the geographical area, representing on average 17.6% and 15.6% of the total PCBs (n = 127) in Antarctic and Mediterranean samples, respectively. In the Adriatic area the highest concentrations were related to the influence of industrial activities or ship traffic, while the highest value found in Antarctic specimens, namely those collected in the austral summer 1997-1998, was ascribed to a local anthropogenic source. The occurrence of PCB-11 in the other samples from Terra Nova Bay may be related to Long-Range Atmospheric Transport (LRAT), facilitated by the higher volatility of the analyte compared to the heavier PCB congeners. Nevertheless, more in-depth studies are needed in order to evaluate the relative contribution of local and distant sources.

Liquid chromatography-tandem mass spectrometry and passive sampling: powerful tools for the determination of emerging pollutants in water for human consumption.

Among the wide range of emerging pollutants, perfluorinated compounds and various pharmaceuticals, such as nonsteroidal anti-inflammatory drugs, are showing growing concern. These contaminants can be found in freshwater ecosystems because of their incomplete removal during wastewater treatments so, their water solubility and poor degradability result in their continuous discharge and pseudo-persistent contamination. Usually, expected levels of these analytes are particularly low; therefore, sensitive and selective analytical techniques are required for their determination. Moreover, sampling and preconcentration are fundamental steps to reach the low detection limits required. The polar organic chemical integrative sampler (POCIS) represents a modern sampling approach that allows the in-situ preconcentration of ultra-trace pollutants. In this work, a fast liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) method was developed for the determination of diclofenac, ketoprofen, mefenamic acid, naproxen, ibuprofen, perfluorooctanoic acid, perfluorooctanesulfonate and caffeine in water for human consumption. The chromatographic separation of analytes was achieved in less than 6 min. Quantitative analysis was performed in multiple reaction monitoring mode using ketoprofen-d3 as internal standard. Two different sites of Northern Italy were studied deploying POCIS for four weeks in both inlet and outlet of two drinking water treatment plants. The evaluation of time-weighted average concentration of contaminants was accomplished after the calibration of POCIS; to this aim, the sampling rate values for each compound were obtained by means of a simple calibration system developed in our laboratory. Ketoprofen, perfluorooctane sulfonate, perfluorooctanoate and caffeine were measured in both sites at the ng l(-1) level. Copyright © 2016 John Wiley & Sons, Ltd.

Effect of silver nanoparticles on marine organisms belonging to different trophic levels.

Silver nanoparticles (Ag-NPs) are increasingly used in a wide range of consumer products and such an extensive use raises questions about their safety and environmental toxicity. We investigated the potential toxicity of Ag-NPs in the marine ecosystem by analyzing the effects on several organisms belonging to different trophic levels. Algae (Dunaliella tertiolecta, Skeletonema costatum), cnidaria (Aurelia aurita jellyfish), crustaceans (Amphibalanus amphitrite and Artemia salina) and echinoderms (Paracentrotus lividus) were exposed to Ag-NPs and different end-points were evaluated: algal growth, ephyra jellyfish immobilization and frequency of pulsations, crustaceans mortality and swimming behavior, and sea urchin sperm motility. Results showed that all the end-points were able to underline a dose-dependent effect. Jellyfish were the most sensitive species, followed by barnacles, sea urchins, green algae, diatoms and brine shrimps. In conclusion, Ag-NPs exposure can influence different trophic levels within the marine ecosystem.

Year-round record of dissolved and particulate metals in surface snow at Dome Concordia (East Antarctica).

From January to December 2010, surface snow samples were collected with monthly resolution at the Concordia station (75°06'S, 123°20'E), on the Antarctic plateau, and analysed for major and trace elements in both dissolved and particulate (i.e. insoluble particles, >0.45 µm) phase. Additional surface snow samples were collected with daily resolution, for the determination of sea-salt sodium and not-sea-salt calcium, in order to support the discussion on the seasonal variations of trace elements. Concentrations of alkaline and alkaline-earth elements were higher in winter (April-October) than in summer (November-March) by a factor of 1.2-3.3, in agreement with the higher concentration of sea-salt atmospheric particles reaching the Antarctic plateau during the winter. Similarly, trace elements were generally higher in winter by a factor of 1.2-1.5, whereas Al and Fe did not show any significant seasonal trend. Partitioning between dissolved and particulate phases did not change with the sampling period, but it depended only on the element: alkaline and alkaline-earth elements, as well as Co, Cu, Mn, Pb and Zn were for the most part (>80%) in the dissolved phase, whereas Al and Fe were mainly associated with the particulate phase (>80%) and Cd, Cr, V were nearly equally distributed between the phases. Finally, the estimated marine and crustal enrichment factors indicated that Cd, Cr, Cu, Pb and Zn have a dominant anthropogenic origin, with a possible contribution from the Concordia station activities.

Innovative sampling and extraction methods for the determination of nonsteroidal anti-inflammatory drugs in water.

Two different innovative approaches were used for the determination of nonsteroidal anti-inflammatory drugs (NSAIDs) in water: stir bar sorptive extraction (SBSE) and passive sampling, followed by electrospray ionization liquid chromatography-tandem mass spectrometry. SBSE was developed by comparing EG-Silicone and PDMS stir bars and optimizing main parameters to attain high preconcentration. Quantitative analysis was carried out by mass spectrometry in negative ionization mode and multiple reaction monitoring. The SBSE-LC-MS/MS method provided satisfactory figures of merit with LOD (7.5-71 ng L(-1)) and LOQ (22.5-213 ng L(-1)). The developed method was successfully applied to real samples collected from river water and wastewater effluents. The obtained results showed the presence of all analytes at trace levels, in a wide range of concentrations. The passive sampling approach was carried out by using Polar Organic Chemical Integrative Sampler (POCIS); samplers were deployed for 15 days in river and tap water, allowing to detect analytes at ultra-trace levels. Time-Weighted Average concentration of NSAIDs in river water was estimated in the range 0.33-0.46 ng L(-1), using the sampling rates previously obtained by means of a simple calibration system.