Presence, behaviour, and risk assessment of volatile methylsiloxanes in wastewater: A year-long comprehensive study within a wastewater treatment plant.

The awareness of possible environmental hazards caused by the widespread global use of volatile methylsiloxanes (VMSs) in personal care products (PCPs) and industrial processes has been increasing. Sewage containing these compounds may reach wastewater treatment plants (WWTPs), which are hotspots of their release into the environment. The levels, distribution, and potential risks of VMSs were studied in an unprecedently comprehensive sampling strategy (four seasonal campaigns) along the water line of a WWTP: the main influent entrance (SA1), after the preliminary treatment (SA2), after the primary treatment (SA3) and after the secondary treatment (the treated effluent; SA4). This WWTP was selected as a representative of the conventional set up based on a secondary treatment, allowing a similar approach in numerous facilities worldwide. Seven VMSs (L3, L4, L5, D3, D4, D5, D6) were analysed in wastewater samples by a small-scale liquid-liquid extraction (LLE) protocol, followed by gas chromatography-mass spectrometry (GC-MS), and the cyclic VMSs were dominant at all sampling sites and in all seasons. Considering the whole year, the total VMSs ranged from 0.4 to 22.5 µg L-1 for SA1, 0.03 to 33.7 µg L-1 for SA2, below method detection limit (MDL) to 13.2 µg L-1 for SA3 and 98 %). According to the risk quotients (RQ), only 18 SA4 samples (32 %) presented a minimal risk to the receiving media (0.01 ≤ RQ < 0.1). However, considering the absence of a secondary treatment or a direct discharge without treatment, there may be a risk to the environment.

Are volatile methylsiloxanes in downcycled tire microplastics? Levels and human exposure estimation in synthetic turf football fields.

Downcycled rubber, derived from end-of-life tires (ELTs), is frequently applied as crumb rubber (CR) as infill of synthetic turf in sports facilities. This practice has been questioned in recent years as numerous studies have reported the presence of potentially hazardous chemicals in this material. CR particles fall into the category of microplastics (MPs), making them possible vectors for emerging micropollutants. A preliminary study where volatile methylsiloxanes (VMSs) were found in CR originated the hypothesis that VMSs are present in this material worldwide. Consequently, the present work evaluates for the first time the levels and trends of seven VMSs in CR from synthetic turf football fields, while attempting to identify the main sources and impacts of these chemicals. A total of 135 CR samples and 12 other of alternative materials were analyzed, employing an ultrasound-assisted dispersive solid-phase extraction followed by gas chromatography-mass spectrometry (GC-MS), and the presence of VMSs was confirmed in all samples, in total concentrations ranging from 1.60 to 5089 ng.g-1. The levels were higher in commercial CR (before field application), a reflection of the use of VMS-containing additives in tire production and/or the degradation of silicone polymers employed in vehicles. The VMSs generally decreased over time on the turf, as expected given their volatile nature and the wearing of the material. Finally, the human exposure doses to VMSs in CR (by dermal absorption and ingestion) for people in contact with synthetic turf in football fields were negligible (maximum total exposure of 20.5 ng.kgBW-1.year-1) in comparison with the European Chemicals Agency (ECHA) reference doses: 1.35 × 109 ng.kgBW-1.year-1 for D4 and 1.83 × 109 ng.kgBW-1.year-1 for D5. Nevertheless, more knowledge on exposure through inhalation and the combined effects of all substances is necessary to provide further corroboration. This work proved the presence of VMSs in CR from ELTs, another family of chemical of concern to take into account when studying MPs as vectors of other contaminants.

Personal care products in soil-plant and hydroponic systems: Uptake, translocation, and accumulation.

Personal care products (PCPs) are organic compounds that are incorporated in several daily life products, such as shampoos, lotions, perfumes, cleaning products, air fresheners, etc. Due to their massive and continuous use and because they are not routinely monitored in the environment, these compounds are considered emerging contaminants. In fact, residues of PCPs are being discharged into the sewage system, reaching wastewater treatment plants (WWTPs), where most of these compounds are not completely degraded, being partially released into the environment via the final effluents and/or accumulating in the sewage sludges. Environmental sustainability is nowadays one of the main pillars of society and the application of circular economy models, promoting the waste valorisation, is increasingly encouraged. Therefore, irrigation with reclaimed wastewater or soil fertilization with sewage sludge/biosolids are interesting solutions. However, these practices raise concerns due to the potential risks associated to the presence of hazardous compounds, including PCPs. When applied to agricultural soils, PCPs present in these matrices can contaminate the soil or be taken up by crops. Crops can therefore become a route of exposure for humans and pose a risk to public health. However, the extent to which PCPs are taken up and bioaccumulated in crops is highly dependent on the physicochemical properties of the compounds, environmental variables, and the plant species. This issue has attracted the attention of scientists in recent years and the number of publications on this topic has rapidly increased, but a systematic review of these studies is lacking. Therefore, the present paper reviews the uptake, accumulation, and translocation of different classes of PCPs (biocides, parabens, synthetic musks, phthalates, UV-filters) following application of sewage sludge or reclaimed water under field and greenhouse conditions, but also in hydroponic systems. The factors influencing the uptake mechanism in plants were also discussed.

Helping WWTP managers to address the volatile methylsiloxanes issue-Behaviour and complete mass balance in a conventional plant.

Volatile methylsiloxanes (VMSs) are a group of additives employed in different consumer products that can affect the quality of the biogas produced in wastewater treatment plants (WWTPs). The main objective of this study is to understand the fate of different VMSs along the treatment process of a WWTP located in Aveiro (Portugal). Thus, wastewater, sludge, biogas, and air were sampled in different units for two weeks. Subsequently, these samples were extracted and analyzed by different environment-friendly protocols to obtain their VMS (L3-L5, D3-D6) concentrations and profiles. Finally, considering the different matrix flows at every sampling moment, the mass distribution of VMSs within the plant was estimated. The levels of ∑VMSs were similar to those showed in the literature (0.1-50 µg/L in entry wastewater and 1-100 µg/g dw in primary sludge). However, the entry wastewater profile showed higher variability in D3 concentrations (from non detected to 49 µg/L) than found in previous studies (0.10-1.00 µg/L), likely caused by isolated releases of this compound that could be related to industrial sources. Outdoor air samples showed a prevalence of D5, while indoor air locations were characterized by a predominance of D3 and D4. Differences in sources and the presence of an indoor air filtration system may explain this divergence. Biogas was characterized by ∑VMSs concentrations (8.00 ± 0.22 mg/m3) above the limits recommended by some engine manufacturers and mainly composed of D5 (89%). Overall, 81% of the total incoming mass of VMSs is reduced along the WWTP, being the primary decanter and the secondary treatment responsible for the highest decrease (30.6% and 29.4% of the initial mass, respectively). This reduction, however, is congener dependant. The present study demonstrates the importance of extending sampling periods and matrices (i.e., sludge and air) to improve sample representativity, time-sensitivity, and the accuracy of mass balance exercises.

Per- and Poly-Fluoroalkyl Substances in Portuguese Rivers: Spatial-Temporal Monitoring.

Eighteen per-and polyfluoroalkyl substances (PFASs) were investigated in surface waters of four river basins in Portugal (Ave, Leça, Antuã, and Cértima) during the dry and wet seasons. All sampling sites showed contamination in at least one of the seasons. In the dry season, perfluorooctanoate acid (PFOA) and perfluoro-octane sulfonate (PFOS), were the most frequent PFASs, while during the wet season these were PFOA and perfluobutane-sulfonic acid (PFBS). Compounds detected at higher concentrations were PFOS (22.6 ng L-1) and perfluoro-butanoic acid (PFBA) (22.6 ng L-1) in the dry and wet seasons, respectively. Moreover, the prospective environmental risks of PFASs, detected at higher concentrations, were evaluated based on the Risk Quotient (RQ) classification, which comprises acute and chronic toxicity. The results show that the RQ values of eight out of the nine PFASs were below 0.01, indicating low risk to organisms at different trophic levels in the four rivers in both seasons, wet and dry. Nevertheless, in the specific case of perfluoro-tetradecanoic acid (PFTeA), the RQ values calculated exceeded 1 for fish (96 h) and daphnids (48 h), indicating a high risk for these organisms. Furthermore, the RQ values were higher than 0.1, indicating a medium risk for fish, daphnids and green algae (96 h).

Plant uptake potential and soil persistence of volatile methylsiloxanes in sewage sludge amended soils.

Volatile methylsiloxanes (VMSs) are organosilicon compounds, ubiquitous in modern life. Due to their high use in consumer products, large amounts of these compounds are released into sewer systems, reaching wastewater treatment plants (WWTPs). Its frequent detection in sewage sludge can be of concern when considering its land application, not only due to potential negative impacts on the environment, but also on human health. In this work, the effects of sewage sludge application on plant development and crop productivity were studied, as well as VMSs persistence in the soil and their plant uptake. This study focused on 7 VMSs (D3, D4, D5, D6, L3, L4 and L5) and consisted of a 12-week greenhouse pot experiment, where sewage sludge-amended soils were used to cultivate Pisum sativum (peas). Sewage sludge application to soils had no negative effects on plant development and was tied to crop productivity improvements. Most of the VMSs were still present in soils at the end of the experiment and plant uptake and translocation of the 4 cyclic VMSs (D3, D4, D5, D6) occurred. VMSs were detected in plant tissues up to 161 ± 27 ng g-1 dw (samples of stems, leaves and tendrils), but did not exceed 50 ± 19 ng g-1 dw in peas, which did not translate into a human exposure risk due to ingestion, according to an intake risk assessment. However, soil risk assessments showed that for L5 the hazardous ratios were higher than the threshold value of 1. This means a potential environmental risk despite the low levels of this compound in soils (up to 7.3 ± 0.7 ng g-1 dw). Considering these results, sewage sludge monitoring plans should be defined for VMSs, namely when its final destination is land application, thus allowing a safer management of this residue, taking advantage of its valorization potential.

Uptake and translocation of synthetic musk fragrances by pea plant grown in sewage sludge-amended soils.

Sewage sludges are rich in organic matter and several essential nutrients for plant growth, making them very appealing for application in agricultural soils. However, they may also contain a wide range of emerging pollutants, which has raised concerns about the potential risks of this practice to crops, the environment, and public health - accumulation in soils and/or plant uptake and translocation of contaminants. Therefore, there is a need to study plant-soil interactions and assess the uptake potential of these contaminants by food crops to better understand these risks. The main aim of this work was to assess the possible drawbacks of sludge application to cropland, by observing the impact on the growth and yield of a model crop (pea plant - Pisum sativum) grown over an 86-day greenhouse experiment and by assessing the uptake potential of synthetic musk fragrances. Different sewage sludge application rates (4-30-ton ha-1) and initial concentrations of contaminants were tested. The application of sludge yielded benefits to the cultivated plants, finding improved crop productivity with an application rate of 30-ton ha-1. At the end of the experiment, soil samples and plants separated into sections were analysed using a QuEChERS extraction methodology followed by gas chromatography-mass spectrometry (GC-MS) quantification. Galaxolide (HHCB) and tonalide (AHTN) underwent uptake by the plant roots, having been detected in concentrations up to 346 ng g-1 on a dry weight basis (dw), but only HHCB was detected in above ground tissues. At the end, a decrease in the levels of synthetic musks in the amended soils (>80% in several instances) was observed. Assuming the worst-case scenario, no risk to human health was observed from the ingestion of peas grown on sewage sludge-amended soils. However, a soil hazard quotient analysis yielded worryingly high quotient values for AHTN in nearly all tested conditions.

Presence of metals and metalloids in crumb rubber used as infill of worldwide synthetic turf pitches: Exposure and risk assessment.

Crumb rubber derived from end-of-life tires (ELTs) is frequently used as infill of synthetic turf pitches, promoting circular economy. Although important to reduce the accumulation of waste, the use of recycled ELTs can be a problem to human health and the environment, both by direct contact during pitch use and by the release of these elements to the surroundings, mostly via volatilization and leaching. The present study aimed to evaluate the distribution of metals in ELT-derived crumb rubber collected in artificial turf worldwide and assess possible trends by country, pitch age and type (indoor vs. outdoor). The concentration ranges observed are very wide, especially in outdoor fields and for the most abundant metals, namely Zn (2989-5246 mg/kg), Fe (196-5194 mg/kg), Mg (188-1795 mg/kg) and Al (159-1882 mg/kg). For Zn, the levels were mostly above the safe limits set in European directives for relatable matrices (soils and toy materials), and the same happened for Pb, a much more toxic metal at lower concentrations. A multi-pathway human exposure study was also performed, and the risk assessment shows non-carcinogenic and carcinogenic risks from accidental crumb rubber ingestion (with Cr and Pb as major contributors) above the acceptable values for all the receptors except adult bystanders, with a higher significance to younger individuals. These results bring a different perspective regarding most of the studies reporting low risks related with exposure to metals in crumb rubber.

A review of bioaccumulation of volatile methylsiloxanes in aquatic ecosystems.

Volatile methylsiloxanes (VMSs) are found in a broad range of industrial and consumer products. They are categorized as "high production volume chemicals" by the U.S. Environmental Protection Agency and listed as candidates of substances of very high concern in 2018, by the Registration, Evaluation, Authorization and Restriction of Chemicals (REACH). Industrial wastewater and treated effluents may contain VMSs in different amounts, which can be discharged in the receptor media and may lead to environmental contamination. This can result in direct exposure to aquatic receptors in the water column or to benthic invertebrates from contact and/or ingestion of sediments, and indirect exposures through the aquatic food chain. The possible toxicological effects of VMSs for the aquatic biota and human ecology are not very well known since published information regarding this topic is scarce. VMSs have been subjected to regulatory scrutiny for environmental concerns and have already been screened to determine their environmental risk and ecological harm. This paper aims to assess VMSs bioaccumulation and potential biomagnification on food webs, using several bioaccumulation metrics. The result is a high-level overview of all the collected data, comparing the findings and the experimental conditions applied during the assessments. Several studies present conflicting results regarding the bioaccumulation categorization. Some aquatic organisms demonstrated a high bioconcentration and bioaccumulation of these contaminants. Trophic magnification factors (TMFs) have been suggested as the most reliable tool to assess a chemical behaviour in food webs. However, bioaccumulation studies in food webs provided mixed information, with some studies indicating trophic dilution and others presenting a potential of trophic biomagnification of VMSs. Efforts should be directed to obtain field-based levels of VMSs at different trophic levels and a wider range of linear VMSs should be analysed, since most studies focused on D4, D5 and D6.

Gone with the flow - Assessment of personal care products in Portuguese rivers.

Although there are several works in the literature that study the presence of pharmaceuticals and personal care products (PPCPs) in surface waters, the vast majority focus their attention on pharmaceuticals and little information is found about personal care products (PCPs). Therefore, this study focused, for the first time, on the monitoring of five classes of PCPs - fragrance allergens, synthetic musks, phthalates, antioxidants, and ultraviolet-filters - in the surface water of four small-size typically pollution-impacted Portuguese rivers (Ave, Leça, Antuã and Cértima). A solid-phase microextraction (SPME) followed by gas chromatography - tandem mass spectrometry (GC-MS/MS) protocol was employed to analyse surface water samples collected in two seasonal campaigns - summer and winter (34 samples per season). A total of 22 out of 37 target PCPs were detected concomitantly at least once in one sampling point, being the most frequently detected α-isomethyl ionone, galaxolide, tonalide and cashmeran. The highest concentrations were confirmed for diethylhexyl phthalate (610.6 ng L-1), galaxolide (379.2 ng L-1), geraniol (290.9 ng L-1), linalool (271.2 ng L-1), benzophenone-3 (254.1 ng L-1) and citronellol (200.2 ng L-1). Leça River, traversing the more densely urban and industrialized area, had the highest levels of contaminants, which were also found in the sampling points located downstream of wastewater treatment plants discharge points. In general, higher levels were detected in summer, when the river flows are lower. Hazard quotients were determined and octocrylene, tonalide, and geraniol presented values above 1 in some sampling sites, which may indicate an ecotoxicological risk to the aquatic environment. The results presented suggest that these three PCPs should be included as priority pollutants in environmental monitoring schemes in surface waters, due to their high detection, persistence, and potential adverse effects.

Using Design of Experiments to Optimize a Screening Analytical Methodology Based on Solid-Phase Microextraction/Gas Chromatography for the Determination of Volatile Methylsiloxanes in Water.

Volatile methylsiloxanes (VMSs) constitute a group of compounds used in a great variety of products, particularly personal care products. Due to their massive use, they are continually discharged into wastewater treatment plants and are increasingly being detected in wastewater and in the environment at low concentrations. The aim of this work was to develop and validate a fast and reliable methodology to screen seven VMSs in water samples, by headspace solid-phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID). The influence of several factors affecting the extraction efficiency was investigated using a design of experiments approach. The main factors were selected (fiber type, sample volume, ionic strength, extraction and desorption time, extraction and desorption temperature) and optimized, employing a central composite design. The optimal conditions were: 65 µm PDMS/Divinylbenzene fiber, 10 mL sample, 19.5% NaCl, 39 min extraction time, 10 min desorption time, and 33 °C and 240 °C as extraction and desorption temperature, respectively. The methodology was successfully validated, showing low detection limits (up to 24 ng/L), good precision (relative standard deviations below 15%), and accuracy ranging from 62% to 104% in wastewater, tap, and river water samples.

Uptake and translocation of UV-filters and synthetic musk compounds into edible parts of tomato grown in amended soils.

In the last years, the number of wastewater treatment plants (WWTPs) has increased and consequently, sewage sludge production. This residue is very rich in crop nutrients, which makes it prone to be used as organic fertilizer or soil conditioner for agriculture. However, the presence of emerging pollutants in these fertilizers has raised concern, namely their potential accumulation in soil and, eventually their uptake by crops. Therefore, the main goal of this work was to study the potential plant uptake and translocation of ultraviolet-filters (UVFs) and synthetic musk compounds (SMCs). A total of 6 UVFs and 11 SMCs were analysed in Micro-Tom tomatoes grown in soil amended with a commercial sewage sludge-based organic fertilizer. Most of the studied compounds were detected in the tomato fruit, in concentrations ranging from 5 to 147 ng g-1 dw for UVFs and from 1.3 to 68 ng g-1 dw for SMCs. This indicates a potential uptake of these emerging pollutants and a subsequent translocation to the fruits. Besides that, UVFs show bioconcentration factors (BCFs) from 3 (DTS) to 33 (BZ) and SMCs from 0.2 (AHTN) to 23 (HHCB). Nevertheless, no risk by ingestion was observed based on estimation of the weekly exposure dose through hazard quotients (HQ < 0.02). SMCs galaxolide and tonalide seem to pose risk to the amended soils.

Modified dispersive solid-phase extraction and cleanup followed by GC-MS/MS analysis to quantify ultraviolet filters and synthetic musk compounds in soil samples.

A simple method for the analysis of 13 synthetic musk compounds and six ultraviolet filters in soil samples was developed using a modified dispersive solid-phase methodology known as "Quick, Easy, Cheap, Effective, Rugged and Safe," followed by gas chromatography-triple quadrupole mass spectrometry. The methodology was validated by assessing linearity ranges, detection limits, precision, and accuracy. The method detection limit ranged between 0.01 and 10.00 ng/g dry weight and accuracy from 81 to 122%. A good precision was achieved, with relative standard deviation <10%. The applicability of the methodology was tested using different types of soils. Both synthetic musks and ultraviolet filters were detected in all soil samples. The most frequently detected compounds were benzophenone, octocrylene, 2-ethylhexyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-methoxycinnamate, and galaxolide. Higher levels were detected for benzophenone (maximum value of 158 ng/g dry weight) and octocrylene (137 ng/g dry weight). In comparison with conventional techniques, this method uses lower amounts of solvents and sorbents, producing less waste ("greener" technique) and comparable performances. In addition, it presents as main advantages the simplicity, speed (short extraction/cleaning time), low cost, and minimum handling of extracts, which can minimize the possibility of samples cross-contamination.

Headspace solid-phase microextraction based on the metal-organic framework CIM-80(Al) coating to determine volatile methylsiloxanes and musk fragrances in water samples using gas chromatography and mass spectrometry.

A headspace solid-phase microextraction (HS-SPME) method was developed using the metal-organic framework (MOF) CIM-80(Al) as extraction phase and in combination with gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of 6 methylsiloxanes and 7 musk fragrances in different environmental waters. The chromatographic separation was optimized in different GC instruments equipped with different detectors, allowing the correct separation and identification of the compounds. The HS-SPME method was optimized using a Box-Behnken experimental design, while the validation was carried out together with the most suitable commercial fiber (divinylbenzene/polydimethylsiloxane) for comparison purposes. The MOF-based coating was particularly efficient for the determination of volatile methylsiloxanes, showing moderately lower limits of detection (of 0.2 and 0.5 µg L-1versus 0.6 µg L-1 for cyclic methylsiloxanes) and slightly better precision (relative standard deviation values lower than 17% versus 22%) than the commercial coating, while avoiding the cross-contamination issues associated to the polymeric composition of commercial fibers. The method was applied for the analysis of seawater and wastewater samples, allowing the quantification of several analytes and the assessment of matrix effects. The proposed HS-SPME method using the CIM-80(Al) fiber constitutes a more environmentally friendly, simpler, and efficient strategy in comparison with other sample preparation methods using different extraction techniques, while the use of a MOF as fiber sorbent constitutes a potential alternative to exploit the features of SPME for the challenging environmental monitoring of these compounds.

Comparison of Techniques and Solvents on the Antimicrobial and Antioxidant Potential of Extracts from Acacia dealbata and Olea europaea.

Ethnopharmacological use of plant natural extracts has been known since ancient times. The optimization of plant molecule extraction is fundamental in obtaining relevant extraction yields. The main purpose of this study was to understand the role of different extraction techniques (solid-liquid, ultrasound, Soxhlet, and microwave) and solvents (water, methanol, ethanol, acetone, dichloromethane, and hexane) on the antimicrobial and antioxidant activities of extracts from Olea europaea (olive) and Acacia dealbata (mimosa). Crude plant extracts were evaluated for their antimicrobial activity against Staphylococcus aureus and Escherichia coli by the disk diffusion method. The antioxidant capacity of the extracts was determined by ABTS (2,2-azinobis (3-ethyl-benzothiazoline-6-sulfonic acid)) and DPPH (2,2-diphenyl-1-picrylhydrazyl) methods. In terms of extraction yield, ultrasound extraction and the solvents methanol, acetone (O. europaea) or water (A. dealbata) were found to be the best options. However, ethanol and acetone proved to be the best solvents to extract compounds with antimicrobial activity and antioxidant capacity, respectively (regardless of the extraction method employed). Soxhlet and microwave were the best techniques to extract compounds with antimicrobial activity, whereas any of the tested techniques showed the ability to extract compounds with antioxidant capacity. In most of the cases, both plant extracts (mimosa and olive) were more efficient against S. aureus than E. coli. In the present study, both mimosa and olive leaf crude extracts proved to have antimicrobial and antioxidant activities, increasing the demand of these natural products as a source of compounds with health benefits.

Analytical methodology to screen UV-filters and synthetic musk compounds in market tomatoes.

A Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) methodology followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis was developed to extract thirteen synthetic musk compounds (SMCs: cashmeran, celestolide, phantolide, traseolide, galaxolide, tonalide, musk ambrette, musk xylene, musk ketone, musk tibetene, musk moskene, ethylene brassylate and exaltolide) and six ultraviolet-filters (UVFs: 2-ethylhexyl 4-dimethylaminobenzoate, 3-(4'-methylbenzylidene) camphor, 2-ethylhexyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, benzophenone and drometrizole trisiloxane) from tomatoes. The proposed methodology was optimized: 2 g of freeze-dried tomato was extracted with 4 mL of water and 10 mL of ethyl acetate, adding 6 g of MgSO4 and 1.5 g of NaCl, then a dispersive solid-phase extraction was performed using 3 g of MgSO4, 300 mg of primary-secondary amino adsorbent (PSA) and 300 mg of octadecyl-silica (C18). Validation delivered recoveries between 81 (celestolide) and 119% (musk tibetene), with relative standard deviations <10%. The instrumental limit of detection varied from 0.02 (2-ethylhexyl 4-methoxycinnamate) to 3.00 pg (exaltolide and musk xylene). Regarding the method quantification limits, it ranged between 0.4 (celestolide) and 47.9 ng g-1 dw (exaltolide). The method was applied to different varieties of tomatoes (Solanum lycopersicum), revealing UVFs and SMCs between 1 and 210 ng g-1 dw. Higher concentrations were found for benzophenone (29-210 ng g-1 dw) and galaxolide (9-53 ng g-1 dw). The risk associated to the ingestion of contaminated tomatoes has also been estimated, showing that a potential health risk is unlikely.

Determination of multiclass personal care products in continental waters by solid-phase microextraction followed by gas chromatography-tandem mass spectrometry.

A methodology based on solid-phase microextraction (SPME) followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed for the simultaneous analysis of different families of personal care products (PCPs) including fragrance allergens, synthetic musks, phthalates, antioxidants and UV filters in continental waters. The main parameters affecting SPME procedure were optimized by an ANOVA study. The final selected conditions comprised the use of 10 mL of sample with 20% (w/v) of sodium chloride (NaCl), polydimtehylsiloxane/divinylbenzene (PDMS/DVB) fiber and 20 min of extraction time at 100 °C in the head-space mode. Good linearity (R2>0.9925), quantitative recoveries (>79%), and precision (RSD < 15%) were achieved for all compounds under the optimal conditions. Limits of quantification (LOQs) at the sub and low ng L-1 were obtained. The validated methodology was successfully applied to the analysis of river water samples from the North Portuguese coast allowing the determination of five different families of PCPs, including a total of 43 compounds in a single chromatographic run within 23 min.