Fate and distribution of benzotriazole UV filters and stabilizers in environmental compartments from Gran Canaria Island (Spain): A comparison study.

Tourism is an economic sector of great importance worldwide. In coastal areas, this activity is associated with the use of personal care products, such as ultraviolet (UV) filters and stabilizers. Therefore, assessing their presence and the exposure of living organisms to the impact of this kind of pollutant in such areas could be especially important. The Canary Islands (Spain) are considered an outermost region, and their main economic activity is based on tourism, both national and international. Thus, this area could be remarkably vulnerable to this kind of pollution, and its characterization could be useful to infer conclusions for other similar regions. With this aim, the occurrence of organic UV filters and stabilizers in different environmental matrices in Gran Canaria Island is presented in this work. Six benzotriazole compounds, UV-P, UV-326, UV-327, UV-328, UV-329 and UV-360, were found in wastewater, seawater, sludge, sediment, seaweed and fish samples. The numerous studies devoted to establishing the distribution of these target compounds in many different matrices on a touristic and particularly overcrowded island such as Gran Canaria can be used to understand the pollution situation in similar locations. The works in which determination procedures using different extraction techniques were optimized and validated for the analysis of liquid and solid samples are summarized. They are critically discussed regarding their characteristics and analytical parameters. This research is of interest to environmental managers specializing in the conservation of coastal areas where tourism is an important industry since the active components of UV filters and stabilizers can bioaccumulate and biomagnify in the trophic chain.

An assessment of the concentration of pharmaceuticals adsorbed on microplastics.

In the last decade, microplastics (MPs) have become an increasing cause for concerning. These particles are scattered throughout seas and oceans and have the capability of transporting adsorbed pollutants as pharmaceutical compounds, which can cause toxic effects and be transferred along the food chain. The development, optimization and validation of a sensitive and reliable analytical procedure for the extraction and determination of ten common pharmaceuticals adsorbed on MPs is reported in this study. This method involves ultrasound-assisted extraction coupled with ultra-high-performance liquid chromatography and tandem mass spectrometry. All of the variables included in the extraction process, such as the extraction time and type and solvent volume, were studied and optimised. Under optimal conditions, good reproducibility and repeatability, with relative standard deviations lower than 15% in most cases, were obtained while limits of detection between 0.25 and 15.8 ng g-1 were achieved. Last, the method was applied to the analysis of samples collected from beaches in the Canary Islands (Spain). The results indicated the presence of several analytes adsorbed on MPs in concentrations ranging from 34.0 to 111 ng g-1.

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).

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.

Analysis and occurrence of benzotriazole ultraviolet stabilisers in different species of seaweed.

Benzotriazole ultraviolet stabilisers (BUVSs) are emerging compounds used in personal care products and in other products, such as plastics, to absorb UV light. BUVSs have been described as bioaccumulative, persistent and toxic, so it is of great interest to understand their presence in the environment. Some marine organisms, such as seaweeds, have been used as bioindicators of contamination in the environment because they are able to accumulate metals and organic compounds. We have selected seaweeds to develop a novel method to extract, identify and determine six BUVSs (UV P, UV 326, UV 327, UV 328, UV 329, UV 360) based on microwave assisted extraction (MAE) and ultra-high-performance liquid chromatography with diode array (UHPLC-DAD) and mass spectrometry confirmation (UHPLC-MS/MS). Under optimum conditions, recoveries ranging from 49.8 to 92.3% were obtained, while intra-day and inter-day precision values were lower than 10% for most of the compounds. Limits of detection in the ranges 1.79-4.58 and 0.89-1.76 ng g-1 dry weight (dw) were obtained for UHPLC-DAD and UHPLC-MS/MS, respectively. The optimised method was applied for the analysis of twelve species of seaweed sampled during four months in 2018 from Las Canteras beach (Gran Canaria, Spain), with the results confirmed by UHPLC-MS/MS. UV 360 was found in concentrations between 42.5 and 115 ng g-1 (dw) in five of the twelve species. Although the highest concentrations were found in Asparagopsis taxiformis, the presence of UV 360 in other species could suggest that seaweeds can act as potential bioindicators of the occurrence of these compounds in the coastal environment.

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.

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.