Behavior of diclofenac from contaminated fish after cooking and in vitro digestion.

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.

Temporal trends of persistent organic pollutant contamination in Franciscana dolphins from the Southwestern Atlantic.

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.

Survey on endocrine-disrupting chemicals in seafood: Occurrence and distribution.

Currently, the presence of endocrine disrupting chemicals (EDCs) in the marine environment pose а potential risk to both wildlife and human health. The occurrence of EDCs in seafood depends of several factors such as source and amounts of EDCs that reach the aquatic environment, physicochemical features of EDCs, and its accumulation in trophic chain. This review highlights the occurrence and distribution of EDCs along the seafood in the last 6 years. The following EDCs were included in this review: brominated flame retardants (PBDEs, PBBs, HBCDDs, TBBPA, and novel flame retardants); pharmaceuticals (paracetamol, ibuprofen, diclofenac, carbamazepine), bisphenols, hormones, personal care products (Musk and UV Filters), and pesticides (organochlorides, organophosphates, and pyrethroids). Some of them were found above the threshold that may cause negative effects on human, animal, and environmental health. More control in some countries, as well as new legislation and inspection over the purchase, sale, use, and production of these compounds, are urgently needed. This review provides data to support risk assessment and raises critical gaps to stimulate and improve future research.

Occurrence of pharmaceuticals in seafood from two Brazilian coastal areas: Implication for human risk assessment.

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.

Polybrominated diphenyl ethers and their methoxylated congeners in Douro river estuary biota: Seasonal occurrence and risk assessment.

Especially added on many industrial and domestic products as flame retardants (FRs), polybrominated diphenyl ethers (PBDEs) are among the chemicals of high environmental concern because of their potential harmfulness for environmental and human health. Seafood consumption is considered the main source of PBDEs and their methoxylated congeners (MeO-BDEs) for humans. The present study aims to investigate the seasonal occurrence of six PBDEs and eight MeO-BDEs congeners using Douro river biota (different trophic levels) as sentinels, as well as to evaluate the human exposure risk to PBDEs through seafood consumption. Biota samples (n = 273) were collected from one of the most important Portuguese estuaries in the north-western coast of Portugal at four different seasons (2019-2020). The analyses were performed by an environmental-friendly extraction procedure followed by Gas Chromatography coupled to a triple quadrupole detector (GC-MS/MS). PBDEs were detected in all seafood samples analysed, with means ranging from 0.02 ng g-1 ww (flounder in autumn) to 3.75 ng g-1 ww (mussel in winter). Levels of lower-brominated PBDE congeners were significantly higher than higher-brominated ones in all seasons (p < 0.01). MeO-BDEs ranged from 0.001 ng g-1 ww (grey mullet in summer) to 5.66 ng g-1 ww (green crab in spring). Crabs and mussels presented the highest means of PBDEs and MeO-BDEs. Regarding the health risk assessment of the studied PBDE congeners (47, 99, and 153), consumption of Douro river fish is not a case of concern for consumers.

Pyrethroid insecticides along the Southwestern Atlantic coast: Guiana dolphin (Sotalia guianensis) as a bioindicator.

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.

Halogenated natural products in birds associated with the marine environment: A review.

Halogenated natural products (HNPs) are widespread compounds found at high concentrations in top predators such as seabirds. This paper reviews available data on methoxylated polybrominated diphenyl ethers (MeO-BDEs), heptachloro-1'-methyl-1,2'-bipyrrole (Q1) and 1,1'-dimethyl-2,2'-bipyrroles (HDBPs) in these animals. In all, 25 papers reported such HNPs in seabirds. White tailed sea eagle from Sweden was the seabird species with higher MeO-BDEs levels in eggs and blood, while in liver the European shag from Norway was the one. Regarding HDBPs, glaucous gull livers from North Water Polynya and Leach's storm petrel eggs from South Canada (NE Atlantic) showed the highest levels, while brown skua eggs presented the highest concentration of Q1. DBP-Br4Cl2 and DBP-Br6 were the most abundant HDBPs in seabirds, although only one study investigated DBP-Br6. Furthermore, 2'-MeO-BDE-68/6'-MeO-BDE-47 ratios were lower than one in mostly of the studies (91%). The main sources of methoxylated congeners found in seabirds might to be from sponges and/or associated organisms (bacteria). The scarcity of data in seabirds showed the gap in knowledge. Few studies were done especially in tropical areas and Southern Hemisphere and the most were conducted in the northwest part of the globe. This review arouses the need of knowledge about the distribution of these compounds in seabirds worldwide as well as it encourages toxicological studies to better understand the possible effects of HNPs on seabirds.

Clinical signs in free-ranging Guiana dolphins Sotalia guianensis during a morbillivirus epidemic: case study in Sepetiba Bay, Brazil.

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.

Preliminary study of long-range transport of halogenated flame retardants using Antarctic marine mammals.

Eight PBDE congeners, three emerging brominated flame retardants, five dechloranes and eight MeO-PBDEs were monitored in tissues (muscular, adipose, brain) and fur of southern elephant seal and Antarctic fur seal of the South Shetland Islands, Antarctic Peninsula. Total PBDEs and total dechloranes concentrations ranged between n.d.-6 ng/g lw. While PBDEs were not detected in brain tissue, Dec 602 was found in brain tissue of both seal species indicating that dechloranes -with potential neurological toxicity- could cross the blood-brain barrier. Emerging brominated flame retardants were not detected in any sample and only two MeO-PBDEs, which are of natural origin, were found. The presence of the detected compounds in biota from the Antarctic evidences their long-range transportation, being of special interest the detection of emerging compounds such as dechloranes. This is the first time that these contaminants have been detected in marine mammals from the Antarctic. BDE-47 concentrations were lower than previously reported for the same species, suggesting a successful effect of the existing regulation and bans on PBDEs. CAPSULE ABSTRACT: Halogenated flame retardants were in tissues of Antarctic seals proving long-range transport. Dechloranes showed similar behaviour to PBDEs, additionally they crossed the BBB.

Occurrence of organic UV filters and metabolites in lebranche mullet (Mugil liza) from Brazil.

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).

Nontargeted Screening of Halogenated Organic Compounds in Bottlenose Dolphins (Tursiops truncatus) from Rio de Janeiro, Brazil.

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.

Toxic heritage: Maternal transfer of pyrethroid insecticides and sunscreen agents in dolphins from Brazil.

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.

Anthropogenic (PBDE) and naturally-produced (MeO-PBDE) brominated compounds in cetaceans--a review.

This paper reviews the available data on brominated flame retardants, the polybrominated diphenyl ethers (PBDEs), as well as on the naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) in cetacean tissues around the world. Levels and possible sources of both compound classes are discussed. Odontocete cetaceans accumulate higher PBDE concentrations than mysticete species. PBDE contamination was higher in cetaceans from the Northern hemisphere, whereas MeO-PBDE levels were higher in animals from the Southern hemisphere. Southern resident killer whales from NE Pacific presented the highest levels reported in biota, followed by bottlenose dolphins from North Atlantic (U.K. and U.S. coast). Many species presented PBDE concentrations above threshold levels for health effects in odontocetes. Time trend studies indicate that PBDE concentrations in odontocetes from Japan, China, U.S. and Canada coastal zones have increased significantly over the past 30 years. Studies from U.K. waters and NE Atlantic showed a decrease and/or stability of PBDE levels in cetacean tissues in recent decades. The highest MeO-PBDE concentrations were found in dolphins from Tanzania (Indian Ocean), bottlenose dolphins from Queensland, Australia (SW Pacific), and odontocetes from coastal and continental shelf waters off southeastern Brazil (SW Atlantic). The upwelling phenomenon and the presence of coral reef complexes in these tropical oceans may explain the large amounts of the naturally-produced organobromines. Considering that these bioaccumulative chemicals have properties that could cause many deleterious effects in those animals, future studies are required to evaluate the potential ecotoxicological risks.

High accumulation of PCDD, PCDF, and PCB congeners in marine mammals from Brazil: a serious PCB problem.

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.

First determination of UV filters in marine mammals. Octocrylene levels in Franciscana dolphins.

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.

Pyrethroids: a new threat to marine mammals?

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.

Natural and anthropogenically-produced brominated compounds in endemic dolphins from Western South Atlantic: another risk to a vulnerable species.

Liver samples from 53 Franciscana dolphins along the Brazilian coast were analyzed for organobrominated compounds. Target substances included the following anthropogenic pollutants: polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), decabromodiphenylethane (DBDPE), as well as the naturally-generated methoxylated-PBDEs (MeO-PBDEs). PBDE concentrations ranged from 6 to 1797 ng/g lw (mean 166 ± 298 ng/g lw) and were similar to those observed in cetaceans from Northern Hemisphere. PBBs were found in all sampling locations (