An alternative silicone-based passive sampling device to derive organotin concentrations in the aqueous phase.

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.

Legacy and emerging antifouling biocide residues in a tropical estuarine system (Espirito Santo state, SE, Brazil).

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).

Spatial distribution of butyltins and imposex in eastern Brazilian Amazon.

Spatial distribution of Butyltins (BTs) in surface sediments and gastropod tissues were quantified, with samples taken from an estuarine system of the Eastern Amazon, Brazil. The imposex incidence was also assessed using Thaisella coronata (Gastropoda, Mollusca). The sediment sampling was carried out at 19 sites and T. coronata in 6 of those. The highest BTs levels were detected in sediments of a Marine Extractive Reserve (27.1 ng Sn g-1) and in an urban area (19.8 ng Sn g-1). In T. coronata tissues, BTs levels ranged from <5 to 142 ng Sn g-1. Imposex incidence ranged from 0% to 100% and VDSII (penile papillae) was registered in gastropods from 5 out of 6 sampled sites. The results suggest that BTs concentrations are related to sampled area use, but also to the local hydrodynamics, highlighting the importance of an effective control in the use of TBT-based antifouling paints in the Eastern Amazon.

Histological and Behavioral Toxicity of Tributyltin in the Tropical Guppy Poecilia vivipara.

The tropical estuarine guppy Poecilia vivipara was used to address fish early life stage toxicity caused by the antifouling contaminant tributyltin. Six-day-old P. vivipara were exposed for 7 d to control water and waterborne tributyltin at 15.8, 83.8, 716, and 818 ng tin (Sn) L-1 . After exposure, swimming, feeding, growth, and eye histological endpoints were evaluated. Histopathological analysis of the retinal pigment epithelium (RPE) indicated alterations in pigment positioning at all tributyltin concentrations. A dose-dependent increase in photoreceptor layer disorganization and iris melanin hyperpigmentation was verified, and high frequencies of RPE invaginations and iris epithelial cell atrophy were observed even at the lowest exposure concentration of 15.8 ng Sn L-1 . At the highest exposure level (818 ng Sn L-1 ) fish also presented reductions in swimming speed, swimming resistance, daily capture of Artemia nauplii, and growth in weight of 85, 60, 33, and 56% relative to controls, respectively. This association between retinal histopathology and reduced swimming and foraging behavior can reduce recruitment to the adult population. Environ Toxicol Chem 2020;39:1953-1963. © 2020 SETAC.

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.

Imposex and butyltin contamination still evident in Chile after TBT global ban.

Imposex in gastropods (Acanthina monodon, Oliva peruviana and Xanthochorus cassidiformis), butyltin levels in surface sediments (Coquimbo and Concepcion) and tissues (Valparaiso and Concepcion) were assessed in three areas under the influence of maritime activities along the central Chilean coast. The highest TBT concentrations were observed in São Vicente Bay (Concepcion), reaching 122.3ngSng(-1) in surface sediments and 59.7ngSng(-1) in gastropods tissue, while in Valparaiso ranged from 7.4 to 15.8ngSng(-1) in biota. The lowest TBT concentrations were detected in sediments from Coquimbo (<2ngSng(-1)), which can be attributed to a much lower ship/boat traffic (probably using TBT free products) in association to local oceanographic conditions. Despite DBT and MBT were the predominant analytes, recent inputs of TBT were evident in some areas. In fact, fishing boats may be a relevant source since they were the predominant maritime activity in the most contaminated sites. In addition, the absence of significant differences within BTs levels between both genders of A. monodon suggests that tissues from distinct sexes can be indistinctly used for future contamination studies. Imposex incidence was detected in 11 out of 15 sampled sites, indicating that environmental levels of TBT have been sufficient to induce deleterious effects on the exposed organisms. Thus, the impacts caused by TBT in Chilean coastal areas were detectable and consistent with other studies performed in South America. This present environmental contamination is probably due to the lack of regulations forbidding the use of TBT-based antifouling paints in Chile.