Cytostatic compounds in sludge and sediment: extraction and determination by a combination of microwave-assisted extraction and UHPLC-MS/MS.

Cytostatic compounds are an important group of micro-pollutants since they are used to kill cells or stop cell division. For this reason, they are also considered mutagenic. Several cytostatic compounds have been detected in hospital effluents, in the influents and effluents of wastewater treatment plants and even in river water. However, their detection in solid matrices is very scarce. In this work, we have developed a new procedure based on microwave-assisted extraction (MAE) for the extraction of cytostatic compounds from sludge and sediment before determination by ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). To develop this procedure, we have chosen a group of eight widely used cytostatic compounds and carried out a systematic experimental design to optimize the extraction conditions. Under these optimal conditions, the studied cytostatic compounds are extracted with good sensitivity, with recoveries ranging from 65 to 122% in sludge and recoveries varying between 49 and 109% in sediment, with the exception of etoposide, which has a lower recovery from these types of samples. The limits of detection were from 0.42 to 79.8 ng g-1 in sludge and from 0.10 to 87.5 ng g-1 in sediment. Intraday and interday relative standard deviations (RSDs) were below 15% and 18%, respectively, in both matrices at the tested concentrations. The total procedure was applied to samples of sludge taken from the main wastewater treatment plant (WWTP) of the island of Gran Canaria (Spain) and for sediment samples obtained close to the marine outfalls of different wastewater treatment plants for the same island. Graphical abstract.

Occurrence of benzotriazole UV stabilizers in coastal fishes.

Chemicals added in personal care products are of emerging concern because their fate and their effect on the environment is not completely known. Benzotriazole UV stabilizers (BUVSs) are compounds used in different cosmetic products, which may reach the marine environment through marine discharge from treated waters or directly from bathing areas. Once released into the aquatic ecosystem, BUVSs can be bioaccumulated by aquatic organisms. To identify the human exposure risk, it is important to have suitable analytical methods to determine the presence of BUVSs in these organisms. Because of the complexity of such a biological matrix, selective extraction and detection techniques are required to isolate and quantify these kinds of pollutants at trace levels. In the present work, we optimized a method based on microwave-assisted extraction combined with ultra-high performance liquid chromatography and mass spectrometry detection to determine six benzotriazole compounds in fish samples. The absolute extraction yields provided by the proposed method were higher than 40% for most compounds, with intra-day and inter-day relative standard deviations ranging from 0.27 to 6.06 and 1.12-21.3%, respectively. The limits of quantification were in the range of 1.13-9.66 ng g-1 (dry weight). The method was applied to the study of three species of fish (Boops boops, Sphyraena viridensis, Sphoeroides marmoratus) that were collected close to three marine outfalls of treated waters on the Gran Canaria Island (Spain) for two years. Four of the six studied compounds, UV-326, UV-328, UV-329 and UV-360, were found with concentrations ranging from 1.34 ng g-1 to 45.6 ng g-1 (dry weight).

Monitoring and environmental risk assessment of benzotriazole UV stabilizers in the sewage and coastal environment of Gran Canaria (Canary Islands, Spain).

Benzotriazole UV stabilizers (BUVSs) are emerging contaminants that are widely used in personal care products, such as cosmetics and sunscreens, to absorb ultraviolet light. These compounds have been described as bioaccumulative, pseudo-persistent and toxic; therefore, it is of great importance to investigate them and determine their presence and distribution in the environment. In this research, we performed a two-year monitoring study to identify six BUVS compounds (UV-P, UV-326, UV-327, UV-328, UV-329 and UV-360) in different environmental compartments from Gran Canaria (Canary Islands, Spain): influent and effluent from five wastewater treatment plants (WWTPs) and seawater and sediment samples from three marine areas influenced by sewage outfalls discharges from WWTPs. Two methods based on on-line solid-phase extraction and microwave-assisted extraction coupled with ultra-high-performance liquid chromatography with mass spectrometry detection were applied to quantify the analytes in liquid and solid samples, respectively. The target BUVSs were measured in sewage, coastal seawater and sediment samples in concentrations in the ranges of 13.12-1933 ng L-1, 67.01-2419 ng L-1 and 4.42-2162 ng kg-1 dry weight, respectively. The studied compounds exhibited different trends of occurrence in aqueous and solid samples due to their different coefficients of hydrophobicity. The majority of the positive samples belonged to the most touristic sampling location of the island. The estimated hazard quotient, HQ, revealed no risk from the target compounds at the measured concentrations levels.

Application of microwave-assisted extraction and ultra-high performance liquid chromatography-tandem mass spectrometry for the analysis of sex hormones and corticosteroids in sewage sludge samples.

Hormonal compounds are a concern to the international community because they can affect the aquatic biota and are therefore considered to be endocrine-disrupting compounds. These compounds have lipophilic properties, so they tend to accumulate in solid matrices, such as sewage sludge. This work presents the optimization of a microwave-assisted extraction process combined with ultra-high performance liquid chromatography-tandem mass spectrometry for the determination of 15 hormonal compounds in sludge samples. The proposed method has relative standard deviations below 23 %, good recoveries (over 71 %) for all compounds, detection limits that ranged from 1.1 to 7.9 ng g(-1) and quantification limits which ranged from 3.7 to 26.3 ng g(-1). The method was used to analyse sludge samples from four different wastewater treatment plants of Gran Canaria (Spain) with different wastewater treatments. 17ß-estradiol, 17α-ethynylestradiol, norgestrel and cortisone were detected in sludge samples at concentrations that ranged from 17.3 to 1.44 × 10(3) ng g(-1). The developed method permits the use of small quantities of sample and organic solvents, presents short extractions times and is the first one based on microwave-assisted extraction for the analysis of both sex hormones and corticosteroids.

Fabric phase sorptive extraction followed by UHPLC-MS/MS for the analysis of benzotriazole UV stabilizers in sewage samples.

A fast and sensitive sample preparation strategy using fabric phase sorptive extraction followed by ultra-high-performance liquid chromatography and tandem mass spectrometry detection has been developed to analyse benzotriazole UV stabilizer compounds in aqueous samples. Benzotriazole UV stabilizer compounds are a group of compounds added to sunscreens and other personal care products which may present detrimental effects to aquatic ecosystems. Fabric phase sorptive extraction is a novel solvent minimized sample preparation approach that integrates the advantages of sol-gel derived hybrid inorganic-organic nanocomposite sorbents and the flexible, permeable and hydrophobic surface chemistry of polyester fabric. It is a highly sensitive, fast, efficient and inexpensive device that can be reused and does not suffer from coating damage, unlike SPME fibres or stir bars. In this paper, we optimized the extraction of seven benzotriazole UV filters evaluating the majority of the parameters involved in the extraction process, such as sorbent chemistry selection, extraction time, back-extraction solvent, back-extraction time and the impact of ionic strength. Under the optimized conditions, fabric phase sorptive extraction allows enrichment factors of 10 times with detection limits ranging from 6.01 to 60.7 ng L(-1) and intra- and inter-day % RSDs lower than 11 and 30 % for all compounds, respectively. The optimized sample preparation technique followed by ultra-high-performance liquid chromatography and tandem mass spectrometry detection was applied to determine the target analytes in sewage samples from wastewater treatment plants with different purification processes of Gran Canaria Island (Spain). Two UV stabilizer compounds were measured in ranges 17.0-60.5 ng mL(-1) (UV 328) and 69.3-99.2 ng mL(-1) (UV 360) in the three sewage water samples analysed.

Molecularly imprinted solid-phase extraction coupled with ultra high performance liquid chromatography and fluorescence detection for the determination of estrogens and their metabolites in wastewater.

Estrogens are an important class of endocrine-disrupting compounds, and their contamination of environmental waters through the effluents of wastewater treatment plants could have an important impact on aquatic biota, even at low concentrations. For this reason, the development of selective and sensitive extraction methodologies, which permit the identification and quantification of these compounds at trace level concentrations, is very important. In this study, a quantitative method based on molecularly imprinted solid phase extraction coupled to ultra high performance liquid chromatography with fluorescence detection has been developed. It has been used for the simultaneous determination of three estrogens and two of their metabolites in water samples from wastewater treatment plants. The method developed presents satisfactory limits of detection (between 0.18 and 0.45 ng·mL-1 ), good recoveries (higher than 60%) and low relative standard deviations (under 10%). The method was used to analyze wastewater from a veterinary hospital as well as influent and effluent samples of a wastewater treatment plant of Gran Canaria (Spain) The concentrations of the detected hormones ranged from 1.35 to 2.57 ng·mL-1 .

A dispersive liquid-liquid micellar microextraction for the determination of pharmaceutical compounds in wastewaters using ultra-high-performace liquid chromatography with DAD detection.

A dispersive liquid-liquid micellar microextraction (DLLMME) method coupled with ultra-high-performance liquid chromatography (UHPLC) using Diode Array Detector (DAD) detector was developed for the analysis of five pharmaceutical compounds of different nature in wastewaters. A micellar solution of a surfactant, polidocanol, as extraction solvent (100 µL) and chloroform as dispersive solvent (200 µL) were used to extract and preconcentrate the target analytes. Samples were heated above critical temperature and the cloudy solution was centrifuged. After removing the chloroform, the reduced volume of surfactant was then injected in the UHPLC system. In order to obtain high extraction efficiency, the parameters affecting the liquid-phase microextraction, such as time and temperature extraction, ionic strength and surfactant and organic solvent volume, were optimized using an experimental design. Under the optimized conditions, this procedure allows enrichment factors of up to 47-fold. The detection limit of the method ranged from 0.1 to 2.0 µg/L for the different pharmaceuticals. Relative standard deviations were <26% for all compounds. The procedure was applied to samples from final effluent collected from wastewater treatment plants in Las Palmas de Gran Canaria (Spain), and two compounds were measured at 67 and 113 µg/L in one of them.

Development and application of a microwave-assisted extraction and LC/MS/MS methodology to the determination of antifouling booster biocides in sea mullets (Mugil cephalus) organisms.

A method is presented for the extraction, preconcentration, and determination of two commonly used booster biocides, Irgarol 1051 and diuron, in samples of muscle and liver tissues from Mugil cephalus by microwave-assisted extraction (MAE) followed by SPE for the preconcentration and cleanup step, coupled with LC/MS/MS. The optimum conditions for MAE were established as power 200 W and irradiation time 4 min. Using these conditions, the LOD was 0.13 ng/g for diuron and 0.10 ng/g for Irgarol 1051. The recoveries calculated at three concentration levels (0.5, 5, and 50 ng/g) were greater than 74%. Repeatability was less than 7.5% and reproducibility less than 12.7%. The optimized method was used to monitor these compounds in M. cephalus from different harbors of Gran Canaria Island. The samples were collected bimonthly and processed following the optimized method. High levels of Irgarol 1051 (6.9 +/- 1.03 ng/g) were found in the liver, while diuron was undetected. However, diuron was found in the muscle (1.41 +/- 0.45 ng/g). The proposed sentinel organism could be used in tropical and subtropical regions to continuously biomonitor for booster biocides over long periods of time. This technique could be a useful tool for improving the management of ocean and coastal waters.

Microextraction techniques coupled to liquid chromatography with mass spectrometry for the determination of organic micropollutants in environmental water samples.

Until recently, sample preparation was carried out using traditional techniques, such as liquid-liquid extraction (LLE), that use large volumes of organic solvents. Solid-phase extraction (SPE) uses much less solvent than LLE, although the volume can still be significant. These preparation methods are expensive, time-consuming and environmentally unfriendly. Recently, a great effort has been made to develop new analytical methodologies able to perform direct analyses using miniaturised equipment, thereby achieving high enrichment factors, minimising solvent consumption and reducing waste. These microextraction techniques improve the performance during sample preparation, particularly in complex water environmental samples, such as wastewaters, surface and ground waters, tap waters, sea and river waters. Liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS) and time-of-flight mass spectrometric (TOF/MS) techniques can be used when analysing a broad range of organic micropollutants. Before separating and detecting these compounds in environmental samples, the target analytes must be extracted and pre-concentrated to make them detectable. In this work, we review the most recent applications of microextraction preparation techniques in different water environmental matrices to determine organic micropollutants: solid-phase microextraction SPME, in-tube solid-phase microextraction (IT-SPME), stir bar sorptive extraction (SBSE) and liquid-phase microextraction (LPME). Several groups of compounds are considered organic micropollutants because these are being released continuously into the environment. Many of these compounds are considered emerging contaminants. These analytes are generally compounds that are not covered by the existing regulations and are now detected more frequently in different environmental compartments. Pharmaceuticals, surfactants, personal care products and other chemicals are considered micropollutants. These compounds must be monitored because, although they are detected in low concentrations, they might be harmful toward ecosystems.

Microwave-assisted extraction combined with on-line solid phase extraction followed by ultra-high-performance liquid chromatography with tandem mass spectrometric determination of benzotriazole UV stabilizers in marine sediments and sewage sludges.

Benzotriazole ultra-violet stabilisers are compounds widely used in personal care products, which can reach the environment after passing through wastewater treatment plants. In this work, we develop a novel method to evaluate the presence of seven compounds in marine sediments and sewage sludges using microwave-assisted extraction followed by a clean-up step based in on-line solid phase extraction coupled to ultra-high-performance liquid chromatography with MS/MS detection. This method allows for fast and efficient extraction from the solid matrix, subsequent automatic on-line purification and preconcentration, and analysis. For the optimised method, LOD were from 53.3 to 146 ng/kg and LOQ were in the range of 176-486 ng/kg. The method was validated for different environmental solid samples with satisfactory recoveries and relative standard deviations, between 46.1 and 83.9 and 7.8 and 15.5% (sludges) and 50.1 and 87.1% and 8.83 and 16.3% (sediments), respectively. Finally, the studied analytes were quantified in concentrations between 0.18 and 24.0 ng/g in real samples of marine sediments and sewage sludges from Gran Canaria Island (Spain).

Development of a sensitive determination method for benzotriazole UV stabilizers in enviromental water samples with stir bar sorption extraction and liquid desorption prior to ultra-high performance liquid chromatography with tandem mass spectrometry.

Benzotriazole UV stabilizers are emerging compounds used in personal care products and can enter surface water after passing through wastewater treatment plants without being removed. Because these analytes are strongly hydrophobic, there is an environmental risk of accumulation in solid matrices and magnification through the trophic chain. In this work, a method based on stir bar sorption extraction with liquid desorption is presented for the extraction of benzotriazole UV stabilizers from water samples. Stir bar sorptive extraction was combined with ultra-high performance LC with MS/MS detection. All important factors affecting the stir bar sorptive extraction procedure are discussed, and the optimized method was applied to seawater and wastewater samples from Gran Canaria Island, providing good selectivity and sensitivity with LODs and limits of quantification in the range of 18.4-55.1 and 61.5-184 ng/L, respectively. Recoveries between 68.4-92.2% were achieved for the more polar compounds, whereas the recoveries were lower for the two less polar compounds, most likely due to their strong absorption into the polydimethylsiloxane stir bar phase that does not allows the complete desorption. The repeatability studies gave RSDs of between 6.45 and 12.6% for all compounds in the real samples.

Assessment of the presence of UV filters and UV stabilizers in stranded dolphin blubber.

The presence of ultraviolet filters (UVFs) and stabilizers (UVSs) was evaluated for the first time in the common bottlenose dolphin (Tursiops truncatus). UVFs and UVSs are compounds of growing concern because their effects on the environment are not completely known. UVFs and UVSs are added to personal care products (PCPs), such as cosmetics and products related to sun care and once released to the aquatic ecosystem, marine organisms can bioaccumulate these substances. This work aimed to determine the presence of 12 UVFs and UVSs in cetacean blubber samples to assess the pollution to which these animals of the highest trophic chain levels are exposed due to human activity. Analytical determinations were carried out using a method based on microwave-assisted extraction combined with ultrahigh-performance liquid chromatography and tandem mass spectrometry detection. The developed method was successfully applied to determine the target compounds in the blubber tissues of five necropsied common bottlenose dolphins. Three of the 12 studied compounds, namely 2-ethylhexyl 2-cyano-3,3-diphenylprop-2-enoate (octocrilene, OC), 2-hydroxy-4-methoxybenzophenone (benzophenone 3, BP3) and 3-methylbutyl (E)-3-(4methoxyphenyl) prop-2-enoate (IMC), were detected in several samples. Of the identified compounds, OC was present in all the samples and at the highest concentration within the range from 52.61 ± 18.59 to 108.0 ± 11.32 ng·g-1.

Seafood consumption as a source of exposure to high production volume chemicals: A comparison between Catalonia and the Canary Islands.

Seafood plays an important role in diet because of its health benefits. However, the fact that chemical compounds such as high production volume chemicals may be present in seafood means that its consumption can be a potential risk for population. To assess the occurrence of HPVs and estimate the exposure and risk associated with their consumption, specimens of the most consumed seafood species in Catalonia and the Canary Islands, Spain, were collected and analysed. Results showed higher levels of HPVs in samples from Catalonia and a prevalence of phthalate esters and benzenesulfonamides over the other target compounds in samples from both locations. Multivariate analysis showed spatial differences between the mean concentration profiles of HPVs for the samples from Catalonia and the Canary Islands. Exposures were higher for the samples from Catalonia, although the intake of HPVs via seafood was not of any real concern in either of the locations.

On-line solid-phase extraction coupled to ultra-performance liquid chromatography with tandem mass spectrometry detection for the determination of benzotriazole UV stabilizers in coastal marine and wastewater samples.

Benzotriazoles are a group of UV absorbing compounds considered emerging contaminants that are used in different personal care products, and therefore, it is of high interest to develop sensitive and fast methods for investigating their presence in the environment. In this work, we present the development and application of a novel method based on on-line solid-phase extraction coupled to ultra-performance liquid chromatography with tandem mass spectrometry detection (SPE-UPLC-MS/MS) for the determination of seven benzotriazole UV stabilizers (BUVSs) in coastal marine and wastewater samples. This process is compared with a conventional off-line SPE procedure followed by UPLC-MS/MS. The parameters affecting the performance of the sample preparation and determination processes were evaluated. The results indicate that the on-line procedure provides for better sensitivity and reproducibility and is faster and easier than the off-line procedure. The detection limits and quantification limits achieved were in the range of 0.6-4.1 ng∙L(-1) and 2.1-14 ng∙L(-1) and relative standard deviation between 6.2 and 10%. The developed method was applied to coastal marine and wastewater samples from Gran Canaria Island (Spain). All of the BUVSs studied were detected in the samples from wastewater treatment plants and two were found in the seawater samples (UV P in the range of 2.8-4.4 ng∙L(-1) and UV 360 between 3.6 and 5.2 ng∙L(-1)).

Combination of microwave-assisted micellar extraction with liquid chromatography tandem mass spectrometry for the determination of fluoroquinolone antibiotics in coastal marine sediments and sewage sludges samples.

In this work, a method for the analysis of fluoroquinolone antibiotics using microwave-assisted micellar extraction combined with liquid chromatography-mass spectrometry detection has been developed. Different surfactants were tested for use as extractants in the isolation of the analytes from solid samples, and several experimental designs were evaluated for the determination and optimization of the variables that affect recovery from the matrix. Under optimal conditions, we obtained recoveries greater than 73% with relative standard deviations below 8%. Compounds were detected by liquid chromatography-electrospray ionization tandem mass spectrometry with detection limits between 0.15 and 0.55 ng g(-1) and quantification limits between 0.49 and 1.85 ng g(-1) . Finally, the optimized method was applied in the determination of antibiotics in real solid samples. Four fluoroquinolones (levofloxacin, norfloxacin, ciprofloxacin and enrofloxacin) were found in coastal marine sediments taken close to a marine outfall and in sewage sludge samples from a wastewater treatment plant. Concentrations ranged between 0.81 and 34.3 ng g(-1) in the sediments and 3.43 and 206.1 ng g(-1) in the sludge.

Determination and assessment of estradiol-mimicking compounds in the dissolved and particulate phases of wastewater treatment plant samples.

During the last two decades, a large number of publications have clearly shown that anthropogenic compounds that disrupt the endocrine system of wildlife species are a major cause for concern, and this concern has led to a demand for new screening methods. In this work, we have optimized and applied a new method to identify endocrine-disrupting chemicals (EDCs), such as nonylphenol, octylphenol, and their corresponding ethoxylates, 17alpha-ethynylestradiol, bisphenol-A, 17beta-estradiol, and estriol, in sewage samples. For the extraction and preconcentration of all analytes from the dissolved and particulate phases, we used SPE and ultrasonic assisted extraction, respectively. Identification and quantification were achieved by HPLC with fluorescence detection. Satisfactory LODs (between 0.5 and 7.6 ng/L in the dissolved phase and 12.3 and 21.4 ng/g in the particulate phase) and analyte recoveries (between 67 and 102%) were achieved for the target compounds. The optimized method was applied to the determination of EDCs in liquid sewage samples collected from July 2009 to July 2010 from a wastewater treatment plant in Las Palmas de G.C. (Spain). Concentrations of EDCs ranged from <10 to nearly 1300 ng/L in the dissolved phase, and from 0.1 to 7.7 microg/g in the suspended particulate matter.

Analysis of anti-inflammatory, analgesic, stimulant and antidepressant drugs in purified water from wastewater treatment plants using SPE-LC tandem mass spectrometry.

This work presents an effective sample preparation method for the evaluation of seven pharmaceutical compounds belonging to different therapeutic classes in purified water from wastewater treatment plants (WWTPs). The target compounds include caffeine (stimulant), nicotine (stimulant), atenolol (beta blocker), metamizole (anti-inflammatory and analgesic), fluoxetine (antidepressant), paraxanthine (stimulant) and clofibric acid (lipid regulator). Solid-phase extraction (SPE) and liquid chromatography-mass spectrometry (LC-MS) were selected as extraction and detection techniques, respectively. A detailed study of the experimental conditions of extraction was performed. Under optimal conditions, recoveries obtained were in the range of 21% to 100%, and the relative standard deviations were below 12%. The detection and quantification limits of the method were in the range 2.2-97.4 and 21.1-324.7 ng L(-1), respectively. The developed method was successfully applied to evaluate the presence of these pharmaceutical compounds in wastewaters samples from wastewater treatment plants located on the Gran Canaria Island (Spain). Most of the compounds were detected at concentrations up to 12.31 µg L(-1) in the WWTP influents that were studied.

Occurrence and environmental hazard of organic UV filters in seawater and wastewater from Gran Canaria Island (Canary Islands, Spain).

Organic ultraviolet (UV) filters are used in personal care products, but they are also added to industrial products and are constantly released to the environment. This study analyses the occurrence of 8 widely used organic UV filters in seawater from three beaches on the Gran Canaria Island (Spain) and in three wastewater treatment plants (WWTPs) by taking samples from influents and effluents. It also discusses the target compounds' post-treatment removal efficiencies. Sampling was carried out for 6 months and analytes were extracted by solid phase extraction with Sep-pak C18 cartridges. They were determined by ultra-high performance liquid chromatography coupled to mass spectrometry in tandem. The potential environmental hazard associated with the found concentrations was also assessed for marine organisms. Different target compounds were detected on the analysed beaches and in the wastewater. Benzophenone-3 (BP3) was the most recurrent compound in the seawater samples (frequency detection of 83%) and also in wastewater influents and effluents (measured in all the samples). However, the highest concentrations for seawater (172 µg L-1) and influent wastewater (208 µg L-1) corresponded to octocrylene, while methylene bis-benzotriazolyltetramethylbutylphenol was the compound most concentrated in secondary treatment effluent (34.0 µg L-1) and BP3 in tertiary treatment effluent (8.07 µg L-1). All the analysed samples showed that at least one target UV filter was present. Regarding the removal efficiencies of these compounds in the studied WWTPs, consistent differences between the target compounds were observed in influent concentration terms, where the average removal rates were higher than 50% for most of the compounds. Conventional treatment is unable to completely remove many studied compounds, while tertiary treatment acts as an additional elimination for some of them. An environmental hazard quotient above 1 was found for octocrylene, benzophenone-3 and 4-methylbenzylidene camphor, which indicates a potential high hazard for living species if these compounds are present.

Assessment of anthropogenic pollution by UV filters using macrophytes as bioindicators.

Marine environment pollution has increased in recent decades as a result of anthropogenic activities. Macrophytes can assimilate the compounds dissolved in the water and respond to changes in surround conditions, for that, they can be used as bioindicators of pollution in aquatic environments. Currently organic ultraviolet (UV) filters have shown ever-increasing in pollution levels in marine ecosystems. The anthropogenic pollution produced by eight organic ultraviolet (UV) filters in coastal macrophytes was studied. A microwave-assisted extraction (MAE), followed by ultrahigh-performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS) was applied to 76 macrophyte (seaweeds and seagrass) samples from three different beaches on the Gran Canaria Island (Spain), collected for 6 months. All studied UV filters were found with different detection frequencies from 16% to 100% in macrophyte samples. Octocrylene (OC) was detected in all the analysed samples throughout the sampling period. The highest concentration, 19,369 ng·g-1 dry weight (dw), was for this compound in the seagrass Cymodocea nodosa. The bioconcentration ratio was determined for several seaweed groups (red, brown, green). Different bioconcentration grades were obtained. Those above 1000 indicated significant accumulation, which increases the possibility of chronic effects on seaweed and at upper tropic levels.

Fabric Phase Sorptive Extraction of Selected Steroid Hormone Residues in Commercial Raw Milk Followed by Ultra-High-Performance Liquid Chromatography-Tandem Mass Spectrometry.

Hormones in edible matrices, such as milk, are a subject of concern because of their adverse effects on the endocrine system and cell signaling and the consequent disruption of homeostasis in human consumers. Therefore, the assessment of the presence of hormones in milk as potential endocrine-disrupting compounds is warranted. However, the complexity of milk as a sample matrix and the ultra-low concentration of hormones pose significant analytical challenges. Fabric phase sorptive extraction (FPSE) has emerged as a powerful analytical technique for the extraction of emerging pollutants from complex aqueous matrices. FPSE allows for substantially simplified sample handling and short extraction and desorption times, as well as the decreased use of organic solvents. It is considered a green alternative to traditional extraction methodologies. In this work, the FPSE technique was evaluated to perform the simultaneous extraction of 15 steroid hormones from raw milk without employing any sample pretreatment steps. Clean and preconcentrated hormone solutions obtained from FPSE of raw milk were analyzed using ultra-high-performance liquid chromatography-tandem mass spectrometry to achieve low detection limits, which ranged from 0.047 to 1.242 ng·mL-1. Because of the presence of many interferents in milk, such as proteins, lipids, and sugar, the effect of fat content on the extraction procedure was also thoroughly studied. Additionally, for the first time, the effect of lactose on the extraction of steroid hormones was evaluated, and the results showed that the extraction efficiencies were enhanced in lactose-free samples. Finally, the optimized methodology was applied to commercial samples of cow and goat milk, and no measurable concentrations of the studied hormones were detected in these samples.