Butyltins Research Articles

Growth of Pacific staghorn sculpin (Leptocottus armatus) is reduced at contaminated sites in the Lower Duwamish River, Washington

The Lower Duwamish River is a highly industrialized waterway flowing into the densely urbanized Puget Sound waterfront of Seattle, Washington, USA. The river has been profoundly altered from its natural state following more than a century of channelization, recurrent dredging, shoreline armoring, and pollution discharges. As part of a Natural Resource Damage Assessment addressing historical pollution at three designated Superfund sites (i.e., the assessment area), juvenile Pacific staghorn sculpin (Leptocottus armatus) were sampled throughout the lower river in order to evaluate injury from exposure to polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDTs), and butyltins (BTs). Sculpin live in close association with the river sediments within and upriver of the assessment area. Fish were collected for analysis of contaminant concentrations in composited whole bodies and stomach contents, as well as individual fish health metrics including daily somatic growth rates measured from otoliths. Sediment contaminant concentrations were also measured at sites near to fishing locations. Fish growth rates varied from 0.65 to 1.05 mm/day, and were significantly lower at unremediated downriver sites compared to upriver and remediated locations. Sculpin growth rates were negatively correlated with concentrations of PCBs in fish bodies, PAHs in stomach contents, as well as PCBs, DDTs and PAHs in sediment. Mixed effects models for whole-body and stomach content contaminants showed positive correlations between growth rate and water temperature. Temperature was not a significant confounding variable for the relationship between growth rate and sediment contaminants. Overall, these results show that juvenile sculpin are harmed by contaminant exposure in the Lower Duwamish River. Furthermore, this study demonstrates the utility of using paired biological and chemical indicators of pollutant-induced injury in a resident fish to inform a complex Natural Resource Damage Assessment and associated restoration efforts.

Study on by-products synthesis of powder coating polyester resin catalyzed by organotin

Abstract In the production of powder-coating polyester, a strong odor emanates from the water, prompting us to investigate its composition and origin. We studied the process of powder coating epoxy/polyester 50/50, which employs butyl tin tris (2-ethyl hexanoate) as a catalyst. The esterified water was extracted using ethyl acetate. It was analyzed via GC–MS to identify the side reactions and by-products that arise during the tin-catalyzed esterification process. Then we discussed their formation mechanism. Our results indicate that butyl tin tris (2-ethyl hexanoate) triggers side reactions such as cyclization and transesterification, leading to the production of by-products such as heterocyclic compounds (1,4-dioxane), anhydride compounds (propionic anhydride), and others. Notably, the unpleasant odor was found to be derived from propionic anhydride. These findings provide insights into the chemistry of tin-catalyzed esterification and highlight the importance of addressing the formation of unwanted by-products in the production of powder-coating polyester.

On the effectiveness of tributyltin ban part II: Temporal and spatial trends of organotin pollution in intense sediment accumulation areas and dumping sites of the Baltic Sea

Based on the knowledge gained from our previous study, our aim is to observe the current levels of butyltin (BTs) pollution, changes during different seasons, and the factors that affect these trends in the areas of highest concern. These areas include semi-enclosed bays in the Port that were previously affected by large tributyltin (TBT) inputs, as well as the dumping sites of dredged sediment in the Baltic Sea. Compared to previous studies, there has been a significant decrease in the levels of BTs in the Klaipeda Port. However, the sediment in the semi-enclosed bays still contained BTs, ranging from less than 0.5 ng Sn g−1 dw to as high as 728.5 ng Sn g−1 dw. Some BTs were also detected in the currently exploited dumping sites of the Baltic Sea. Moreover, butyltin degradation index (BDI) revealed occasional fresh TBT input or slow degradation both in the Port and in the Sea. Some trends in butyltin concentrations were indicative of the impact of climate change in Lithuania, which are consistent with global trends. We also found that variations in BTs concentrations were closely related to dredging and cleaning activities taking place in the Klaipeda Port. Correlation, principal component, and cluster analysis revealed close relationship between TBT and its degradation products, as well as between TBT and Zn, Pb, Cu. Ship cleaning/maintenance activities were identified as the main source of pollution in the study area. Despite the gradually decreasing BTs concentration in the Klaipeda Port, the problem is not yet completely solved.

Bioaccumulation of antifouling biocides in mangroves and seagrasses in coastal ecosystems

Abstract We measured the concentrations of antifouling biocides in sediment, mangrove leaves and seagrasses from Merambong and Tinggi Island, Johor, Malaysia to evaluate their contamination levels. Although the concentrations of tributyltin (TBT) in mangrove leaves in Merambong in 2013 were significantly lower than those in 2012, the Sea-Nine 211 concentration in 2013 was significantly higher than that in 2012, suggesting that the use of antifouling biocides changed from TBT to Sea-Nine 211. The concentration of each BT (butyltin) and PT (phenyltin) in the mangrove area was significantly higher than the corresponding concentration in the seagrass area in Merambong, but the concentrations of Sea-Nine 211, diuron, chlorothalonil, Irgarol 1051 and M1 in seagrasses were significantly higher than those in mangrove leaves. There were differences in the accumulation profiles of OTs (organotins) and alternative biocides between the seagrass shoots and roots. The concentration of OTs in the seagrass roots was almost the same or higher than those in the shoots, whereas those of alternative biocides shows the opposite pattern to the OTs. Significant high relationships were observed between stable carbon isotope (δ13C) and OTs, Sea-Nine 211 and Irgarols in mangrove leaves. The concentrations of these compounds increased along with the δ13C values of the mangroves. These results suggest that mangroves take up the bicarbonate ions and nutrients in sediment and/or seawater through their roots, along with OTs, Sea-Nine 211 and Irgarols which were accumulated in sediment.

Concentrations of organotin compounds in aquatic biota in coastal waters of Johor, Malaysia

AbstractThe concentrations of organotin (OT) compounds, butyltin (BT) and phenyltin (PT), in aquatic organisms from Merambong and Tinggi Island, Malaysia, which differ in industrial and economic activities, were measured. Tributyltin (TBT) compounds among BTs ranged from 2.9–28 and <0.1–21 ng g−1 ww in aquatic organisms from Merambong and Tinggi Island, respectively. Triphenyltin (TPT) compounds among PTs ranged from <0.1–25 ng g−1 ww and <0.1–61 ng g−1 ww in aquatic organisms from Merambong and Tinggi Island, respectively. A survey of OT concentrations among the species of OT compounds revealed that the concentrations of BTs and PTs in crabs and clams were high while those in fish were low. Correlation analysis with stable nitrogen isotopes suggest that OT compounds did not accumulate in aquatic organisms through the food web. The measurement of OT compounds in tissues and organs of fish revealed that BT concentrations in liver were higher than those in muscle and that BTs were detected in eggs of fish.

Organotin contamination in seafood from the Yucatán Peninsula, Mexico: Is there a potential risk for the health of consumers?

Since seafood is considered an important source of organotin compounds (OTCs), the present study assessed the potential risk to human health of ingesting butyltins (BTs) and phenyltins (PhTs) along with this type of food. Seafood samples were collected at five fishing sites in the Yucatán Peninsula (Mexico) during February and March 2018. In general, organotins were detected in all samples, suggesting a widespread occurrence of these compounds in the investigated region. The average concentration of total organotins in the muscle of demersal fish (Lutjanus synagris, Lutjanus campechanus, Calamus pennatula, Haemulon plumierii, Rhomboplites aurorubens), pelagic fish (Euthynnus alletteratus, and Opisthonema oglinum), gastropods (Melongena bispinosa and Strombus pugilis), oyster (Crassostrea virginica) and shrimp (Penaeus duorarum) was 146.7 ± 76.2, 93.1 ± 92.6, 61.0 ± 53.0, 76.7 ± 2.6, and 28.8 ± 2.7 ng Sn g−1 dry weight, respectively. Overall, MPhT among PhTs was the dominant compound in fish, while TBT among BTs was the dominant compound in shellfish. Regarding the toxic OTCs, TBT followed by DBT were the predominant compounds in all seafood species, while TPhT was below the quantification limit in most samples. The estimated daily intake values were lower than the tolerable daily intake (TDI) for the sum of organotins established by the European Food Safety Authority (EFSA). Furthermore, the hazard quotients (HQ) and hazard indices (HI) values were all lower than 1, suggesting that daily exposure to these levels of organotins is unlikely to cause any harm to the human health of seafood consumers at the Yucatán Peninsula. Thus, consumers may not be at risk through the inclusion of these investigated seafood species in their normal diet. However, due to the increasing coastal urbanization, maritime activities, and the likely illegal use of tin-based paints in Mexico, additional monitoring is needed to assess organotin levels in other regions along the Mexican coastal zone and using other seafood species.

Before-During-After Biomonitoring Assessment for a Pipeline Construction in a Coastal Lagoon in the Northern Adriatic Sea (Italy)

During 2006–2008, a pipeline was buried in Vallona lagoon in the Northern Adriatic Sea (Italy). A Before-During-After environmental monitoring programme was scheduled to monitor possible alterations. Bioaccumulation of metal(loid)s, BTs (butyltins) and HMW-PAHs (High Molecular Weight Polycyclic Aromatic Hydrocarbons), and biological responses (Condition index, air Survival—LT50, Acetylcholinesterase, Micronuclei—MN, acyl-CoA oxidase, catalase, malondialdehyde—MDA, and the total oxyradical scavenging capacity—TOSCA) were investigated in Manila clams (Ruditapes philippinarum) from November 2005 to June 2015. In opera (IO) results showed higher levels of HMW-PAHs (73 ± 13 ng/g), BTs (90 ± 38 ng Sn/g) and increasing levels of Pb (6.7 ± 0.7 mg/kg) and Zn (73.6 ± 6.08 mg/kg) probably linked to works. Other contaminant alterations, especially metal(loid)s, before (AO) and after (PO) the burial, were attributed to a general condition of the area and mostly unrelated to works. In addition, LT50, MN and TOSCA showed alterations, probably due to hotspots occurring in IO. TOSCA and MDA increases, right after the burial, were considered delayed responses of IO, whilst other biological responses detected later were connected to the general condition of the area. Comparisons between results of Principal Component Analyses (PCAs) highlighted partial overlapping of AO and IO, whilst PO differed only for contaminants. Visual correlations between PCAs highlighted the biomarkers’ latter response.

Organotin compounds (OTs) in surface sediments, bivalves and algae from the Russian coast of the Barents Sea (Kola Peninsula) and the Fram Strait (Svalbard Archipelago).

Organotin pollution in components of benthic ecosystems was investigated in 2019 in the Barents Sea (South shore, Kola Peninsula) and the Fram Strait (Icefjord, Svalbard Archipelago). Six species of organotin compounds (OTs), including monobutyltin, dibutyltin, tributyltin, tetrabutyltin, triphenyltin and tricyclohexyltin, were measured in the surface sediments, bivalve molluscs (Ciliatocardium ciliatum, Macoma calcarea, Chlamys islandica) and macrophyte algae (Saccharina latissima, Palmaria palmata, Ulvaria obscura, Fucus serratus, Fucus distichus). The results obtained showed moderate contamination of the studied samples with OTs. The total content of six tin compounds was in the ranges 35-139ngg-1, 13-108ngg-1 and 2.9-75ngg-1 (dry weight) in the samples of sediments, bivalves and algae, respectively. In most cases, the concentrations of tributyltin in bottom sediments and mollusc tissues did not exceed the established international regulations. The degradation indices analysis of butyl tin derivatives indicated the active transformation of tributyltin and tetrabutyltin in bottom sediments and macrophyte algae and the accumulation of these compounds in the soft tissues of molluscs. The sediment and mollusc concentrations of OTs measured in this study were comparable to those reported for other areas of the Arctic region.

Organotin Compounds (OTCs) in Saccharina latissima (Phaeophyceae) from the Barents Sea.

The degree of contamination of Saccharina latissima, the dominant species among macrophyte algae in the sublittoral zones of the Kola Bay and Eastern Murman of the Barents Sea, with organotin compounds (monobutyltin, dibutyltin, tributyltin, tetrabutyltin, triphenyltin, and tricyclohexyltin) has been assessed. The results show a moderate degree of contamination of the studied samples with organotin compounds. The total concentration of six tin compounds was 17-74 ng/g (dry weight) in algal samples. Analysis of the indices of degradation of butyl tin derivatives showed active processes of tributyltin and tetrabutyltin transformation in algae.

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.

Synthesis and Diagnosis New Metallotropic LCs from Organotin (IV) Complex

Organotin (IV) complex is part of the organometallic chemistry and in recently decades have a variety of interesting and application used it. A new class of metallomesogens LC (A) Ph3Sn(VAL), (B) Bu3Sn(VAL), (C) Ph2Sn(VAL)2 and (D) Bu2Sn(VAL)2 was synthesis through the reaction of valsartan ligand with (di- or tri- butyl tin chloride salt) and (di- or tri- phenyl tin chloride salt) in methanol solvent. 1H NMR,119 Sn NMR, FTIR and CHN elemental analyses were measure and the liquid crystalline properties were study by POM. The mesophase in all organotin (IV) carboxylate complexes are thermotropic nematic phase. In complexes (A, C) the optical textures of A show a typical droplet texture and thread shape LC phase transition between (400-440⁰C) higher than mesophase textures in C between (230 -250⁰C). In complexes (B, D) the optical textures of B appearance a thread shape and the LC phase transition temperature between (200 -400⁰C) and in D thread shape and the transition temperature beginning up to 280⁰C. From a temperature of phase transition show that the complexes (C, D) are start liquid crystal mesophase in lower than complex (A, C) because effect of R-group and types which due to an asymmetric arrangement of the molecule and a geometry was calamitic in which the length of the molecule is major in compare with its diameter.

Distribution of biocides in selected marine organisms from South of Johor, Malaysia

The emerging of organotins (OTs) have adverse effect toward marine organisms and expose health problem through dietary uptake of contaminated seafood. While the booster biocide creates significant environmental risks mainly on the base of the marine food chain. The present study reported on the baseline data on the level and distribution of organotin and booster biocide in the primary producers (Ulva sp., Enhalus acoroides), mollusks (Strombus turturella, Perna viridis, Pinna nobilis) and fish species (Otolithus ruber, Polydactylus sextarius, Thryssa dussumieri) collected from the seagrass bed of Sungai Pulai estuary. The samples were extracted by mechanical shaking with acetone before analyses using GC–MS. The primary producers of Ulva sp. and Enhalus acoroides have the highest tributyltin (TBT) and mobobutyltin (MBT) concentration with values of 433 ± 22 and 35±1.8μg/kg, respectively. Meanwhile, mollusks and fish species have the highest monophenyltin (MPT) concentration which indicated phenyltin (PT) was dominant over butyltin (BT) compound. Dichlorofluanid and M1 are two compounds which mostly detectable in Polydactylus sextarius and Ulva sp. with the highest measured values of 130±3.7μg/kg and 86±4.3μg/kg, respectively. The elevated biocides detected in the selected marine organisms proved increasing application of these compounds in the shipping system, agricultural runoff, and domestic activities.

Evaluation of dredged sediment for aquatic placement: interpreting contaminant bioaccumulation.

The potential bioaccumulation of sediment-associated contaminants is one of the primary concerns associated with the aquatic placement of dredged sediment. Laboratory bioaccumulation tests with representative infaunal organisms exposed to dredged sediment and reference sediment are used to assess the potential for contaminant-related bioaccumulation impacts. Dredged sediment testing and evaluation guidance provides statistical inferences and numerous assessment factors (e.g., the magnitude of difference (MOD)) to interpret results; however, detailed information for applying these factors is lacking. Therefore, the focus of this work was to provide context for the application of the MOD as a line of evidence for evaluating bioaccumulation risk associated with dredged material placement in aquatic environments by considering variance (as coefficient of variation (CV)), MOD, and statistical differences associated with bioaccumulation bioassay tissue concentrations in three case studies. Based on peer-reviewed data and dredged material monitoring data, relatively low within-sample variability (CVs < 50%) of tissue concentrations can be achieved for commonly assessed constituents (e.g., polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), metals, and butyl tins). Thus, statistical comparisons were generally able to detect significant differences (p < 0.05; α = 0.05) across tissue concentrations with relatively low MODs (< 2-fold difference). Based on the observed variance, MOD, and statistical differences associated with bioaccumulation bioassay tissue concentrations, a 2-fold MOD can provide an additional line of evidence to evaluate bioaccumulative risk when statistical significance is observed. These results indicated that a judicious consideration of the sample variance and MOD is a useful factor when discerning meaningful differences among contaminant tissue concentrations.

Persistent and emerging pollutants assessment on aquaculture oysters (Crassostrea gigas) from NW Portuguese coast (Ria De Aveiro)

The study aim was to determine a range of relevant persistent and emerging pollutants in oysters produced in an aquaculture facility located in an important production area, to assure their safety for human consumption. Pollutants, including 16 PAHs, 3 butyltins (BTs), 29 flame retardants (FRs, including organophosphate and halogenated FRs), 35 pesticides (including 9 pyrethroid insecticides) and 13 personal care products (PCPs, including musks and UV filters), were determined in oysters' tissues collected during one year in four seasonal sampling surveys. The seasonal environmental pollution on the production site was evaluated by water and sediment analysis. Furthermore, oysters' nutritional quality was also assessed and related with the consumption of healthy seafood, showing that oysters are a rich source of protein with low fat content and with a high quality index all year around. Results showed that most analysed pollutants were not detected either in oyster tissues or in environmental matrixes (water and sediments). The few pollutants detected in oyster tissues, including both regulated and non-legislated pollutants, such as a few PAHs (fluorene, phenanthrene, anthracene, fluoranthene, pyrene and indenopyrene), FRs (TPPO, TDCPP, DCP, BDE-47, BDE-209 and Dec 602) and PCPs (galaxolide, galaxolidone, homosalate and octocrylene), were present at low levels (in the ng/g dw range) and did not represent a significant health risk to humans. The observed seasonal variations related to human activities (e.g. tourism in summer) highlights the need for environmental protection and sustainable resource exploration for safe seafood production.

A review of organotin contamination in arctic and subarctic regions

Abstract Organotin (OT) compounds are of continued Arctic concern as they are still widely used despite the most well-studied OT, tributyl tin (TBT), being restricted from use on marine vessels to prevent fouling by marine organisms. The highest OT concentrations found in Arctic fauna are in regions associated with human activity especially shipping. There is an overall trend of declining butyl tin (BT) concentrations in Arctic fauna especially molluscs which are the subject of a limited number of long-term monitoring studies. The incidence of imposex has likewise generally declined in molluscs in response to declining TBT concentrations. There are a number of knowledge gaps in OT occurrence and transport in the Arctic that warrant continued monitoring. OTs, in particular octyl tins, are heavily used in the production of plastic, hence leaching from plastic may be an unrecognized source to Arctic regions. This review also found several studies reporting volatile tin species in the atmosphere suggesting atmospheric transport of volatile tins to the Arctic is possible. Relative to other more well know persistent organic pollutants, there are few reports of OTs in marine mammals and temporal tend studies are needed to define trends in BTs and search for the occurrence of other tin species.

Organotins in the aquatic media of secondary anabranches in the Three Gorges Reservoir Region, China

The Three Gorges Reservoir Region (TGRR) is one of the most sensitive areas of ecological environment in China. As vital backwater areas, the secondary anabranches of the TGRR were prone to eutrophication in Spring which would affect the distribution and transfer of organotins (OTs) among aquatic media. This study quantified the concentrations of butyltins (BTs) and phenyltins (PhTs) in water columns and aquatic media of two anabranches of the TGRR, the Daning River (DR) and the Xiaojiang River (XR) during the state of eutrophication. Our results showed that the average concentrations of BTs and PhTs in surface water are 43.91, 81.25 ng Sn L−1 in the DR, and 63.49, 69.21 ng Sn L−1 in the XR, respectively, and there were no obvious differences in the concentrations of BTs and PhTs across the water columns in the DR and XR. PhTs, especially monophenyltin (MPhT), are predominated in the dissolved phase, whereas BTs, especially dibutyltin (DBT), are predominated in both suspended particulate matter (SPM) and the sediment. Shipping and agricultural activity were likely the sources of OTs in both the DR and XR. High concentrations of tributyltin (TBT) and triphenyltin (TPhT) are still present in the aquatic media of the TGRR, and pose a significant risk to aquatic organisms due to the potential for bioaccumulation. Therefore, it is necessary to further monitor and assess OTs especially PhTs in surface water, and to continue to restrict the use of OTs to protect the aquatic environment of the TGRR.

Occurrence and health risk assessment of organotins in waterworks and the source water of the Three Gorges Reservoir Region, China.

The occurrence and health risks of organotins (OTs) in the waterworks and source water in the Three Gorges Reservoir Region (TGRR), China were assessed in this study. Water samples were collected at four waterworks (A, B, C, and D) in March and July 2012 to analyze butyltins (BTs) and phenyltins (PTs) using a gas chromatography-mass spectrometry (GC-MS) system. Our results showed that both the waterworks and their nearby water sources were polluted by OTs, with PTs being the most dominant species. Monobutyltin (MBT), monophenyltin (MPT), diphenyltin (DPT), and triphenyltin (TPT) were detected in most of the analyzed water samples. The highest concentrations of OTs in influents, effluents, and source water in March were 52.81, 17.93, and 55.32ngSnL-1, respectively. Furthermore, significant seasonal changes in OTs pollution were observed in all samples, showing pollution worse in spring compared with summer. The removal of OTs by the conventional treatment processes was not stable among the waterworks. The removal efficiency of OTs in July reached 100% at plant B, while that at plant C was only 38.8%. The source water and influents shared similar composition profiles, concentrations, and seasonal change of OTs, which indicated that OTs in the waterworks were derived from the source water. A health risk assessment indicated that the presence of OTs in the waterworks would not pose a significant health risk to the population, yet their presence should not be ignored.

Ballast water management system: Assessment of chemical quality status of several ports in Adriatic Sea

Oxidant treatment of ballast water (BW) is commonly used in BW systems in order to minimize the transport of alien species. The release of disinfection by-products (DBPs) associated to the treatment of BW and cross-contamination of butyltin (BT) compounds through BW discharge is a topic of environmental concern. A chemical port baseline survey has been conducted in seven ports of the Adriatic Sea. Analysis have been performed on transplanted mussels, surface sediment, seawater, BW. Results showed an evidence of BT contamination, particularly in sediments, probably related to their illegal usage or to intensive shipping activities. Therefore, BW may act as a vector and contribute to re-buildup of BT contamination in the coastal regions.A baseline set of data concerning DBPs is provided, showing the preferential distribution of these compounds in the marine environment that will be useful for future considerations on monitoring and assessment of chemical contamination associated with BW.

Effects of copper and butyltin compounds on the growth, photosynthetic activity and toxin production of two HAB dinoflagellates: The planktonic Alexandrium catenella and the benthic Ostreopsis cf. ovata

Controlled laboratory experiments were conducted to test the effects of copper (Cu2+) and butyltins (BuT) on the growth, photosynthetic activity and toxin content of two HABs (Harmful Algal Blooms) dinoflagellates, the planktonic Alexandrium catenella and the benthic Ostreopsis cf. ovata. Microalgae were exposed to increasing concentrations of Cu2+ (10−4 to 31 nM) or BuT (0.084 to 84 nM) for seven days. When considering the growth, EC50 values were 0.16 (±0.09) nM and 0.03 (±0.02) nM of Cu2+ for A. catenella and O. cf. ovata, respectively. Regarding BuT, EC50 was 14.2 (±6) nM for O. cf. ovata, while A. catenella growth inhibition appeared at BuT concentrations ≥27 nM. Photosynthetic activity of the studied dinoflagellates decreased with increasing Cu and BuT concentrations. For O. cf. ovata, the response of this physiological parameter to contamination was less sensitive than the biomass. Cu exposure induced the formation of temporary cysts in both organisms that could resist adverse conditions. The ovatoxin-a and -b concentrations in O. cf. ovata cells increased significantly in the presence of Cu. Altogether, the results suggest a better tolerance of the planktonic A. catenella to Cu and BuT. This could result in a differentiated selection pressure exerted by these metals on phytoplankton species in highly polluted waters. The over-production of toxins in response to Cu stress could pose supplementary health and socio-economic threats in the contaminated marine ecosystems where HABs develop.

Bioaccumulation of persistent and emerging pollutants in wild sea urchin Paracentrotus lividus

Marine pollution has been increasing as a consequence of anthropogenic activities. The preservation of marine ecosystems, as well as the safety of harvested seafood, are nowadays a global concern. Here, we report for the first time the contamination levels of a large set of 99 emerging and persistent organic contaminants (butyltins (BTs), polycyclic aromatic hydrocarbons (PAHs), pesticides including pyrethroids, pharmaceuticals and personal care products (PCPs) and flame retardants) in roe/gonads of sea urchin Paracentrotus lividus. Sea urchins are a highly prized worldwide delicacy, and the harvesting of this seafood has increased over the last decades, particularly in South West Atlantic coast, where this organism is harvested mainly for exportation. Sampling was performed in three harvesting sites of the NW Portuguese coast subjected to distinct anthropogenic pressures: Carreço, Praia Norte and Vila Chã, with sea urchins being collected in the north and south areas of each site.Butyltins and pharmaceuticals were not found at measurable levels. Several PAHs, four pyrethroids insecticides, four PCPs and eleven flame retardants were found in roe/gonads of sea urchins, though in general at low levels. Differences among harvesting sites and between areas within each site were found, the lowest levels of contaminants being registered in Carreço. The accumulation of contaminants in sea urchins’ roe/gonads seemed to reflect the low anthropogenic pressure felt in the sampling sites. Nevertheless, taking into account the low accumulated levels of chemicals, results indicate that sea urchins collected in South West Atlantic coast are safe for human consumption.