Organotin compounds and booster biocides remain persistent contaminants in coastal environments despite international restrictions. This study presents the first integrated assessment of butyltins, phenyltins, and selected booster biocides (Irgarol/Cybutryne, DCOIT, diuron, and dichlofluanid) in sediments and six gastropod species from the Colombian Caribbean coast, using GC–MS and LC–MS/MS. Sediment contamination was highest in Cartagena, particularly in marinas (ΣBTs: 186 ± 121 ng Sn g⁻¹), harbors (232 ± 217 ng Sn g⁻¹), and industrial areas (106 ± 35 ng Sn g⁻¹). Lower concentrations were observed in Santa Marta (15.4 ± 6.4 ng Sn g⁻¹), the Gulf of Morrosquillo (35 ± 50 ng Sn g⁻¹), and Barranquilla (

Biofouling presents severe economic challenges for maritime transport, prompting the widespread application of antifouling paint formulations (APFs). However, the subsequent leaching of active ingredients, including banned organotin compounds (OTs) and modern booster biocides (BBs), threatens non-target aquatic organisms. This study utilized silicone rubber-based passive sampling to determine the time-weighted average freely dissolved concentrations (Cw) of OTs and BBs in the water column at the entrance of the main navigation channel of the Vitória Estuarine System (VES), SE Brazil, over two years. OTs concentrations ranged from ≥0.02 to 0.3 ng Sn L-1 for TBT, 0.1 to 0.4 ng Sn L-1 for DBT, and 0.5 to 1.8 ng Sn L-1 for MBT, while TPhT, DPhT, and MPhT remained below the limit of detection (

This study constitutes the most comprehensive assessment of imposex along the Portuguese coast. It is based on a 22-year biomonitoring program using Nucella lapillus and Tritia reticulata, comparing new measurements from 2022 with historical data collected at the same locations. Since the EU ban on organotin (OT) antifouling (AF) systems in 2003, the intensity of imposex and OT tissue concentrations have declined in both species; however, in 2022, imposex remained widespread, with moderate to high levels still recorded in several areas. N. lapillus met the OSPAR Ecological Quality Objective (EcoQO) at all sampled sites, whereas T. reticulata failed to meet this target at 44% of the locations. This contrast reflects species distribution: T. reticulata inhabits a broader range of habitats, including more contaminated areas, making it a more effective bioindicator of OT pollution along the entire coast. Despite OT-based AF systems being banned on small vessels in 1993 by the Directive 89/677/EEC - nearly three decades before the current survey - and banned on all vessels in 2003 by the Regulation (EC) No. 782/2003, TBT continues to cause imposex, particularly in areas dominated by small-boat activity. These findings indicate spatially heterogeneous recovery patterns and suggest that vessel-size-dependent management and monitoring frameworks may influence post-ban environmental outcomes. Strengthened monitoring strategies targeting small-vessel-dominated areas may therefore support more effective long-term recovery.

Extreme climatic events can trigger severe flooding, with the post-event period characterized by enhanced atmospheric dust resuspension. In this study, transplants of the bromeliad Tillandsia usneoides were used to evaluate the temporal (15 and 45 days of exposure: 50 samples) and spatial (five regions: 25 sites) patterns of atmospheric contamination during the subsequent dry post-flood period in southern Brazil. Twelve elements, including those of greatest toxicological concern, arsenic, cadmium, lead, and mercury, were analyzed by atomic absorption spectrometry, while particulate matter (PM2.5, PM10, and PM > 10) was assessed by scanning electron microscopy. Significant increases (p < 0.05) in median concentrations between 15 and 45 days were recorded for aluminium (134 and 264 mg kg−1), copper (1.39 and 1.59 mg kg−1), iron (44.4 and 84.5 mg kg−1), and manganese (2.96 and 4.95 mg kg−1). The Exposed-to-Control ratio revealed increases for arsenic (South Region: 2.88), and for cadmium and nickel (Central Region: 3.27 and 2.67, respectively). The modified Degree of Contamination index identified the Metropolitan Region, the South Region, and the Taquari Valley as the most contaminated by trace elements, whereas the Mountain Region, which was not directly affected, was the least contaminated. Flood-affected regions were dominated by inhalable particles (PM2.5-PM10: 96–100%), whereas the non-affected Mountain Region showed a relatively higher contribution of super-coarse particles (PM > 10: 11%). These results show that extreme hydrometeorological events can increase human exposure to atmospheric contamination, highlighting the importance of biomonitoring in climate-impacted regions.

The antifouling booster biocides are frequently studied for toxic effects on the aquatic ecosystems. The present investigation proposes passive silicone rubber samplers as a collection method for biocides, once these methods can concentrate substances in aqueous matrices at very low levels. Through the passive sampler-water partition coefficient (Ksw) and the analyte chemical nature, we can optimize their extraction from the membrane to apply in the sample medium. We used the co-solvent method to determine the Ksw of three third-generation antifouling biocides, chlorothalonil, dichlofluanid, and dichlorooctylisothiazolinone (DCOIT), with log Ksw = 2.24, 4.01, and 2.38, respectively. Improving extraction also led to a recovery range higher than 70%, determinations were carried out by gas chromatography with an electron capture detector. Biocides concentration in seawater samples from Itaqui port (São Marcos Bay, northern Brazil) ranged from 0.058 to 0.72 μg L-1 for chlorothalonil, 0.001 to 0.008 μg L-1 for dichlofluanid, and 0.018 to 0.64 μg L-1 for DCOIT.

Contamination by antifouling paint residues (TBT, DBT, MBT, diuron, Irgarol, chlorothalonil, dichlofluanid, DCOIT, and antifouling paint particles (APPs)) was assessed in 113 sediments from 10 regions under the influence of maritime activities (boats/shipyard, traffic zones, marina, and port) along the Brazilian coast. The relatively low levels of butyltins (BTs) in sediments associated with commercial ports (mean of 25 ng Sn g-1), in addition to butyltin degradation indexes pointing to old TBT inputs, confirmed the effectiveness of the IMO Antifouling Systems Convention. However, hotspots of TBT were observed at boat/shipyards (mean BTs of 349.9 ng Sn g-1) and marinas (mean BTs of 118.5 ng Sn g-1) probably due to the presence of APPs. DCOIT, followed by diuron, were the most frequently detected booster biocides (BB), reflecting their current use in antifouling paints. Moreover, APPs emerged as a relevant source of contamination due to high associated concentrations of antifouling biocides (i.e., DCOIT - 43,139 ng g-1; TBT - 311,474 ng Sn g-1). Approximately 75 % of the assessed sites presented concentrations of of TBT and/or BB above safe values that potentially trigger effects on organisms. In summary, contamination by antifouling paint residues was widespread along the Brazilian coastal areas under the influence of maritime activities. Thus, environmental and governmental agencies must act and seek regulatory and protective measures to reduce potential risks to aquatic organisms.

Measuring dissolved concentrations of polybrominated diphenyl ethers (PBDEs) and non-BDE flame retardants on a global scale provides critical insights into the effectiveness of the Stockholm Convention. In the present study, we deployed passive sampling devices at 43 seawater and freshwater sites covering 21 countries from 2016 to 2020. The detection frequencies were 20-94% for BDE congeners and 33-42% for dechlorane plus, higher than those (0-20%) for other target compounds. The median concentrations of dissolved Σ9PBDE (sum of BDE-28, -47, -66, -85, -99, -100, -153, -154, and -183) were 0.28 and 0.64 pg L-1 in seawater and freshwater, respectively. The concentrations of dissolved Σ9PBDE, along with published data, slightly increased before 2016 and remained steady from 2016 to 2018, indicating delayed effects of the global phaseout of technical Penta- and Octa-BDEs. The log-transformed concentrations of individual BDE congeners were better correlated with regional gross domestic product than with population density. The potential ecological risk of BDE-47 was low, and there was a lack of key risk indicators for other compounds. The present study documented the delayed response of the aquatic environment to the regulatory actions on reducing PBDE emissions.

Organotin compounds (OTs) are well studied in various environmental compartments, with a critical focus on the water column as their primary entry point into aquatic ecosystems. In this context, a method for the analysis of organotin (OTs) in water using silicone rubber-based passive sampling was optimized, validated, and field-tested. Validation covered crucial parameters, including the limit of detection (LOD), limit of quantification (LOQ), accuracy, precision, linearity, and matrix effect. The method was shown to be robust (R2 ≥ 0.99), with recoveries between 70.2 and 114.6%, and precise (CV < 12.8%) (N = 3). LODCw and LOQCw were ≤ 15 and ≤ 48 pg Sn L-1, respectively, for TBT and TPhT. The matrix effect showed to be low (>-20% ME < 20%) for all OTs but TPhT (69.4%). The silicone rubber–water partition coefficients (Log Ksr,w) were estimated at 3.37 for MBT, 3.77 for DBT, 4.17 for TBT, 3.49 for MPhT, 3.83 for DPhT, and 4.22 for TPhT. During the field study carried out between October 2021 and February 2022 at the entrance of the Port of Santos navigation channel (Southeastern Brazil), sampling rates ranged between 4.1 and 4.6 L d-1, and the equilibrium was achieved for MBT, DBT, MPhT, and DPhT after ∼45 days of deployment. The freely dissolved concentrations varied between 134 and 165 pg Sn L-1 for TBT, 388 and 610 pg Sn L-1 for DBT, and 1114 and 1509 pg Sn L-1 for MBT, while MPhT, DPhT, and TPhT were below the limit of detection. Results pointed out that J-FLEX® rubber-based passive sampling is a suitable and reliable alternative method for the continuous monitoring of OTs in the water column.

The present study evaluated the matrix effect associated to determination of butyltin compounds (tripropyltin (TPrT), tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT)) in sediment and mussel tissues using derivatization by Grignard reaction and quantification by gas chromatography coupled mass spectrometry (GC-MS). A non-negligible matrix effect was verified for sediments (54.2, 20.3, 13.6 and -53.6 %) and mussel tissues (-12.5, -32.0, 59.4 and 65.7 %) for TPrT, TBT, DBT and MBT respectively. However, this matrix effect was prevailed by preparing the analytical curves using standard addition techniques. Thus, an analytical method was optimized and validated for a more accurate and precise determination of butyltin compounds in sediment and mussel tissue samples.

Sediments represent an important environmental compartment, because they provide substrate for a range of species and may accumulate contaminants in high concentrations. However, the universe of methods to assess the quality of sediments is still small. This investigation aimed to assess the quality of sediments from some sites of Ubatuba (SE Brazil). To achieve that, sediments were analyzed for the presence of PAHs, by immunoassay ELISA kit for the carcinogenic PAH (c-PAH) RaPID Assay, and for toxicity to amphipods, sea-urchin embryos and direct exposure of mussel hemocytes and measurements of the nuetral red retention time (NRTT). Results showed higher levels of PAHs in sediments from Itagua and Ribeira, those more intensely affected by contamination sources. The ecotoxicological analyses indicated these two sites as more degraded, together with the sediments from Lamberto Beach, which is also influenced by nautical activities. The NRRT correlated with the quantities of PAHs in sediments. We concluded that Ribeira Bay and Itaguá Beach need more detailed investigation on pollution and that the NRRT assay exposing directly hemocytes to sediment elutriates can be a useful tool to assessing sediment quality.

Ecotoxicological tests have been used as an important tool in assessing the environmental quality. In order to improve the use of marine and estuarine native organisms in chronic toxicity tests, this study evaluated the potential of the copepod Acartia tonsa in reproduction test. The sensitivity of A. tonsa was determined by exposing adults to 0.5, 0.75, 1.0, 1.5, 2.0 and 2.5 mg.L-1 of zinc sulphate (ZnSO4.7H2O). The production of eggs per female was measured after 48 hours of exposure, resulting in the EC50 of 2.05 mg.L-1 of zinc sulphate (CI 95% = 1.77 - 2.20 mg.L-1). Acute toxicity test was also performed, exposing adults to 2.5, 5.0, 7.5, 10, 12.5 and 15 mg.L-1 ZnSO4.7H2O. Compared to acute effects, the chronic test was 1.9 lower than the lethal concentration (LC50 of 3.80 mg.L-1). The sensitivity response of A. tonsa exposed to zinc presented an EC50 3 to 4 times higher than the others test organism described in the literature, so further studies are needed to improve sensitivity by developing and applying other sublethal endpoints.

Organotin compounds (OTs) used to be the most widely used biocide in antifouling paint systems, but the International Maritime Organization (IMO) banned them because of their high environmental toxicity to non-target organisms. Currently, at least 25 active ingredients are being employed as biocides in antifouling paint formulations. In the present study, silicone rubber-based passive sampling was used to determine the freely dissolved concentrations (Cw) of 6 OTs and 4 booster biocides in the water column at the entrance of Santos Port's main navigation channel, the largest Port of South America (southeastern Brazil). Fifteen sampling events of ∼45 days long were conducted over 2 years. Cw of OTs ranged from 1.1 to 2.5 ng Sn L-1 for monobutyltin (MBT), 0.2 to 4.7 ng Sn L-1 for dibutyltin (DBT), and 0.06 to 0.7 ng Sn L-1 for tributyltin (TBT), while triphenyltin (TPhT), diphenyltin (DPhT), and monophenyltin (MPhT) were always below their limits of detection (<LOD). For booster biocides, Cw ranged from 3.9 to 6.3 ng L-1 for diuron, 0.03 to 0.49 ng L-1 for Irgarol, <0.55 to 44.3 ng L-1 for DCOIT, and <0.01 to <0.02 ng L-1 for dichlofluanid. Levels found in the water column are likely explained by a combination of sources, including simultaneous releases from marinas and shipyards located in adjacent areas, dredging operations, intense vessel traffic in the Santos Port, and desorption from APPs previously released along sediments of the Santos-São Vicente Estuarine System (SSES). Although OTs and booster biocide levels in the Port of Santos were relatively lower than in other studies worldwide, levels detected for TBT, DCOIT, and diuron pose a risk to non-target organisms.

The new generation of antifouling biocides, as well as other emerging contaminants, has not yet been included in sediment quality guidelines or present standard protocols for sediment spiking. Most of these biocides have short half-lives in water, but little information is available regarding their degradation in sediments. Thus, there is a need to establish a reliable duration of the equilibrium phase for sediment spiking prior to sediment toxicity testing to determine the actual exposure concentrations during ecotoxicological tests. This study aimed to evaluate the degradation of DCOIT, Irgarol, Diuron, and Dichlofluanid during a spiking equilibrium phase of 24 h at three different time intervals (0, 6, and 24 h) and concentrations (10, 100, and 1000 ng g-1), by applying kinetic degradation models. The models presented a better fit for the 1000 ng g-1 treatments, in which the half-lives of DCOIT and Diuron were < 5 h, Dichlofluanid < 2 h, and Irgarol < 6h. Our results also indicate that, except for Dichlofluanid, the degradation rates of the other antifouling biocides were reduced dramatically after 6 h of equilibrium. Therefore, an equilibrium phase of 24 h (or greater than 6 h) was considered viable for sediment spiking. Our findings provide valuable information to guide future sediment toxicity tests using these compounds.

Polycyclic aromatic hydrocarbons (PAHs), released from petrogenic, pyrogenic or diagenetic sources (degradation of wood materials), are of global concern due to their adverse effects, and potential for long-range transport. While dissolved PAHs have been frequently reported in the literature, there has been no consistent approach of sampling across water bodies. Passive samplers from the AQUA/GAPS-MONET initiative were deployed at 46 sites (28 marine and 18 freshwater), and analyzed for 28 PAHs and six polycyclic musks (PCMs) centrally. Freely dissolved PAH concentrations were dominated by phenanthrene (mean concentration 1500 pg L-1; median 530 pg L-1) and other low molecular weight compounds. Greatest concentrations of phenanthrene, fluoranthene, and pyrene were typically from the same sites, mostly in Europe and North America. Of the PCMs, only galaxolide (72% of samples) and tonalide (61%) were regularly detected, and were significantly cross-correlated. Benchmarking of PAHs relative to penta- and hexachlorobenzene confirmed that the most remote sites (Arctic, Antarctic, and mountain lakes) displayed below average PAH concentrations. Concentrations of 11 of 28 PAHs, galaxolide and tonalide were positively correlated (P < 0.05) with population density within a radius of 5 km of the sampling site. Characteristic PAH ratios gave conflicting results, likely reflecting multiple PAH sources and postemission changes.

In this study the acute and sub-lethal effects caused by the Water Soluble Fraction (WSF) of a light crude oil were assessed for the first time on the planktonic copepod Acartia tonsa. Chromatographic analysis was also performed to quantify the levels of hydrocarbons (total, aliphatic and polyaromatic hydrocarbons) to which copepods were exposed to. Male and female individuals were exposed to hydrocarbon concentrations varying from 12 to 196 μg.L–1 (Total hydrocarbons). The LC50 was 69.5 (24 hours) and 48.0 μg.L–1 (48 hours) for females and 84.8 (24 hours) and 70.1 μg.L–1 (48 hours) for males. Sub-lethal effects were also evaluated by exposing females to the equivalent of LC10. Females showed significant reduction in egg and fecal pellet production, and also a delay in the eggs hatching time. Thus, the toxic effects of WSF of oil may be crucial for the specie population maintenance, possibly influencing the equilibrium of marine ecosystems.

Persistent organic pollutants (POPs) are recognized as pollutants of global concern, but so far, information on the trends of legacy POPs in the waters of the world has been missing due to logistical, analytical, and financial reasons. Passive samplers have emerged as an attractive alternative to active water sampling methods as they accumulate POPs, represent time-weighted average concentrations, and can easily be shipped and deployed. As part of the AQUA-GAPS/MONET, passive samplers were deployed at 40 globally distributed sites between 2016 and 2020, for a total of 21 freshwater and 40 marine deployments. Results from silicone passive samplers showed α-hexachlorocyclohexane (HCH) and γ-HCH displaying the greatest concentrations in the northern latitudes/Arctic Ocean, in stark contrast to the more persistent penta (PeCB)- and hexachlorobenzene (HCB), which approached equilibrium across sampling sites. Geospatial patterns of polychlorinated biphenyl (PCB) aqueous concentrations closely matched original estimates of production and use, implying limited global transport. Positive correlations between log-transformed concentrations of Σ7PCB, ΣDDTs, Σendosulfan, and Σchlordane, but not ΣHCH, and the log of population density (p < 0.05) within 5 and 10 km of the sampling sites also supported limited transport from used sites. These results help to understand the extent of global distribution, and eventually time-trends, of organic pollutants in aquatic systems, such as across freshwaters and oceans. Future deployments will aim to establish time-trends at selected sites while adding to the geographical coverage.

DCOIT is an effective antifouling biocide, which presence in the environment and toxicity towards non-target species has been generating great concern. This study evaluated the waterborne toxicity of DCOIT on marine invertebrates (i.e., survival of brine shrimp Artemia sp., larval development of the sea urchin Echinometra lucunter and the mussel Perna perna), as well as DCOIT-spiked-sediment toxicity on the fecundity rate of the copepod Nitrocra sp. And the mortality of the amphipod Tiburonella viscana. The data outcomes were used to calculate environmental hazards and risks, which were compared to their corresponding values obtained from temperate regions. Waterborne toxicity can be summarized as follows: Artemia sp. (LC50-48h = 163 (135-169) μg/L), E. lucunter (EC50-36h = 33.9 (17-65) μg/L), and P. perna (EC50-48h = 8.3 (7-9) μg/L). For whole-sediment toxicity, metrics were calculated for T. viscana (LC50-10d = 0.5 (0.1-2.6) μg/g) and Nitrocra sp, (EC50-10d = 200 (10-480) μg/kg). The DCOIT hazard was assessed for both tropical and non-tropical pelagic organisms. The predicted no-effect concentration (PNEC) for tropical species (0.19 μg/L) was 1.7-fold lower than that for non-tropical organisms (0.34 μg/L). In whole-sediment exposures, DCOIT presented a PNEC of 0.97 μg/kg, and the risk quotients (RQs) were >1 for areas with constant input of DCOIT such as ports ship/boatyards, marinas, and maritime traffic zones of Korea, Japan, Spain, Malaysia, Indonesia, Vietnam, and Brazil. The presented data are important for supporting the establishment of policies and regulations for booster biocides worldwide.

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).