Endocrine disrupting bisphenol A, 4-tert-octylphenol and 4-nonylphenol in gonads of long-tailed ducks Clangula hyemalis wintering in the southern Baltic.

This paper focuses on determining the concentrations of phenol derivatives in the gonads of seabirds and examining the potential factors (age, sex and region) affecting the degree of their bioaccumulation. The study involved assays of bisphenol A (BPA), 4-tert-octylphenol (4-t-OP) and 4-nonylphenol (4-NP) in the gonads of long-tailed ducks taken as bycatch from the Southern Baltic region in 2015-2016. Among phenol derivatives, 4-NP was found to reach the highest concentrations in the gonads of long-tailed ducks, and its concentrations were in the range of <0.1-717.5 ng g-1 dw. The concentrations of BPA and 4-t-OP were similar and amounted to <0.4-181.6 ng g-1 dw and <0.1-192.4 ng g-1 dw respectively. The concentration levels of phenol derivatives in the birds' gonads were similar to the levels which had been observed to have negative endocrine effects in other authors studies. This shows that the studied xenoestrogens can interfere with the reproduction and development of birds. Moreover, adult long-tailed ducks had higher concentrations of phenol derivatives compared to immature ones, possibly resulting from long-term bioaccumulation, as well as from diverse pollution in their respective habitats. Particularly in the case of 4-NP, the median concentrations in gonads of adult birds were 2-fold higher than in immature ones. In turn, among adult long-tailed ducks, phenol derivatives were characterized by higher concentrations in males than in females, with almost 3 times and approx. 3.5 times higher median concentrations of BPA and 4-t-OP, respectively. Lower concentrations of phenol derivatives in female gonads may result from the additional elimination of pollutants from their bodies through the transfer of pollutants from mother to egg. The results show the need for further research on phenol derivatives in the gonads of birds, focusing on their impact on the reproductive system and early development.

Elimination of endocrine disrupting phenolic compounds via feathers and claws in seabirds moulting in the Baltic and Russian Arctic.

This paper investigates the effectiveness of phenol derivatives removal from bird organisms via claws and remiges, and performs a preliminary assessment of the usefulness of these epidermal products for environmental biomonitoring and estimating bird exposure levels. Concentrations of bisphenol A (BPA) and alkylphenols: 4-tert-octylphenol (4-t-OP) and 4-nonylphenol (4-NP) were determined in claws and remiges of long-tailed ducks Clangula hyemalis and razorbills Alca torda, obtained during a by-catch in the winter period (2014-2016) in the Southern Baltic region. For razorbills, the Baltic is a permanent habitat, while long-tailed ducks are migratory and stay in the Southern Baltic only during the non-breeding season. Their remiges are replaced in the Arctic seas of Siberia. The removal of phenol derivatives, depending on the compound and the epidermal product, ranges from 12 % to 34 %. Among these compounds, in both bird species, the highest degree of elimination was observed for 4-NP in remiges (<0.1-656.0 ng.g-1 dw) as well as claws (<0.1-338.6 ng.g-1 dw). On the other hand, the least removed compound in both the long-tailed duck and the razorbill was 4-t-OP. The removal of phenol derivatives from claws in both bird species was at the same level. However, 4-NP concentrations were found to be statistically significantly higher in razorbill remiges compared to those of the long-tailed duck (p < 0.05). Comparison of concentrations in the remiges of the long-tailed duck and the razorbill, moulted in two different environments with different levels of pollution and distances from sources, indicated that the Baltic Sea is approximately 3 times more polluted with 4-NP than the marine areas of the Russian Arctic. This demonstrates the potential for the use of 4-NP and remiges as indicators of environmental pollution with phenol derivatives.

Concentrations of bisphenol a (BPA) in fresh pork loin meat under standard stock-farming conditions and after oral exposure - A preliminary study.

Bisphenol A (BPA) is a substance commonly used in the production of plastics. It may be leached from plastics, penetrate to food and has multidirectional negative effects on living organisms. The aim of this study was to evaluate BPA levels in fresh pork meat collected immediately after the death of animals kept in standard stock-farming conditions, as well as from animals receiving various oral doses of BPA (0.05 mg/kg body weight (b.w.)/day and 0.5 mg/kg b. w./day). In animals kept in standard conditions, the average concentration of BPA in loin meat amounted to 37.03 ± 6.18 ng/g dry weight (d.w.). In animals receiving lower and higher doses of BPA, this value achieved 47.44 ± 4.39 ng/g d. w. and 214.30 ± 66.73 ng/g d. w, respectively. The results show that pork meat may be a source of BPA in human food and the presence of BPA in the meat may result from the exposure of animals over their lifetime. This observation shows that the elimination of BPA from the production of items used for animal husbandry and animal feed may reduce meat contaminated with this substance and, therefore, increase consumer safety.

Distribution paths of endocrine disrupting phenolic compounds in waterbirds (Mergus merganser, Alca torda, Clangula hyemalis) from the Southern Baltic.

This study determined the distribution of phenol derivatives in the organisms of waterbirds and the factors influencing their bioaccumulation and affinity to specific tissues. Concentrations of bisphenol A (BPA), 4-tert-octylphenol (4-t-OP) and 4-nonylphenol (4-NP) were determined in the brains, subcutaneous fat, kidneys, livers and pectoral muscles of goosanders Mergus merganser (GO), long-tailed ducks Clangula hyemalis (LO) and razorbills Alca torda (RA). The birds came from the winter by-catch (2014-2016) in the Southern Baltic. Different distribution routes of individual phenol derivatives in the birds were established, most likely due to their ability to bind to proteins and/or dissolve in lipids. BPA and 4-NP accumulated most in the muscles (BPA <2.0-223.0 ng.g-1 dw, 4-NP 26.0-476.4 ng.g-1 dw), livers (BPA <2.0-318.2 ng.g-1 dw, 4-NP 60.7-525.8 ng.g-1 dw), and kidneys (BPA <2.0-836.1 ng.g-1 dw, 4-NP 29.3-469.2 ng.g-1 dw), while 4-t-OP was stored mainly in the brains (2.6-341.1 ng.g-1 dw), subcutaneous fat (0.7-173.7 ng.g-1 dw) and livers (<0.5-698.8 ng.g-1 dw). The liver was the only organ where all compounds showed a positive correlation with each other and alkylphenols were also positively correlated with each other in tissues with high fat content (brains and subcutaneous fat), and negatively in muscles. Despite the different trophic levels of birds, the concentrations of phenol derivatives in the tissues between individual species in most cases did not differ significantly. However, between the species on a similar trophic level, the higher biomagnification coefficient was calculated for LO feeding on benthos, and the lower for RA feeding on pelagic fish (p < 0.05). The good condition of birds, resulting in large intestinal fat stores, promoted on the one hand the penetration of phenol derivatives from the intestine to the liver, and on the other hand their accumulation in subcutaneous fat, thereby protecting the brain.

Bioaccumulation of phenolic endocrine disruptors in the clam Rangia cuneata: Storage in shells and influence of size and sex.

This study aimed to investigate the sequestration of phenolic endocrine disrupting compounds (EDCs) such as bisphenol A (BPA), 4-t-octylphenol (4-t-OP), and 4-nonylphenol (4-NP) in the shells of the mature clam Rangia cuneata from the Vistula Lagoon (southern Baltic Sea) and to determine the influence of sex and shell length on bioaccumulation of these contaminants. Even though there is broad interest in EDCs influences on aquatic organisms, these basic parameters are poorly understood, yet necessary for assessing environmental risks for clams. Average proportions of the total body burden (ng/individual) deposited in shells of R. cuneata were more than 70% for BPA and 4-NP and up to 32% for 4-t-OP. These results indicate that shell storage can be an important route for elimination of specific EDCs. Relationships between EDCs concentrations and the size and sex of R. cuneata indicate that females and large individuals experience greater exposures to the adverse effects of these pollutants than males and smaller clams. This effect could have significant impacts on population ecology and ultimately affect the entire ecosystem, in which bivalves play an important role. In the context of using clams to assess water pollution, the co-variation of EDCs concentrations with the size and sex of bivalves could influence the quality of monitoring data, unless accounted for in sampling design and data analysis.

Gastrointestinal and respiratory exposure of water birds to endocrine disrupting phenolic compounds.

Aquatic birds found at the top of the trophic chain are exposed to xenobiotics present both in food and inhaled air. The aim of this study was to indicate and assess the routes and levels of exposure of aquatic birds to bisphenol A (BPA), 4-tert-octylphenol (4-t-OP) and 4-nonylphenol (4-NP). The birds constituting the study material (Clangula hyemalis, Alca torda, Mergus merganser) originated from by-catches (winter 2014-2016) in the Southern Baltic. The studies show that the exposure of birds to phenol derivatives is determined by the specifics of a compound, the habitat area, trophic level and food consumed. BPA was characterized by the highest intestinal concentrations in all birds (6.6-1176.2 ng.g-1 dw). Higher concentrations of 4-t-OP were determined in the lungs of birds from the eastern part of the Southern Baltic (9.1-135.7 ng.g-1 dw) and in the intestines of birds from the western part (<0.5-191.4 ng.g-1 dw). In the case of 4-NP, higher concentrations were found in the intestines of carnivorous species (64.9-524.5 ng.g-1 dw), and the lungs of benthos-eating species (39.4-399.7 ng.g-1 dw). The intestines that were most burdened with 4-NP were those of birds from the highest trophic level. Correlations between the concentrations of phenol derivatives in the blood and the intestines and lungs indicated that birds are exposed to the penetration of phenol derivatives through the digestive and respiratory tracts. BPA and 4-NP were characterized by the highest concentrations in the intestines and lungs, whereas 4-t-OP in blood (3.2-39.2 ng.cm-3), which may indicate the largest endocrine potential of this compound in birds. Significant differences in phenol derivatives concentrations in the intestines and lungs of birds from the western and eastern part of the Southern Baltic, shows that these tissues can be useful for assessing the contamination of the environment with EDCs.

Could biotransport be an important pathway in the transfer of phenol derivatives into the coastal zone and aquatic system of the Southern Baltic?

Bird guano and the faeces of marine mammals appear to be a significant yet undisclosed biotransporter of Endocrine Disrupting Compounds in the marine environment. The authors determined the concentration of bisphenol A (BPA), 4-tert-octylphenol (4-t-OP) and 4-nonylphenol (4-NP) removed from birds and seals in their droppings into the coastal zone of the Gulf of Gdansk (Southern Baltic Sea).The research was carried out on samples of bird guano collected during the breeding season and after in 2016 at nesting sites, as well as on faecal samples from grey seals (Halichoerus grypus grypus) living in the Seal Centre of the Marine Station in Hel between 2014 and 2018. Measurements were carried out using high performance chromatography with fluorescence detector. Results have shown that the presence of seabird habitats and grey seal colonies in the coastal zone of the Gulf of Gdansk can have an impact on the pollution of the seashore (beach sand, bottom sediment and surface seawater) with phenol derivatives. The concentrations of BPA, 4-t-OP and 4-NP ranged from 0.1 to 32.97 ng∙g-1dw in sediment and beach sand, and from 0.23 to over 800 ng dm-3 in seawater. In the cases of bisphenol A and 4-tert-octylphenol safe concentration levels in the waters were exceeded. Bisphenol A concentrations were almost always found to be the highest. This was also noted in bird guano and seal faeces, although it was found to be much higher in the seal faeces - average 10149.79 ng g-1 dw, than in bird guano. An experiment conducted to assess BPA, 4-t-OP, 4-NP leaching from bird guano and seal faeces into seawater, also confirmed the importance of animal excrement in the circulation of these compounds in the marine ecosystem. The highest % of leaching related to BPA was noted at 20 °C and reached 84%. The lowest % of leaching was for 4-nonylphenol (44%).

Analytical methods for determination of bisphenol A, 4-tert-octylphenol and 4-nonylphenol in herrings and physiological fluids of the grey seal.

•The aim of this work was to develop the methods of determination for phenol derivatives: bisphenol A (BPA), 4-tert-octylphenol (OP) and 4-nonylphenol (NP), in the whole body of herring Clupea harengus and in physiological fluids of the Baltic grey seal Halichoerus grypus grypus (blood and milk).•Methods were based on liquid chromatography coupled with a fluorescence detector (HPLC-FL).•These methods were satisfactorily validated, each showing good recovery (>80%) and precision (RSD < 15%). Regarding the limit of quantification (LOQ), this was established at <2 ng g-1 for herring, <0.07 ng cm-3 for blood and <0.1 ng cm-3 for milk.

Maternal transfer of phenol derivatives in the Baltic grey seal Halichoerus grypus grypus.

Studies of circulating levels in difference sex and age classes, and maternal transfer of bisphenol A, 4-tert-octylphenol and 4- nonylphenol in the Baltic grey seal were performed from 2014-2017. Blood was collected from long-term captive adult males, pregnant females and pups. Milk was collected from nursing females. The aim of this study was not only to determine the concentrations of phenol derivatives, i.e. bisphenol A (BPA), 4-tert-octylphenol (OP) and 4-nonylphenol (NP), but also to try to evaluate the transfer of these compounds to the next generation in the final stage of foetal life and in the first few weeks of life in juvenile marine mammals. The measurements were carried out using high performance liquid chromatography. The obtained data show that all phenol derivatives are present in the blood of males, females and pups (range <0.07-101 ng·cm-3) and in female milk (range <0.1-406.3 ng·cm-3). The main source of phenol derivatives in organisms is food exposure. Gender, age, or number of births were not observed to have a significant effect on changes in phenol derivative levels in seal blood within the breeding group. In the prenatal stage of life, a small amount of BPA and alkylphenols was passed on to the offspring through the placenta. In the blood of the offspring the concentration of these compounds exceeded the concentration in the mother's blood 1.5-fold. During nursing, females detoxified their systems. Level of phenol derivatives in the pups blood increased linearly with its increasing concentrations in the mother's milk. On the other hand, the seafood diet which started after the physiological fasting stage of the pup, stabilised the levels of phenol derivatives below 10 ng ∙ cm-3.