Development of methodology for the visual identification of Tributyltin (TBT) in antifouling paint matrices.

Organotin compounds (OTC), mainly tributyltin (TBT), have been used since the 1970s as biocides in the composition of antifouling paints. Due to its physical-chemical characteristics, TBT has high toxicity to the marine environment affecting non-target organisms. The present study aims to develop a method of direct visual identification of TBT in antifouling paints using the cyclopalladate complex, 4- (2-thiazolylazo) resorcinol (TAR-Pd), synthesized in our laboratory. Tests were performed in blank and in the paint matrix with the following OTC: TBT-O; TBT-Cl; TPT-Cl; DBT-Cl (tributyltin oxide, tributyltin chloride, triphenyltin chloride, dibutyltin chloride), in addition to the SnCl4 and SnCl2 compounds (tin IV chloride and tin II chloride), all at a concentration of approximately 20 g/ kg of dry paint). The test was performed by applying paint samples to test bodies and scraping a few tens of milligrams of the dry paint film. The scraped paint samples were submitted to the test, showing a different staining reaction for the TBT-Cl and SnCl4 samples concerning blank and other samples (TBT-O, TPT, DBT-Cl, and SnCl2). Solution tests were performed to characterize reaction products by spectroscopy in the visible band. The method developed has potential for application in real samples, being selective for TBT-Cl and SnCl4 in an acid medium, obtaining a limit of detection, in the range of 1-10 mg/kg dry paint.

Multivariate optimization of microwave-assisted digestion methods for Cu and Sn determination in antifouling paints using inductively coupled plasma optical emission spectrometry.

Antifouling paints containing Cu, Zn, organotins, and many organic booster biocides may be found in ships and watercraft hulls to avoid the fouling of marine organisms. This type of paint can be harmful to the environment, therefore, the monitoring of toxic elements and compounds in antifouling paints are of great importance to access its quality and potential toxicity to the environment. Hence, this work describes the development of microwave-assisted digestion methods for the determination of Cu and Sn in antifouling paints by inductively coupled plasma optical emission spectrometry (ICP OES). The factors: sample mass and solutions of HNO3, HF, and HCl were optimized using the central composite design (CCD). Dry ashing with a muffle furnace and laser ablation-ICP-MS were used for methodological comparison with the microwave digestion-assisted ICP-OES methods. All the mixtures of acids allowed efficient extraction of the analytes; however, the one that stood out was the use of HF, HNO3, and H2O2.

Comparative Analysis of Spatial Distribution of Cholera by Temporal Fragments from 2000 to 2018.

Cholera is caused by V.cholerae (serogroups O1 and O139) and has a close relationship with socio-environmental conditions, especially basic sanitation. Analytical methodologies for collecting quantitative data on health indicators are widely used to support epidemiological surveillance actions in human health. This work aims to verify the fluctuation of the spatial distribution of cholera in the world, by temporal fragments, between 2000 and 2018. During the analyzed period, approximately 5.3 billion cases with 75.6 thousand deaths occurred, with emphasis on the regions of Africa, South Asia, and the Caribbean, showing that the disease is still a serious public health problem, especially in populations in precarious situations. Although the methodology employed in this study presents practical obstacles of underreporting and integration between the different collection platforms, it is an important tool in the construction of health surveillance measures for infectious diseases.

Populations Collapses in Marine Invertebrates Due to Endocrine Disruption: A Cause for Concern?

In the beginning of the twenty first century, the International Program on Chemical Safety published a document entitled Global Assessment of the State-Of-The-Science of Endocrine Disruptors. The work indicated only weak evidence of endocrine-related effects in human populations, and in wild animal populations. This document was revised in 2012 (State of the Science of Endocrine Disrupting Chemicals-2012) (1). The new document and the extensive scientific evidence it provided showed clearly that ED effects could be a risk to human and wildlife health. These works, however, were focused in human health and related animal models, mainly vertebrates and particularly mammals. It can be argued that invertebrates and many other taxa are important parts of all ecosystems, and, in many instances, have been shown to be also vulnerable to endocrine disruption. Thus, this work is aimed to show some observations on important marine invertebrate taxa, from an ecological point of view. The most important example of endocrine disruption in marine wild populations is the imposex response of marine gastropods, known for more than 40 years, and worldwide used to evaluate marine antifouling pollution. Among the mollusks, other important natural resources are bivalve species, used as human food sources and cephalopods, free-living, highly specialized mollusks, and also human food sources. Effects derived from endocrine disruptors in these species indicate that consumption could bring these compounds to human populations in an almost direct way, sometimes without any form of cooking or preparation. While discussing these questions, this work is also aimed to stimulate research on endocrine disruption among the invertebrate taxa that inhabited our oceans, and on which these effects are poorly known today.

Determination and speciation of cadmium in microcosms with Bunodosoma caissarum and Perna perna using isotopically enriched 116Cd.

The study of the uptake and distribution of elements in marine environments is of great interest for understanding their pathways and accumulation. Here, we investigated in laboratory experiments the accumulation behavior of Cd in the sea anemone Bunodosoma caissarum and the mussel Perna perna. Specimens were incubated with isotopically enriched 116Cd in aquariums. Cd concentrations in the seawater and in the tissues of B. caissarum and P. perna were followed by inductively coupled plasma-mass spectrometry (ICP-MS) by means of isotope dilution analysis. Bioconcentration factors for B. caissarum and P. perna exposed to 0.9µg·L-1 of 116Cd were determined to be 80.5 and 850, respectively. P. perna specimens exposed to 4.5µg·L-1 of 116Cd reached 530. Cytosolic proteins associated with Cd from the tissues were extracted and further analyzed by size-exclusion chromatography coupled to ICP-MS. Cd accumulation could be detected in both organisms ranging from high-molecular to low-molecular species.

Do pharmaceuticals reach and affect the aquatic ecosystems in Brazil? A critical review of current studies in a developing country.

Pharmaceutical residues are not completely removed in wastewater treatment plants (WWTPs) becoming contaminants in aquatic ecosystems. Thereby, it is important to investigate their concentrations in the environment and the possible consequences of their occurrence, including for human health. Here, we briefly reviewed the paths of pharmaceuticals to reach the environment, their behavior and fate in the environment, and the possible consequences of their occurrence. Moreover, we synthetized all the studies about the detection of pharmaceuticals in Brazilian water bodies and the available ecotoxicological knowledge on their effects. In this study, when we compare the data found on these compounds worldwide, we observed that Brazilian surface waters present considerable concentrations of 17α-ethinylestradiol, 17ß-estradiol, and caffeine. In general, concentrations found in aquatic systems worldwide seems to be low; however, ecotoxicological tests showed that even these low concentrations can cause sublethal effects in biota. The knowledge about the effects of continuous exposure and mixtures is sparse. In summary, new research is urgently required about the effects of these compounds in biota-including long-term exposition and mixture tests-and on specific technologies to remove these compounds in water bodies and WWTPs, besides the introduction of new policies for pharmaceutical use.

Assessing mercury contamination in a tropical coastal system using the mussel Perna perna and the sea anemone Bunodosoma caissarum.

Total mercury concentrations in the mussel Perna perna and the sea anemone Bunodosoma caissarum were determined to assess Hg contamination in Guanabara Bay, Rio de Janeiro, Brazil, and an adjacent sea area. Concentrations in the tissues of these species were compared. Average total mercury concentrations ranged from 3.54 to 21.01 µg kg-1 (wet wt.) in P. perna and from 4.51 to 23.19 µg kg-1 (wet wt.) for B. caissarum. Concentrations varied according to the sampling stations. Distribution of concentrations for both species was similar along the sampling stations, and a significant correlation was observed. Results suggest that B. caissarum could be a suitable biomonitor species for mercury contamination in the study area and could be used as a complementary species for monitoring studies. Further research is, however, needed to assess how environmental conditions and other variables affect Hg concentrations in B. caissarum.

Mercury distribution, methylation and volatilization in microcosms with and without the sea anemone Bunodosoma caissarum.

Mercury (Hg) has a complex biogeochemical cycle in aquatic environments. Its most toxic form, methylmercury (MeHg), is produced by microorganisms. This study investigated how the sea anemone Bunodosoma caissarum affects Hg distribution, methylation and volatilization in laboratory model systems. (203)Hg was added to microcosms and its distribution in seawater, specimens and air was periodically measured by gamma spectrometry. MeHg was measured by liquid scintillation. After the uptake period, specimens had a bioconcentration factor of 70 and in microcosms with and without B. caissarum, respectively 0.05% and 0.32% of the initial spike was found as MeHg. After depuration, MeHg in specimens ranged from 0.2% to 2.4% of total Hg. Microcosms with B. caissarum had higher Hg volatilization (58%) than controls (17%), possibly due to Hg(2+) reduction mediated by microorganisms associated with its tissues and mucus secretions. Marine organisms and their associated microbiota may play a role in Hg and MeHg cycling.

Organotins: a review of their reproductive toxicity, biochemistry, and environmental fate.

The review purposes are to (1) evaluate the experimental evidence for adverse effects on reproduction and metabolism and (2) identify the current knowledge of analytical procedures, biochemistry and environmental aspects relating to organotins. Organotins are pollutants that are used as biocides in antifouling paints. They produce endocrine-disrupting effects in mollusks, such as imposex. In rodents, organotin exposure induces developmental and reproductive toxicity as well as alteration of metabolic homeostasis through its action as an obesogen. The adverse effects that appear in rodents have raised concerns about organotins' potential health risk to humans in relation to organotin exposure. At present, triorganotin, such as tributyltin, have been demonstrated to produce imposex, and mammalian reproductive and metabolic toxicity. For most mammals, triorganotin exposure predominantly occurs through the ingestion, and this compound can cross the placenta. With these risks in mind, it is important to improve our knowledge of organotins' effects on environmental health.

An easy, non-destructive, probabilistic method to evaluate the imposex response of gastropod populations.

Endocrine disruption in marine populations is a growing concern. One of the best documented examples is imposex, the development of male characteristics in female gastropods, including the development of a penis and/or vas deferens, by exposure to organotins, mainly tributyltin. This syndrome has been an effective and widely used biomarker of organic tin contamination for almost 20 years. However, established imposex evaluation protocols sacrifice all the animals and repeated assessments can result in depletion of populations. To preserve animal lives as much as possible and to have a fast screening of areas subjected to organotin impacts, a non-destructive approach was tested. This approach uses reversible narcotization and a statistical criterion to evaluate the extent of imposex in the populations, instead of imposex indexes, which are based on evaluation of sacrificed, fixed animals. The data consist of two categories: males plus masculinized females in one category and normal females in another. The probability is then calculated that this sample could have been drawn from a normal population. This new method was tested in two contrasting areas of Brazil and with two different species, and the results compared to the conventional evaluation. Narcotization was completely reversed with a survival rate of 98%. Impacted sites could be identified with this technique in the same way as with the conventional one. The only limitation was that female sterility could not be verified. This disadvantage could well be compensated by the minimal mortality in the studied populations.

Occurrence of imposex in Thais haemastoma: possible evidence of environmental contamination derived from organotin compounds in Rio de Janeiro and Fortaleza, Brazil

Existem evidências de que a utilização amplamente disseminada de compostos organoestânicos (TBT e TPT) como antiincrustantes, estabilizadores em plásticos e como pesticidas tenha afetado severamente diversas espécies de organismos marinhos. O mais característico efeito do TBT e do TPT como desreguladores endócrinos é o desenvolvimento de caracteres sexuais masculinos em fêmeas de gastrópodos, conhecido como imposex. Esta síndrome pode levar à esterelização e morte dos organismos afetados. O presente trabalho apresenta uma vista geral ao estado atual do conhecimento sobre a ocorrência do imposex, e reporta os resultados de um estudo conduzido na Baía de Guanabara, Rio de Janeiro, e ao longo da costa de Fortaleza, no Ceará. Diferentes estágios de desenvolvimento do imposex foram verificados neste estudo, os mais proeminentes parecendo associados às fontes pontuais locais conhecidas de TBT e TPT.

Occurrence of imposex in Thais haemastoma: possible evidence of environmental contamination derived from organotin compounds in Rio de Janeiro and Fortaleza, Brazil.

There are indications that the widespread use of organotin compounds (TBT and TPT) as antifoulings, as stabilizers in plastic and as pesticides, has severely affected several species of marine organisms. The most striking effect of TBT and TPT as hormonal disruptors is the development of male organs in females of gastropods, currently denominated imposex. This syndrome can lead to the sterilization and death of affected organisms. The present work gives an overview of the present state of knowledge on imposex occurrence and reports results of a survey conducted in Guanabara Bay, Rio de Janeiro and in several sites along the coast of Fortaleza, Ceará State. Different stages of imposex development were verified in this survey, however, the most prominent levels appeared associated to known spot sources of TBT and TPT.