The use of integrative tools and multiple models for aquatic environmental quality assessment: a case study of the Mirim Lagoon, Southern Brazil.

This study performed toxicity assays with microalgae, microcrustaceans, and fish as well as evaluated biochemical and behavioral biomarkers in fish and microcrustaceans to assess the quality of the surface water of Mirim Lagoon, which belongs to one of the largest hydrographic basins in the world, located in southern Brazil. Three distinct sampling periods were chosen (January, March, and June 2022) based on the rice plantation dynamics which is the main activity surrounding the lagoon. In January, the plantation is irrigated; in March, the water is drained into the Mirim Lagoon, and July is the off-season. Concerning toxicity tests, there was significant inhibition in microalgae growth when exposed to water collected in March, but no mortality was observed for Ceriodaphia dubia, Daphnia magna, and Danio rerio. Regarding biomarkers, behavioral variables contributed more to the higher values of the Integrated Biomarker Response (IBR) index for both D. magna and D. rerio, in March. The Redundancy Analysis (RDA) indicated a correlation between the biomarkers for both organisms and abiotic parameters, mainly nutrients (total phosphorus and total nitrogen), thermotolerant coliforms, total solids, and turbidity. Spatially, there was no difference during monitoring, but the most significant ecotoxicological effects were observed in March. Multivariate analysis and the IBR index proved to be useful tools for monitoring of water bodies such as Mirim Lagoon.

Distribution in marine fish and EDI estimation of contaminants of emerging concern by vortex-assisted matrix solid-phase dispersion and HPLC-MS/MS.

Due to their persistence or continuous discharge, toxic substances are present in the aquatic environment, and can bioaccumulate and biomagnify in the food web, generating a significant ecological risk and a threat to human health. The present study assess the occurrence and tissue (muscle, liver, stomach and gills) distribution of 59 anthropogenic contaminants of emerging concern (CECs) in marine fish from Brazil. A simpler and faster analytical methodology based on vortex-assisted matrix solid-phase dispersion (VA-MSPD) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was developed and validated. Limits of quantification ranged from 3.31 to 114 ng g-1 dw with recovery rates between 60 and 140 % and relative standard deviation below 20 %. The ultraviolet filters 4-hydroxybenzophenone (4HB) (benzophenone-3 metabolite) and benzocaine (Et-PABA), and the antibacterial salicylic acid were frequently accumulated in muscle and liver at concentrations between 39.5 and 21.0 ngg-1 dw. The determined concentrations resulted to be lower than the tolerable daily intake recommended by the European Food Safety Authority (EFSA).

Polycyclic Aromatic Hydrocarbons (PAHs) in honey from stingless bees (Meliponinae) in southern Brazil.

This study evaluated sixteen Polycyclic Aromatic Hydrocarbons (PAHs) considered priority pollutants by the United States Environmental Protection Agency (USEPA) in 13 honey samples from seven Meliponinae species, collected in native forests and industrial areas in southern Brazil. All samples contained at least one PAH. ∑PAHs ranged from 1.4 to 23.3 µg kg-1, where 23 % of samples were above the maximum allowed levels in dietary food for special medical purposes. Furthermore, the Excess Cancer Risk (ECR) ranged from 1.67 × 10-5 to 6.17 × 10-3, and 2.97 × 10-6 to 1.10 × 10-3, according to the Brazilian Institute of Geography and Statistics (IBGE) and Food and Agriculture Organization (FAO) daily intakes, respectively, being 61.54 % and 15.38 % of the samples above the threshold classified into sever by the USEPA. Results highlighted that honey has been affected by PAH contamination and that it has the potential to be used as an indicator of environmental pollution.

Updated knowledge, partitioning and ecological risk of pharmaceuticals and personal care products in global aquatic environments.

Over the last few decades, the occurrence of pharmaceuticals and personal care products (PPCPs) in aquatic environments has generated increasing public concern. In this review, data on the presence of PPCPs in environmental compartments from the past few years (2014-2022) are summarized by carrying out a critical survey of the partitioning among water, sediment, and aquatic organisms. From the available articles on PPCP occurrence in the environment, in Web of Science and Scopus databases, 185 articles were evaluated. Diclofenac, carbamazepine, caffeine, ibuprofen, ciprofloxacin, and sulfamethoxazole were reported to occur in 85% of the studies in at least one of the mentioned matrices. Risk assessment showed a moderate to high environmental risk for these compounds worldwide. Moreover, bioconcentration factors showed that sulfamethoxazole and trimethoprim can bioaccumulate in aquatic organisms, while ciprofloxacin and triclosan present bioaccumulation potential. Regarding spatial distribution, the Asian and European continents presented most studies on the occurrence and effects of PPCPs on the environment, while Africa and Asia are the most contaminated continents. In addition, the impact of COVID-19 on environmental contamination by PPCPs is discussed.

Vortex-assisted matrix solid-phase dispersion: An eco-friendly alternative for the determination of halogens in edible seaweed.

Edible seaweed has been widely consumed around the world through oriental cuisine and it is important to monitor the levels of some elements, especially halogens. This study proposes, for the first time, the development of an analytical method using the vortex-assisted matrix solid-phase dispersion (VA-MSPD) combined with alkaline extraction of halogens (F, Cl, Br, and I) in edible seaweed for further determination by ion chromatography. The proposed method was evaluated using edible seaweed of the Nori (Porphyra spp.) type and applied to samples of the Wakame (Undaria pinnatifida), Kombu (Laminaria ochroleuca), and Hijiki (Hizikia fusiformis) types. Important VA-MSPD parameters were investigated and using 0.1 g sample, 1 g sea sand as solid support, 50 mmol L-1 (NH4)2CO3 as extraction solution, and 5 min of maceration, higher extraction efficiencies were obtained. The method was linear within the evaluated range (R2 > 0.99) for all elements and no matrix effect was observed. The detection limits of the method were 27, 26, 19, and 28 µg g-1 for F, Cl, Br, and I, respectively. The accuracy was evaluated by a recovery test (ranging from 92 to 108%) and analysis of certified reference materials for apple leaves (NIST 1515) and peach leaves (NIST 1547), which had a good agreement (ranging from 97 to 101%) with the certified values. Comparing the results with those obtained by inductively coupled plasma-mass spectrometry after microwave-induced combustion, no significant difference was found between the results, and the relative standard deviations were lower than 12%. The proposed method proved to be efficient for the determination of halogens in different algae species, showing advantages such as simplicity and low cost, combined to the use of a material from renewable sources (sea sand) as a solid support, contributing to the principles of Green Analytical Chemistry.

Does pH variation influence the toxicity of organic contaminants in estuarine sediments? Effects of Irgarol on nematode assemblages.

Natural pH values in coastal waters vary largely among locations, ecosystems, and time periods; still, there is an ongoing acidification trend. In this scenario, more acidic pH values can alter bioavailability of organic contaminants, to organisms. Despite this, interactive effects between pH and chemical substances are not usually considered in Ecological Risk Assessment protocols. This study investigated the effects of pH on the toxicity of a hydrophobic organic compound on a benthic community using a microcosm experiment setup to assess the response of nematode assemblages exposed to environmentally relevant concentrations of Irgarol at two natural pH conditions. Estuarine nematode assemblages were exposed to two concentrations of Irgarol at pH 7.0 and 8.0 for periods of 7 and 35 days. Lower diversity of nematode genera was observed at the highest tested Irgarol concentration (1281 ± 65 ng.g-1). The results showed that the effects of Irgarol contamination were independent of pH variation, indicating no influence of acidification within this range on the toxicity of Irgarol to benthic meiofauna. However, the results showed that estuarine nematode assemblages are impacted by long-term exposure to low (but naturally occurring) pHs. This indicates that estuarine organisms may be under naturally high physiological pressure and that permanent changes in the ecosystem's environmental factors, such as future coastal ocean acidification, may drive organisms closer to the edges of their tolerance windows.

Emerging contaminants in Brazilian aquatic environment: identifying targets of potential concern based on occurrence and ecological risk.

Although studies have shown the presence of Contaminants of Emerging Concern (CECs) in the Brazilian environment in recent decades, several biological effects on the aquatic ecosystem are unknown. Brazil is the fifth largest country in extension in the world, and its wide territory presents geographic regions with diverse demographic and economic characteristics. In order to identify targets of potential concern based on occurrence and ecological risk, available data from previous studies were examined to conduct environmental risk analysis and provide a ranking of CECs in Brazilian aquatic environment based on environmental concentration measured in the last 10 years. The results indicate that 17α-ethynylestradiol, 17ß-estradiol, acetaminophen, Bisphenol A, caffeine, diclofenac, ibuprofen, methylparaben, sulfamethoxazole and triclosan are the CECs that represent the greatest threats to the Brazilian environment. Therefore, these contaminants should be considered as a priority in future monitoring studies. Besides, identification of target monitoring compounds can facilitate the selection of pollutant candidates in future legislations.

Meliponinae and Apis mellifera honey in southern Brazil: Physicochemical characterization and determination of pesticides.

This study evaluated the physicochemical parameters and the occurrence of pesticides in multi-flower honey produced by six species of Meliponinae and Apis mellifera and collected in different seasons, floral species and sites in southern Brazil. Meliponinae honey were found to exhibit higher moisture, free acidity and sucrose concentration and lower concentration of reducing sugars than the standard of Apis mellifera honey in Brazil. Regarding Apis mellifera honey, reducing sugars and sucrose did not comply with the legislation. The Principal Component Analysis (PCA) showed that most of the composition variability was defined by free acidity, moisture, soluble solids, fructose, glucose, and reducing sugars. Determination of pesticides was carried out by the citrate QuEChERS method and gas chromatography tandem mass spectrometry (GC-MS/MS). However, no pesticide residues at concentrations above the limit of quantification were found in the twenty honey samples. Results show that this region has the potential to produce honey.

Rapid and cost-effective multiresidue analysis of pharmaceuticals, personal care products, and antifouling booster biocides in marine sediments using matrix solid phase dispersion.

Currently, there are many contaminants of concern that need to be accurately determined to help assess their potential environmental hazard. Despite their increasing interest, yet few environmental occurrence data exist, likely because they are present at low levels and in very complex matrices. Therefore, multiresidue analytical methods for their determination need to be highly sensitive, selective, and robust. Particularly, due to the trace levels of these chemicals in the environment, an extensive extraction procedure is required before determination. This work details the development of a fast and cheap vortex-assisted matrix solid-phase dispersion-high performance liquid chromatography tandem-mass spectrometry (VA-MSPD-HPLC-MS/MS) method for multiresidue determination of 59 contaminants of emerging concern (CECs) including pharmaceuticals, personal care products, and booster biocides, in sediment. The validated method provided high sensitivity (0.42-36.8 ngg-1 dw quantification limits), wide and good linearity (r2 > 0.999), satisfactory accuracy (60-140%), and precision below 20% for most target analytes. In comparison with previous methods, relying on traditional techniques, the proposed method demonstrated to be more environmentally friendly, cheaper, simpler, and faster. The method was applied to monitor the occurrence of these compounds in sediments collected in Brazil, using only 2 g dw sediment samples, free-solid support, and 5 mL methanol as extraction solvent. The UV filter avobenzone, the UV stabilizer and antifreeze methylbenzotriazole, the preservative methylparaben, the fluoroquinolone antibiotic ciprofloxacin, and the biocides irgarol and 4,5-dichloro-2-octyl-4-isothiazolin-3-one were determined at concentrations in the range 1.44-69.7 ngg-1 dw.

Effect of the UV filter, Benzophenone-3, on biomarkers of the yellow clam (Amarilladesma mactroides) under different pH conditions.

This work aimed to investigate effects of the ocean contamination by the sunscreen Benzophenone-3 (BP3) and acidification, caused by CO2 enrichment, to the yellow clam, Amarilladesma mactroides. Biochemical biomarkers were analyzed in tissues (gills, digestive gland, and mantle) of clams exposed to the environmental concentration of 1 µg/L BP3, at seawater natural pH (pH 8.1) and at lower pH (pH 7.6). The tissues responded in different ways considering their physiological roles. In general, BP3 altered activity of the enzymes, glutathione-S-transferase (GST) and glutathione cysteine ligase (GCL); but mostly increased the level of glutathione (GSH). These effects were enhanced by acidification, without augmenting lipid peroxidation (LPO). Carbonic anhydrase activity (CA) increased after BP3 exposure in the digestive gland and decreased in the gills at pH 7.6, while Ca2+-ATPase activity was affected by acidification only. Changing levels of these enzymes can alter shell formation and affect the bivalve maintenance in impacted environments.

Pharmaceuticals and personal care products in a Brazilian wetland of international importance: Occurrence and environmental risk assessment.

Despite the fact that the occurrence of emerging contaminants in the environment has become frequent in recent decades, the seasonal dynamics of contaminants in different environmental compartments are little studied in protected areas influenced by effluent discharges. In this study, the seasonal and spatial occurrence of 33 pharmaceuticals and personal care products (PPCPs) was investigated in surface waters and sediments from Anil and Bacanga rivers (northeast of Brazil). The studied area is located within a Wetland of International Importance by Ramsar Convention (Amazon Estuary and its Mangroves). Sample preparation was carried out using solid-phase extraction and QuEChERS, for water and sediment samples, respectively and all determinations were performed by liquid chromatography tandem mass spectrometry. Eleven PPCPs were detected in water samples and 14 in sediments. In aqueous samples, caffeine was the most occurring compound reaching 13,798 ng L-1. In addition, high levels of acetaminophen, ibuprofen, sulfamethoxazole, carbamazepine and diclofenac were also observed. In the sediment samples, triclocarban, benzophenone-3, ketoconazole and methylparaben were also detected. The spatial and temporal distribution of the assessed molecules indicates urbanization and anthropic activities as relevant sources of PPCPs in the region. Moreover, the levels of acetaminophen, caffeine, diclofenac, ibuprofen, benzophenone-3, triclosan and triclocarban measured within the Ramsar site pose a high risk to aquatic and terrestrial organisms. These findings indicate potential threats to the allegedly protected biodiversity and, therefore, urgent actions are needed to effectively protect this unique and vulnerable area.

Impacts of the biocide chlorothalonil on biomarkers of oxidative stress, genotoxicity, and sperm quality in guppy Poecilia vivipara.

Chlorothalonil is a fungicide present in antifouling paints and other formulations used in agriculture, although studies have shown this chemical to be toxic to fish species. To clarify the deleterious effects of chlorothalonil for these non-target organisms, the present study evaluated the toxic effects of this biocide for the estuarine guppy Poecilia vivipara in terms of an acute mortality test (96 h) and the analysis of biomarkers of oxidative stress, genotoxicity, and sperm quality. The LC50 calculated for P. vivipara was 40.8 µg/L of chlorothalonil. For the analysis of biomarkers, fish were exposed (96 h) to 1 and 10 µg/L of chlorothalonil. It was observed that chlorothalonil alters the levels of pro- and antioxidants towards oxidative stress. In the gills, a negative effect on total antioxidant capacity (ACAP) was detected, while there was a reduction in the activity of glutathione S-transferase (GST) in the liver. However, levels of glutathione (GSH) and the activity and glutamate-cysteine-ligase (GCL) increased in both tissues, as a possible detoxification response. Following chlorothalonil exposure, oxidative damage measured by lipoperoxidation (LPO) significantly increased at the cellular level only (red blood cells (RBCs) and sperm cells). An increase in fluidity of membranes, reactive oxygen species concentration and micronuclei (MNs) incidence were also seen in RBCs. In sperm cells, LPO increased, while membrane and mitochondrial functionality as well as sperm motility decreased. Based on these results, chlorothalonil can be considered as a toxic compound for fish, causing genotoxicity and affecting the RBCs physiology and the fertility of males of P. vivipara.

Fast and simple method of simultaneous preservative determination in different processed foods by QuEChERS and HPLC-UV: Method development, survey and estimate of daily intake.

A fast and simple method, which employs QuEChERS and HPLC-UV, was developed to determine preservatives in processed foods from different classes. The method showed correlation coefficients above 0.99, LOQs between 0.13 and 0.33 mg kg-1 and recoveries between 91 and 107%, with RSD ≤ 5.3%. Levels of preservatives were up to 2040 mg kg-1 for benzoates, up to 3185 mg kg-1 for sorbates and up to 452 mg kg-1 for methylparaben. Only four out of 82 samples under analysis were above the maximum level allowed by the legislation. Additionally, daily intakes of preservatives were estimated. Regarding benzoates, relatively high intakes were estimated (25% of the acceptable daily intake - ADI) in comparison with sorbates (5% of ADI) and parabens (<1% of ADI), when mean consumption is considered. This method is a good alternative to determining preservatives in different food samples.

An integrated approach in subtropical agro-ecosystems: Active biomonitoring, environmental contaminants, bioaccumulation, and multiple biomarkers in fish.

Aquatic contamination in agricultural areas is a global problem, characterized by a complex mixture of organic and inorganic pollutants whose effects on biota are unpredictable and poorly investigated. In this context, in the present study, the Neotropical fish Prochilodus lineatus was confined in situ for 120 days in two sites with different levels of anthropic impact: 1) a fish hatchery station, within the State University of Londrina (reference site - REF) and 2) an agro-ecosystem area in one of the most productive regions of southern Brazil (experimental site - EXP). We evaluated multiple biomarkers at different levels of biological organization, such as biotransformation and antioxidant enzymes, oxidative damages, DNA damages and liver histopathology. We also evaluated the occurrence of 22 organochlorine pesticides (OCPs) and 6 trace metals in water and sediment; and 33 current-use pesticides (CUPs) in the water; besides the presence of OCPs in the liver and metals in different tissues of the confined fish. The chemical analysis confirmed that the two environments presented different levels of contamination. We verified a distribution gradient of data in the principal component analysis (PCA), separating the REF fish to one side and the fish at the agricultural area (EXP) to the other side. In general, the biomarker responses were more altered in fish from the EXP than fish from the hatchery station; and this fish presented a greater accumulation of endosulfan (an increase of 18× compared to basal value) and showed oxidative, genetic, and histological damage. Through the Biomarkers Response Index (BRI), we found that the EXP fish demonstrated a decrease in health status compared with the REF fish during the confinement time, due to their exposure to a higher concentration of contaminants. In conclusion, the use of multiple biomarkers at different response levels is an important tool for environmental monitoring.

Trace analysis of parabens preservatives in drinking water treatment sludge, treated, and mineral water samples.

Parabens have been widely used as antimicrobial agents, mainly in food products, pharmaceuticals, and cosmetics. Although they are known as safe preservatives, they also cause some harm to human health, which has been discussed lately. Therefore, the aim of this study was to evaluate the occurrence of nine parabens (including isomers) in mineral and drinking waters, besides in drinking water treatment sludge (DWTS) samples with determination by liquid chromatography tandem mass spectrometry (LC-MS/MS). Both methods solid phase extraction (SPE) and QuEChERS were validated. Calibration curves showed a correlation coefficient of 0.99 for all compounds. LOQ values ranged from 0.04 to 4 µg L-1 in aqueous matrices and from 5 to 500 ng g-1 in DWTS. Recoveries between 70 and 115% were reached with RSD below 20% for all compounds in SPE whereas recoveries between 62 and 119% were found with RSD below 20% for almost all compounds in QuEChERS. Matrix effect had low values (< 20%); it was only above 20% for methylparaben in the SPE and for pentylparaben in the QuEChERS. Using a quick and simple extraction procedures with SPE, QuEChERS, and LC-MS/MS analyses, these methods proved to be selective and sensitive. They were successfully applied to real samples (treated water, mineral water, and sludge), and methylparaben was detected at concentration levels below 0.242 µg L-1 in mineral and treated water samples and 10 ng g-1 in DWTS samples.

The herbicide atrazine affects sperm quality and the expression of antioxidant and spermatogenesis genes in zebrafish testes.

The herbicide atrazine (ATZ) is used worldwide in the control of annual grasses and broad-leaved weeds. The present study evaluated sperm quality parameters in zebrafish Danio rerio after 11-day exposure to nominal ATZ concentrations of 2, 10, and 100 µg L-1. All ATZ concentrations caused a decrease in motility, mitochondrial functionality, and membrane integrity, as measured using conventional microscopy or fluorescence microscopy with specific probes. The DNA integrity of sperm was not affected. The levels of expression of genes related to spermatogenesis, antioxidant defenses, and DNA repair were also investigated using RT-qPCR. The ATZ caused transcriptional repression of the spermatogenesis-related genes SRD5A2 and CFTR, the antioxidant defense genes SOD2 and GPX4B, and the DNA repair gene XPC. This is the first study to show that environmentally relevant concentrations of ATZ significantly affect the sperm quality in fish, possibly resulting in reduced fertility rates. In addition, we showed that the repression of genes related to spermatogenesis and cellular defense could be part of the mechanisms involved in the ATZ toxicity in the testes of male fish.

Chitosan from shrimp shells: A renewable sorbent applied to the clean-up step of the QuEChERS method in order to determine multi-residues of veterinary drugs in different types of milk.

Clean extracts are essential in LC-MS/MS, since the matrix effect can interfere in the analysis. Alternative materials which can be used as sorbents, such as chitosan in the clean-up step, are cheap and green options. In this study, chitosan from shrimp shell waste was evaluated as a sorbent in the QuEChERS method in order to determine multi-residues of veterinary drugs in different types of milk, i. e., fatty matrices. After optimization, the method showed correlation coefficients above 0.99, LOQs ranged between 1 and 50µgkg-1 and recoveries ranged between 62 and 125%, with RSD<20% for all veterinary drugs in all types of milk under study. The clean-up step which employed chitosan proved to be effective, since it reduced both the matrix effect (from values between -40 and -10% to values from -10 to +10%) and the extract turbidity (up to 95%). When the proposed method was applied to different milk samples, residues of albendazole (49µgkg-1), sulfamethazine (

Environmentally friendly procedure based on VA-MSPD for the determination of booster biocides in fish tissue.

Booster biocides have been widely applied to ships and other submerged structures. These compounds can be released into the marine environment as the result of vessel hull leaching and may remain in different environmental compartments. This study aimed at introducing an environmentally friendly procedure for the extraction of irgarol and diuron from fish samples by vortex-assisted matrix solid phase dispersion (VA-MSPD) with detection by liquid chromatography tandem mass spectrometry. Different types of solid supports and solvents were evaluated. The best results were found when 0.5g mussel shell, 0.5g sodium sulfate and 5mL ethanol were used. Analytical recoveries ranged from 81 to 110%, with RSD below 10%, whereas the matrix effect was between -17 and 1% (for all samples under study). LOQ values of irgarol and diuron were 5 and 50ngg-1, respectively. The method under investigation proved to be a promising alternative to controlling contamination of fish by booster biocides, with low consumption of biodegradable reagents.

From TBT to booster biocides: Levels and impacts of antifouling along coastal areas of Panama.

Antifouling biocides in surface sediments and gastropod tissues were assessed for the first time along coastal areas of Panama under the influence of maritime activities, including one of the world's busiest shipping zones: the Panama Canal. Imposex incidence was also evaluated in five muricid species distributed along six coastal areas of Panama. This TBT-related biological alteration was detected in three species, including the first report in Purpura panama. Levels of organotins (TBT, DBT, and MBT) in gastropod tissues and surficial sediments ranged from <5 to 104 ng Sn g-1 and <1-149 ng Sn g-1, respectively. In addition, fresh TBT inputs were observed in areas considered as moderate to highly contaminated mainly by inputs from fishing and leisure boats. Regarding booster biocides, TCMTB and dichlofluanid were not detected in any sample, while irgarol 1051, diuron and DCOIT levels ranged from <0.08 to 2.8 ng g-1, <0.75-14.1 ng g-1, and <0.38-81.6 ng g-1, respectively. The highest level of TBT (149 ng Sn g-1) and irgarol 1051 (2.8 ng g-1), as well as relevant level of DCOIT (5.7 ng g-1), were detected in a marina used by recreational boats. Additionally, relatively high diuron values (14.1 ng g-1) were also detected in the Panama Canal associate to a commercial port. DCOIT concentrations were associated with the presence of antifouling paint particles in sediments obtained nearby shipyard or boat maintenance sites. The highest levels of TBT, irgarol 1051, and diuron exceeded international sediment quality guidelines indicating that toxic effects could be expected in coastal areas of Panama. Thus, the simultaneous impacts produced by new and old generations of antifouling paints highlight a serious environmental issue in Panamanian coastal areas.

Antifouling booster biocide extraction from marine sediments: a fast and simple method based on vortex-assisted matrix solid-phase extraction.

This paper reports the development of an analytical method employing vortex-assisted matrix solid-phase dispersion (MSPD) for the extraction of diuron, Irgarol 1051, TCMTB (2-thiocyanomethylthiobenzothiazole), DCOIT (4,5-dichloro-2-n-octyl-3-(2H)-isothiazolin-3-one), and dichlofluanid from sediment samples. Separation and determination were performed by liquid chromatography tandem-mass spectrometry. Important MSPD parameters, such as sample mass, mass of C18, and type and volume of extraction solvent, were investigated by response surface methodology. Quantitative recoveries were obtained with 2.0 g of sediment sample, 0.25 g of C18 as the solid support, and 10 mL of methanol as the extraction solvent. The MSPD method was suitable for the extraction and determination of antifouling biocides in sediment samples, with recoveries between 61 and 103% and a relative standard deviation lower than 19%. Limits of quantification between 0.5 and 5 ng g-1 were obtained. Vortex-assisted MPSD was shown to be fast and easy to use, with the advantages of low cost and reduced solvent consumption compared to the commonly employed techniques for the extraction of booster biocides from sediment samples. Finally, the developed method was applied to real samples. Results revealed that the developed extraction method is effective and simple, thus allowing the determination of biocides in sediment samples.