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Studies on the occurrence of POPs and other persistent compounds in pristine areas are extremely valuable, as they offer insights on the long-range transportation of POPs and the occurrence of natural compound producers' areas. In this regard, this study aimed to report data of both anthropogenic (polychlorinated biphenyls, PCBs, and polybrominated diphenyl ethers, PBDEs) and natural (methoxylated PBDEs, MeO-BDEs) compounds in tissues of the black triggerfish, Melichthys niger (Tetraodontiformes, Balistidae), specimens (n = 30) sampled in 2018 during a scientific expedition conducted at Trindade Island. Concentrations of ∑28PCBs ranged from 73 to 1052 ng g-1 lw in liver, 334 to 1981 ng g-1 lw in gonads, and 20 to 257 ng g-1 lw in muscle, with the predominance of PCB-180 in liver and PCB-52 in gonad and muscle. Concentrations of ∑7PBDEs ranged from

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BACKGROUND: Seafood consumers are widely exposed to diclofenac due to the high contamination levels often present in aquatic organisms. It is a potential risk to public health due its endocrine disruptor properties. Limited information is available about diclofenac behavior after food digestion to enable a more realistic scenario of consumer exposure. This study aimed to evaluate cooking effects on diclofenac levels, and determine diclofenac bioaccessibility by an in vitro digestion assay, using commercial fish species (seabass and white mullet) as models. The production of the main metabolite 4'-hydroxydiclofenac was also investigated. Fish hamburgers were spiked at two levels (150 and 1000 ng g-1) and submitted to three culinary treatments (roasting, steaming and grilling). RESULTS: The loss of water seems to increase the diclofenac levels after cooking, except in seabass with higher levels. The high bioaccessibility of diclofenac (59.1-98.3%) observed in both fish species indicates that consumers' intestines are more susceptible to absorption, which can be worrisome depending on the level of contamination. Contamination levels did not affect the diclofenac bioaccessibility in both species. Seabass, the fattest species, exhibited a higher bioaccessibility of diclofenac compared to white mullet. Overall, cooking decreased diclofenac bioaccessibility by up to 40% in seabass and 25% in white mullet. The main metabolite 4'-hydroxydiclofenac was not detected after cooking or digestion. CONCLUSION: Thus, consumption of cooked fish, preferentially grilled seabass and steamed or baked white mullet are more advisable. This study highlights the importance to consider bioaccessibility and cooking in hazard characterization studies. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

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Pest control is a main concern in agriculture. Indiscriminate application of synthetic pesticides has caused negative impacts leading to the rapid development of resistance in arthropod pests. Plant secondary metabolites have been proposed as a safer alternative to conventional pesticides. Monoterpenoids have reported bioactivities against important pests; however, due to their high volatility, low water solubility and chemical instability, the application of these compounds has been limited. Nanosystems represent a potential vehicle for the broad application of monoterpenoids. In this study, an 1,8-cineole nanoemulsion was prepared by the low energy method of phase inversion, characterization of droplet size distribution and polydispersity index (PDI) was carried out by dynamic light scattering and stability was evaluated by centrifugation and Turbiscan analysis. Fumigant bioactivity was evaluated against Tetranychus urticae, Rhopalosiphum maidis and Bemisia tabaci. A nanoemulsion with oil:surfactant:water ratio of 0.5:1:8.5 had a droplet size of 14.7 nm and PDI of 0.178. Formulation was stable after centrifugation and the Turbiscan analysis showed no particle migration and a delta backscattering of ±1%. Nanoemulsion exhibited around 50% more bioactivity as a fumigant on arthropods when compared to free monoterpenoid. These results suggest that nanoformulations can provide volatile compounds of protection against volatilization, improving their bioactivity.

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Persistent organic pollutants (POPs) were analyzed in 136 blubber samples of Franciscana dolphins from Brazil (Pontoporia blainvillei), which is the most threatened dolphin in the Southwestern Atlantic. The dolphins were caught by the fishery fleet and collected from 2000 to 2018 in three regions of São Paulo state: northern São Paulo (SPN), central São Paulo (SPC), and southern São Paulo (SPS). The POPs analyzed in this study were polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDTs), Mirex, hexachlorobenzene (HCB), chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs), and polybrominated diphenyl ethers (PBDEs). The concentrations ranged from 36 to 7200 ng g-1 lipid weight (lw) and 113-42200 ng g-1 lw for predominant compounds DDTs and PCBs, respectively. Similar profiles of PCB congeners were observed with a predominance of hexachlorinated compounds, representing approximately 50% of the total PCB amount; the highest PCB concentrations were observed from Baixada Santista (SPC) proximate to a highly urbanized and industrial coastal area. Significant differences were observed between the sexes and maturity of dolphins, mainly for PCBs, DDTs, and Mirex. In general, POPs other than HCB in Franciscana dolphins showed downward temporal trends, matching the regulatory periods for restricting and/or banning these compounds. Although POP concentrations are declining, PCB levels remain high in small dolphins, suggesting adverse health effects on Franciscanas. As organic contaminants are one of the numerous threats Franciscanas have been vulnerable to along the Brazilian coast, we recommend monitoring POPs levels every five years to check for declining (or stabilizing) trends.

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Accumulation of pesticides has a harmful impact on the environment and human health. The main goal of this work was to develop a method to determine and quantify the residues of thirteen pesticides in edible fish and bivalves such as parati (Mugil curema), seabass (Centropomus ssp.), mullet (Mugil brasiliensis), clams (Anomalocardia brasiliana) and mussel (Mytilus galloprovincialis) collected from Sepetiba Bay and Parnaiba River Delta (Brazil) between 2019 and 2020. Matrix solid-phase dispersion (MSPD) was used for extraction and quantification through gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). The method was validated (linearity, accuracy and precision) for fatty fish (Salmo salar), lean fish (Mugil curema) and bivalves (Mytilus edulis). The survey found linear correlation coefficients (r) equal to or greater than 0.9 for almost all analytes. The relative standard deviations (RSD) of five replicates were less than 20% for almost all analytes at different concentrations in lean fish, fatty fish and bivalves. Most analytes showed satisfactory accuracy. Alachlor herbicide was found in samples of seabass, mussels, clams and parati with levels ranging between 0.55 to 420.39 µg kg-1 dw. Ethion was found in parati (maximum 211.22 µg kg-1 dw), mussels (15.1 µg kg-1 dw) and clams (maximum 44.50 µg kg-1 dw). Alachlor was found in clams (maximum 93.1 µg kg-1 dw), and bifenthrin was found in parati (maximum 43.4 µg kg-1 dw) and clams (maximum 42.21 µg kg-1 dw). The validated method was satisfactory for the determination of eleven pesticides in the fatty fish matrix, and thirteen pesticides in the samples of lean fish and bivalves. The presence of alachlor, ethion and bifenthrin stands out.

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Pharmaceuticals (PhACs) are considered emerging contaminants with potential accumulation in aquatic organisms. Thus, seafood consumption may cause long-term effects and health risk for consumers. In the present study, the occurrence of PhACs in seafood from two Brazilian coastal areas, Sepetiba Bay (n = 43) and Parnaiba Delta River (n = 48), was determined for the first time, and their potential risk for human health was assessed. An eco-friendly multi-analytes method was used, after being validated for the different types of matrices (mussels, fatty and lean fish). All compounds under study were detected at least in four seafood species, including chloramphenicol, an antibiotic prohibited in animal foods. Most PhACs had mean concentrations below limit of quantification. Ibuprofen and other nonsteroidal anti-inflammatory drugs (NSAIDs), as well as simvastatin and carbamazepine were the main PhACs bioaccumulated in edible parts of seafood species from Brazil. The high trophic level carnivorous species, snook, was the most contaminated by NSAIDs, while bivalves were the seafood more contaminated by lipid regulators. The profile of contamination did not vary among different types of matrix, except in relation to carbamazepine and ketoprofen. These PhACs were more abundant in species from Sepetiba Bay, an area highly impacted by human influence. The estimated daily exposure for Brazilian population that consumes the studied species was up to 20.3 ng/kg bw/day via carib pointed-venus and 25.7 ng/kg bw/day via snooks, lower than acceptable daily intake. Thus, consumption of seafood species from Sepetiba Bay and Parnaiba Delta River seems to be safe to the population in what concerns the PhACs studied.

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Emerging infectious diseases have become a major global problem with public health and economic consequences. It is an urgent need to develop new anti-infective therapies. The natural diterpene carnosol exhibit a wide variety of interesting antibacterial and antiviral properties, and it is considered a theoretical inhibitor of COVID-19 Mpro. However, this compound is present in the family Lamiaceae in low quantities. To obtain carnosol in concentrations high enough to develop pharmacological studies, we evaluated the efficiency of a micropropagation protocol of Rosmarinus officinalis using a solid medium and a temporary immersion system (TIS), as well as the effect of 6-benzylaminopurine (6-BAP) and α-naphthaleneacetic acid (NAA) on the growth of shoots. Moreover, we developed and validated an analytical method to quantify carnosol using the H-point standard additions method in the high-performance liquid chromatography diode array detector (HPLC-DAD). After 30 days of culture, TIS produced the maximum number of shoots per explant (24.33 ± 1.15) on a liquid medium supplemented with 6-BAP at 5.0 mg L-1. Next, we also evaluated the effect of immersion time and frequency for TIS. After 72 days of culture, the best results were obtained with an immersion cycle of 1 min every 12 h, yielding 170.33 ± 29.40 shoots. The quantification of carnosol on the samples was performed at a flow rate of 1.2 mL min-1 using binary isocratic mobile phase system 60:40 (v/v) 10 mM formic acid (pH 3.0) (A) and acetonitrile (B) on a reverse-phase column. The content of carnosol in the in vitro cultures was around 8-fold higher than in the wild plant. The present study represents an efficient alternative method to obtain carnosol for its pre-clinical and clinical development.

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Polybrominated diphenyl ethers (PBDEs) and their methoxylated analogues (MeO-BDEs) are widely distributed in the environment. The main concern about the presence of PBDEs and MeO-BDEs in fish is due to their potential endocrine disruption effects in the specimens, and their potential risk to the health of human consumers. Considering these concerns, the goal of this study was to investigate the occurrence of PBDEs and MeO-BDEs in muscle tissues of blue shark (BSH), Prionace glauca, and yellowfin tuna (YFT), Thunnus albacares, caught in the Equatorial Atlantic Ocean (EAO), North-eastern Brazilian waters, and to evaluate the potential risk of human exposure by consumption. Muscle tissues of YFT and BSH were extracted using a Soxhlet apparatus and an Accelerated Solvent Extractor (ASE), respectively. PBDEs and MeO-BDEs were analysed by GC-NCI-MS. Concentrations of PBDEs ranged from not detected (nd) to 10 ng g-1 lipid weight (lw) in YFT muscle samples, while PBDE levels in BSH muscle samples ranged from

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In the current study, chemical composition of cultivated Salvia canariensis L was determined. Carnosol was the main product isolated. We prepared more lipophilic derivatives from carnosol, and both isolated and semisynthetic abietane diterpenes were evaluated in vitro as inhibitors of squalene synthase. Among the compounds tested, carnosol was the most potent inhibitor (IC50 = 17.6 µM). These results highlight the great potential of this species for the production of new ingredients in nutritional supplements for the treatment of hyperlipidemia.

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The available scientific literature regarding tanshinones is very abundant, and after its review, it is noticeable that most of the articles focus on the properties of tanshinone I, cryptotanshinone, tanshinone IIA, sodium tanshinone IIA sulfonate and the dried root extract of Salvia miltiorrhiza (Tan- Shen). However, although these products have demonstrated important biological properties in both in vitro and in vivo models, their poor solubility and bioavailability have limited their clinical applications. For these reasons, many studies have focused on the search for new pharmaceutical formulations for tanshinones, as well as the synthesis of new derivatives that improve their biological properties. To provide new insights into the critical path ahead, we systemically reviewed the most recent advances (reported since 2015) on tanshinones in scientific databases (PubMed, Web of Science, Medline, Scopus, and Clinical Trials). With a broader perspective, we offer an update on the last five years of new research on these quinones, focusing on their synthesis, biological activity on noncommunicable diseases and drug delivery systems, to support future research on its clinical applications.

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The presence of pyrethroid compounds in hepatic tissue of Guiana dolphins (Sotalia guianensis) is reported for the first time. Twelve pyrethroids were determined in 50 animals from eight locations of the Brazilian coast. The highest average concentration of total pyrethroids (∑PYR) was 1166 ng.g-1 lw, with values ranging from 148 to 5918 ng.g-1 lw, in Ilha Grande Bay, Rio de Janeiro State, while the Espírito Santo State had the highest median, 568 ng.g-1 lw. Permethrin was the predominant compound in most areas, contributing for 42% to 81% of the ∑PYR, whereas cypermethrin was the most abundant compound in Guanabara and Sepetiba bays (79% and 81%, respectively), both located in Rio de Janeiro State. Biological factors were not correlated with pyrethroids concentration. Tetramethrin and es/fenvalerate compounds were negatively correlated to the age, suggesting degradation/metabolization capacity in these animals that increases throughout life. Despite being metabolized and excreted, the wide use of these pollutants is reflected in relevant concentrations found in Guiana dolphins. This is the first study evaluating pyrethroids in a representative number of hepatic samples and covering >2600 km of coast. The overall lack of information on pyrethroids in cetaceans highlights the importance of understanding the profile and distribution of these pollutants in dolphins which exclusively inhabit the Southwestern Atlantic coast.

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The present study aimed to evaluate the efficacy of traditionally used antibacterial plants (Euphorbia prostrata, Schinus molle, Brickellia veronicaefolia and Lepidium virginicum) in Santa Rosa Range in Guanajuato against major mastitis-causing pathogens. The selected plants were phytochemically screened for alkaloids, flavonoids, polyphenols, saponins, anthraquinone, cardiac glycosides, steroids and terpenoids. Moreover, to achieve the main purpose of the present research, extracts of selected plants were tested for in vitro antibacterial activity against Staphylococcus aureus, Escherichia coli, Shigella spp., Bacillus subtilis, Clavibacter spp., Proteus vulgaris and Salmonella spp. All these bacterial were isolated from clinical mastitis in dairy cows. The results indicated that the ethanolic extract of the aerial part of L. virginicum exhibited the strongest antimicrobial activity, and it could be potential candidate specie for the development of novel veterinary drugs with low cost and fewer side effects.

O presente estudo teve como objetivo investigar a eficácia de plantas antibacterianas tradicionalmente usadas (Euphorbia prostrata, Schinus molle, Brickellia veronicaefolia e Lepidium virginicum) na cordilheira Santa Rosa, em Guanajuato, contra os principais patógenos causadores de mastite. As plantas selecionadas foram rastreadas fitoquimicamente quanto a alcalóides, flavonóides, polifenóis, saponinas, antraquinona, glicosídeos cardíacos, esteróides e terpenóides. Além disso, para atingir o objetivo principal da presente pesquisa, extratos de plantas selecionadas foram testados quanto à atividade antibacteriana in vitrocontra Staphylococcus aureus, Escherichia coli, Shigella spp., Bacillus subtilis, Clavibacter spp., Proteus vulgaris e Salmonella spp. Todas essas bactérias foram isoladas de mastite clínica em vacas leiteiras. Os resultados indicaram que o extrato etanólico da parte aérea de L. virginicum exibia a atividade antimicrobiana mais forte e poderia ser uma espécie potencial candidata ao desenvolvimento de novos medicamentos veterinários com baixo custo e menos efeitos colaterais.

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From November 2017 to March 2018, a cetacean morbillivirus (CeMV) outbreak caused an unprecedented mass mortality among Guiana dolphins Sotalia guianensis in Ilha Grande Bay and Sepetiba Bay, Rio de Janeiro, Brazil. Small boat surveys were conducted to document the behavior and clinical signs presented by diseased dolphins. We observed 5 abnormally behaving, disoriented Guiana dolphins on separate days, of which 1 died stranded and 2 sank. Signs of ataxia included difficulties with swimming and maintaining a course, balance and buoyancy. At least 40 other individuals were emaciated, and 10 photo-identified dolphins had miscellaneous skin lesions, some ulcerated. Labored breathing suggestive of airway obstruction was heard in several groups. These neurological, respiratory and cutaneous signs may comprise part of the clinical constellation of CeMV infection in dolphins. The combined threat of anthropogenic pressures and CeMV lethal disease is of concern for the survival of the Guiana dolphin population in Sepetiba Bay.

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UV filters (UV-Fs) constitute a heterogeneous group of chemicals used as protection against the effects of UV radiation, widely used in all sort of goods and ubiquitous in the environment. The presence of these chemicals in fish is a matter of concern, because many UV-Fs display hormonal activity. In this study, muscle, gills, and liver from 11 Mugil liza individuals from the highly urbanized Guanabara Bay (Rio de Janeiro, Brazil) were analysed in order to detect eight UV-Fs and metabolites (4-dihydroxybenzophenone [BP1] (2-hydroxy-4-methoxybenzophenone [BP3], 4-methylbenzylidiene camphor [4MBC], ethylhexyl methoxycinnamate [EHMC], ethylhexyl dimethyl p-aminobenzoic acid [ODPABA], octocrylene [OC], 4-hydroxybenzophenone [4HB], and 4,4'-dihydroxybenzophenone [4DHB]) using liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Results showed that both target UV-Fs and metabolites were ubiquitous in the analysed tissues. Lower concentrations were observed in muscle and gills (3.07-31.6ngg-1 dry weight (dw)), whereas in liver significant amounts of metabolites (5.47-451ngg-1 dw) were present. With the concentrations determined in the fish, an estimation of the daily intake revealed that consumption of muscle in the diet represent from 0.3 to 15.2ng UV-Fs (kg body weight-1) d-1, higher than those reported in fish for selected persistent organic pollutants (POPs).

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To catalog the diversity and abundance of halogenated organic compounds (HOCs) accumulating in high trophic marine species from the southwestern Atlantic Ocean, tissue from bottlenose dolphins (Tursiops truncatus) stranded or incidentally captured along the coast of Rio de Janeiro, Brazil, were analyzed by a nontargeted approach based on GC×GC/TOF-MS. A total of 158 individual HOCs from 32 different structural classes were detected in the blubber of 4 adult male T. truncatus. Nearly 90% of the detected compounds are not routinely monitored in the environment. DDT-related and mirex/dechlorane-related compounds were the most abundant classes of anthropogenic origin. Methoxy-brominated diphenyl ethers (MeO-BDEs) and chlorinated methyl- and dimethyl bipyrroles (MBPs and DMBPs) were the most abundant natural products. Reported for the first time in southwestern Atlantic cetaceans and in contrast to North American marine mammals, chlorinated MBPs and DMBPs were more abundant than their brominated and/or mixed halogenated counterparts. HOC profiles in coastal T. truncatus from Brazil and California revealed a distinct difference, with a higher abundance of MeO-BDEs, mirex/dechloranes and chlorinated bipyrroles in the Brazilian dolphins. Thirty-six percent of the detected HOCs had an unknown structure. These results suggest broad geographical differences in the patterns of bioaccumulative chemicals found in the marine environment and indicate the need to develop more complete catalogs of HOCs from various marine environments.

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Pyrethroids (PYR) and UV filters (UVF) were investigated in tissues of paired mother-fetus dolphins from Brazilian coast in order to investigate the possibility of maternal transfer of these emerging contaminants. Comparison of PYR and UVF concentrations in maternal and fetal blubber revealed Franciscana transferred efficiently both contaminants to fetuses (F/M > 1) and Guiana dolphin transferred efficiently PYR to fetuses (F/M > 1) different than UVF (F/M < 1). PYR and UVF concentrations in fetuses were the highest-ever reported in biota (up to 6640 and 11,530 ng/g lw, respectively). Muscle was the organ with the highest PYR and UVF concentrations (p < 0.001), suggesting that these two classes of emerging contaminants may have more affinity for proteins than for lipids. The high PYR and UVF concentrations found in fetuses demonstrate these compounds are efficiently transferred through placenta. This study is the first to report maternal transfer of pyrethroids and UV filters in marine mammals.

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Blubber samples from three delphinid species (false killer whale, Guiana and rough-toothed dolphin), as well as liver samples from franciscana dolphins were analyzed for dioxins and related compounds (DRCs). Samples were collected from 35 cetaceans stranded or incidentally captured in a highly industrialized and urbanized area (Southeast and Southern Brazilian regions). Dioxin-like PCBs accounted for over 83% of the total TEQ for all cetaceans. Non-ortho coplanar PCBs, for franciscanas (82%), and mono-ortho PCBs (up to 80%), for delphinids, constituted the groups of highest contribution to total TEQ. Regarding franciscana dolphins, significant negative correlations were found between total length (TL) and three variables, ΣTEQ-DRCs, ΣTEQ-PCDF and ΣTEQ non-ortho PCB. An increasing efficiency of the detoxifying activity with the growth of the animal may be a plausible explanation for these findings. This hypothesis is reinforced by the significant negative correlation found between TL and PCB126/PCB169 concentration ratio. DRC concentrations (ng/g lipids) varied from 36 to 3006, for franciscana dolphins, as well as from 356 to 30,776, for delphinids. The sum of dioxin-like and indicator PCBs varied from 34,662 to 279,407 ng/g lipids, for Guiana dolphins from Rio de Janeiro state, which are among the highest PCB concentrations ever reported for cetaceans. The high concentrations found in our study raise concern not only on the conservation of Brazilian coastal cetaceans, but also on the possibility of human health problem due to consumption of fish from Brazilian estuaries.

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Most current bioexposure assessments for UV filters focus on contaminants concentrations in fish from river and lake. To date there is not information available on the occurrence of UV filters in marine mammals. This is the first study to investigate the presence of sunscreen agents in tissue liver of Franciscana dolphin (Pontoporia blainvillei), a species under special measures for conservation. Fifty six liver tissue samples were taken from dead individuals accidentally caught or found stranded along the Brazilian coastal area (six states). The extensively used octocrylene (2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate, OCT) was frequently found in the samples investigated (21 out of 56) at concentrations in the range 89-782 ng·g(-1) lipid weight. São Paulo was found to be the most polluted area (70% frequency of detection). Nevertheless, the highest concentration was observed in the dolphins from Rio Grande do Sul (42% frequency of detection within that area). These findings constitute the first data reported on the occurrence of UV filters in marine mammals worldwide.

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F-ring opening in spirostanes with the 16ß,22:22,25-diepoxy-23-acetoxymethyl-24-methyl side chain produces a Δ(22)-intermediate with an allylic acetoxy group. For this reason the reactivity profile of these compounds deviates from that observed in other naturally occurring or synthetic spirostanes and furospirostanes.

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The present study constitutes the first investigation to demonstrate pyrethroid bioaccumulation in marine mammals, despite the assumption that these insecticides are converted to non-toxic metabolites by hydrolysis in mammals. Twelve pyrethroids were determined in liver samples from 23 male franciscana dolphins from Brazil. The median concentration values for total pyrethroids were 7.04 and 68.4 ng/g lw in adults and calves, respectively. Permethrin was the predominant compound, contributing for 55% of the total pyrethroids. Results showed a distinct metabolic balance of pyrethroids through dolphin life. High loads are received at the beginning of their lives and, when they reach sexual maturity, these mammals seem to degrade/metabolize pyrethroids. Maternal transfer of these compounds was also evaluated through the analysis of breast milk and placenta samples. Pyrethroids were detected in both matrices, with values between 2.53-4.77 ng/g lw and 331-1812 ng/g lw, respectively. Therefore, for the first time, a study shows mother-to-calf transfer of pyrethroids by both gestational and lactation pathways in dolphins.

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