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.

A broad-spectrum fungicide, dichlofluanid is widely used in antifouling paints and agricultural pesticides. In this study, the acute and chronic effects of sublethal concentrations, namely, no observable effect concentration (NOEC) and 50% lethal concentration (LC₅₀) of dichlofluanid (1/10 NOEC, NOEC, 1/10 LC₅₀, and LC₅₀) were evaluated on the marine mysid, Neomysis awatschensis. Acute toxicity test (96 h) showed higher sensitivity to dichlofluanid in juvenile mysids (LC₅₀ 3.1 μg L⁻¹) than adults (LC₅₀ 24.5 μg L⁻¹), with lower survival rate and reduction in food consumption. Exposure with dichlofluanid considerably induced oxidative imbalance, as NOEC (0.006 μg L⁻¹ for juveniles and 0.074 μg L⁻¹ for adults) and 1/10 LC₅₀ values increased intracellular concentrations of malondialdehyde and glutathione, and the enzymatic activities of catalase and superoxide dismutase, whereas exposure to LC₅₀ value decreased the values of oxidative parameters. Enzymatic activity of acetylcholinesterase decreased considerably when exposed to LC₅₀ value. In the case of chronic effects, exposure to NOEC for 4 weeks markedly decreased the juvenile survival rate, while adults showed tolerance. Multigenerational monitoring in response to NOEC showed a significant growth retardation with an increase in intermolt duration as well as a decrease in the number of newborn mysids from females of the third generation. Consistent exposure to environmentally relevant sublethal concentrations of dichlofluanid would be detrimental to mysid individuals and the survival of the mysid population.

Elasmobranchs are particularly prone to accumulating contaminants due to their life history patterns and relatively high trophic position. However, several compounds, especially contaminants of emerging concern, have still not been well studied in this group. Here, we aimed to determine the occurrence and concentrations of several inorganic and organic contaminants in different tissues of the Brazilian guitarfish Pseudobatos horkelii. This species is a critically endangered species, endemic from the Southwest Atlantic which uses southern Brazilian waters as a nursery habitat. Polycyclic aromatic hydrocarbons (PAHs), emerging pesticides, pharmaceutical and personal care products (PPCPs) and trace metals were determined in five biological tissues in order to assess the accumulation and organotropism of these compounds. Except for chlorothalonil and triclosan, all compounds were detected in, at least, one tissue, mostly in liver samples. All compounds differed among tissues, with liver presenting the higher concentrations of several contaminants, followed by muscle and gills. PAHs and PPCPs were the most detected analytes and presented the highest concentrations among tissues. Diclofenac levels were determined, for the first time in elasmobranchs, and were relatively high, when compared to other fishes. Finally, relatively high concentrations of PAHs, dichlofluanid and octocrylene in muscle might be suggestive of chronic exposure, presenting also human health implications. Regarding trace metals, contrary to most elasmobranch studies, Hg levels were low in all tissues, whereas Cd and Pb here higher in liver, and gills and blood samples, respectively. Our results indicate that P. horkelii is exposed to several organic and inorganic which might affect this species in a long-term scale. Concerning the determination of emerging contaminants, it is likely that other elasmobranchs are also exposed to these compounds and special attention should be given to this issue in order to predict future effects on this group.

Fouling organisms fix and grow on submerged surfaces and may cause several economic losses. Thus, antifouling biocides have been introduced in antifouling paints in order to avoid this phenomenon. However, their widespread use became a global problem, since these substances can be highly toxic to non-target organisms, mainly in high boat traffic areas. The occurrence and environmental behavior of antifouling biocides are especially unknown in areas of ecological relevance, as Amazonian and pre-Amazonian regions. Thus, the aim of this work was to evaluate, for the first time, levels and the partitioning behavior of the antifouling organic biocides irgarol, diuron and also stable degradation products of dichlofluanid and diuron (DMSA and DCPMU, respectively) in sediments and porewaters from a high boat traffic area located in the Northeast of Brazil. Our results showed high concentrations of irgarol and diuron in sediments, and their contamination patterns suggested that misuse and discard of antifouling residues contribute for a serious risk in this environment. Additionally, DCPMU and DMSA were detected for the first time in porewaters of the Brazilian coast. This work represents one of the few registers of contamination, especially by antifouling substances, in Amazonian areas, despite their environmental relevance.

The contamination by antifouling biocide residues (booster biocides - diuron, Irgarol, chlorothalonil, dichlofluanid and DCOIT; butyltin compounds-BTs (TBT, DBT and MBT); and antifouling paint particles-APPs) was appraised in sediments of Vitoria Estuarine System (VES). Even at its historical lower (ΣBTs ≤113 ng Sn g⁻¹ dry wt), the current environmental levels of BTs in areas with a predominance of boatyards still pose a risk to the local biota and human population. DCOIT, among booster biocides, was the most frequently detected, especially in boatyards (≤40 ng g⁻¹ dry wt) and Vitoria Port (64 ng g⁻¹ dry wt), while APPs were also detected mainly in sediments of boatyards (≤5,969 μg g⁻¹ dry wt). Since levels of diuron and DCOIT in APPs were as high as 1,670,000 and 899,000 ng g⁻¹ dry wt, respectively, they are acting as secondary sources of these antifouling biocides. Therefore, VES is threatened by antifouling biocide residues due to the multiple diffuse sources of contamination, showing the need for more efforts on public policies (including temporal trend monitoring studies).

The occurrence and distribution of tributyltin (TBT) and alternative biocides were investigated in sediment from semi-enclosed bays, fishing ports, and large commercial harbors in Korea. Extremely high concentration of TBT (55,264ngSn/g) was detected near a large shipyard, even after a total ban on its use in Korea. Diuron was the biocide with the highest detection frequency and concentration levels, followed by Irgarol 1051. Sea-Nine 211 was detected at 3 of 32 stations surveyed. Dichlofluanid, zinc and copper pyrithiones levels were below the detection limits at all the stations surveyed. The relatively high levels of Diuron (9–62.3ng/g) and Irgarol 1051 (1.5–11.5ng/g) were detected in harbor and shipyard areas. Diuron and Irgarol 1051 levels including TBT in sediments from hot spots in Korea exceeded global sediment quality guidelines.

Dichlofluanid is a fungicide employed as a booster biocide in antifouling paints, but information its toxicity to aquatic organisms is scarce. This study aims to evaluate biomarker responses in the mussel Perna perna exposed to dichlofluanid. Mussels were exposed to 0 (control), 0.1 μg/L (environmental concentration), 10, and 100 μg/L of dichlofluanid for 24 and 96 h. Byssus formation, oxygen consumption, and oxidative stress response were evaluated in gills and digestive glands. The results demonstrated that even the lowest dichlofluanid concentration causes a reduction in byssus biomass and water content. The higher concentrations caused an acute increase in oxygen consumption, which only returned to control levels after 96 h of exposure. ACAP levels and antioxidant enzyme activities were affected in both tissues with a larger effect observed in gill tissues as demonstrated by the IBR index. The overall results demonstrated that environmentally relevant concentrations of dichlofluanid would be deleterious to aquatic organisms.

The toxicity of the antifouling biocides Irgarol 1051, Diuron, Chlorothalonil, Dichlofluanid, Sea-nine 211, Copper pyrithione, Zinc pyrithione, Ziram and Zineb were evaluated on Nitzschia pungens and Artemia larvae. Results showed that EC50 for Irgarol 1051 was 0.586μgl−1 was the strongest effect on N. pungens following by Copper pyrithione (4.908μgl−1), Ziram (5.421μgl−1), Zinc pyrithione (5.513μgl−1), Diuron (6.640μgl−1), Zineb (232.249μgl−1), Sea-nine 211(267.368μgl−1), Chlorothalonil (360.963μgl−1) and Dichlofluanid (377.010μgl−1) in 96h. In Artemia larvae, the biocides were evaluated the LC50 for larval survivals at 48h. Sea-nine 211 and Copper pyrithione were 0.318 and 0.319mgl−1. Chlorothalonil, Zinc pyrithione and Ziram were 2.683, 3.147 and 4.778mgl−1. Irgarol 1051, Diuron, Zineb and Dichlofluanid were 9.734, 30.573, 41.170 and 154.944mgl−1. These results provide baseline data concerning the toxicity of antifouling biocides against marine environment.

Since the ban on tributyltin (TBT) in 2008, dozens of alternative antifouling agents have been used instead. Unfortunately, these alternative antifouling agents contain diverse toxic components, which have contaminated the coasts. From 2006 to 2013, the concentration of chlorothalonil, dichlofluanid, and Irgarol 1051 were monitored continuously, and their mean concentrations increased due to the increase in maritime cargo and consequent increase in the incoming and outgoing ships in harbors. An analysis of the sampling points according to harbor type showed that the contamination was more severe in fishing and big harbors, where there are more incoming and outgoing ships. A correlation analysis indicated a high correlation between chlorothalonil and dichlofluanid. Unlike Irgarol 1051, which is only used as an antifouling agent, the other two substances are used as agricultural chemicals as well, which could explain the high correlation. This study suggests that these alternative antifouling agents should be tracked continuously.

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.