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.

Comparison of prenatal and postnatal exposure to endocrine active phenol derivatives in mammals - Humans and Baltic grey seals.

Bisphenol A (BPA), 4-tert-octylphenol (4-t-OP), and 4-nonylphenol (4-NP) are characterised by their endocrine active properties. Their negative effects on the development of the body are doubly important in the reproduction process. The goal was to compare the maternal transfer of phenol derivatives in humans and seals and identify factors that may affect the load of phenol derivatives entering the mother's body, which translates into a risk to the offspring. Phenol derivatives were determined using HPLC-FLD. It was shown that higher concentrations of phenol derivatives in blood or milk were detected in humans (mothers and newborns) compared to concentrations in Baltic seals. This was influenced by external exposure factors, i.e., leaching of phenol derivatives from food packaging or dermal contact. The authors conclude that milk is the main component in the maternal transfer of BPA to the next generation in humans, while blood is a carrier of alkylphenols, particularly 4-tert-octylphenol.

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.

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.

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%).

137Cs and 40K in gray seals Halichoerus grypus in the southern Baltic Sea.

This study presents levels of 137Cs and 40K concentrations in the placentas of seals gathered in the period 2007-2015. The mean activity of 137Cs and 40K was 5.49 Bq kg-1w.w. and 136.6 Bq kg-1 ww respectively. Statistically significant correlation was observed between the 137Cs activities in placenta and in herring-the staple food for seals. The concentrations of 137Cs and 40K were also determined in other tissues (muscle, liver, lung, and brain) of wild seals. The concentrations of 137Cs were from 2.59 Bq-1 ww (lungs) to 24.3 Bq kg-1 ww (muscles). The transfer factor values for 137Cs (seal tissue/fish) ranged from 0.89 to 2.42 in the case of the placentas and from 1.35 to 8.17 in the case of the muscle. For adults seal, the effective dose from 137Cs was 2.98 nGy h-1. The mean external radiation dose to pup was 0.77 nGy h-1 from 137Cs and 6.69 nGy h-1 from 40K.

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.

Transfer of mercury and phenol derivatives across the placenta of Baltic grey seals (Halichoerus grypus grypus).

The placenta is an intermediary organ between the female and the developing foetus. Some chemical substances, including the most harmful ones, exhibit the ability to accumulate in or penetrate through the placenta. The aim of the study was to determine the role of the placenta of the Baltic grey seal (Halichoerus grypus grypus) in the transfer of endocrine disrupting compounds (EDCs) - (bisphenol A, 4-tert- octylphenol, 4- nonylphenol), as well as total and organic mercury. 30 placentas were collected from grey seals pupping under human care at the Hel Marine Station in the years 2007-2016. The assays were conducted using the technique of high-preformance liquid chromatography (phenol derivatives) and atomic absorption spectrometry (mercury and selenium). A measurable level of EDCs was indicated in the placentas of grey seals. It was established that the inorganic Hg form was accumulated in the placenta, and that its concentrations were an order of magnitude higher than the concentrations of the organic form, which penetrated to the foetus. Similar observations were made for phenol derivatives - bisphenol A, 4-tert- octylphenol and 4-nonylphenol. For this compound group the placenta was a barrier, but the properties of phenol derivatives suggest the possibility of their penetration through this organ.

Human Hair, Baltic Grey Seal (Halichoerus grypus) Fur and Herring Gull (Larus argentatus) Feathers as Accumulators of Bisphenol A and Alkylphenols.

The purpose of the study was to determine the concentration of bisphenol A (BPA), 4-tert-octylphenol (OP), and 4-nonylphenol (NP), in human hair, the fur of Baltic grey seals and the feathers of herring gulls. Hair was collected from 42 volunteers, while grey seal fur (n = 17) came from the seal centre in Hel (Marine Station of Institute of Oceanography, University of Gdansk) and gull covert feathers (n = 26) were collected from dead herring gulls along the Southern Baltic coast. Assays of phenol derivatives were conducted using the high performance liquid chromatography with fluorescence detection technique. In human hair, the mean BPA concentration amounted to 411.2 ng g-1 dw, OP 131.2 ng g-1 dw, NP 4478.4 ng g-1 dw, in seal fur BPA 67.5 ng g-1 dw, OP 62.8 ng g-1 dw, NP 39.1 ng g-1 dw, and in feathers BPA 145.1 ng g-1 dw, OP 162.0 ng g-1 dw, NP 37.7 ng g-1 dw. The increase of the analysed EDCs in hair was significantly influenced by diet rich in products of marine origin, as well as hair colouring, heating up food in plastic containers, using home cleaning products without protective gloves and wearing newly purchased clothes without washing them first. The concentration of phenol derivatives in seal fur was influenced solely by the uniform diet rich in fish. In birds, the feeding area during molting significantly influenced the concentration of BPA, OP and NP found in covert feathers.

Inhalation - Route of EDC exposure in seabirds (Larus argentatus) from the Southern Baltic.

Despite the presence of endocrine disrupting mercury, PAHs, alkylphenols and bisphenol A in inhaled air, scientific literature lacks information on their penetration into the lungs. Large lung capacity in birds makes this route of penetration more significant than in other animals. The studies were conducted on lungs of herring gulls found in the Gulf of Gdansk area. The results were juxtaposed with other tissues, including the intestines, which reflect the main, alimentary penetration route of harmful substances into the organism. It was determined that the capacity of bird's lungs, affects the efficiency with which mercury is absorbed from the air. Birds found to have high mercury concentrations in lungs had low PAHs concentrations, what was determined by the fact that the birds foraged in two different areas, as well as on different trophic levels. The alimentary route of phenol derivatives into the organism was of greater significance than inhalation.

Factors determining accumulation of bisphenol A and alkylphenols at a low trophic level as exemplified by mussels Mytilus trossulus.

The aim of the study was to investigate abiotic and biotic factors influencing the accumulation of endocrine disrupting compounds (EDCs) such as bisphenol A (BPA), 4-tert-octylphenol (OP) and 4-nonylphenol (NP) in mussels Mytilus trossulus from the Gulf of Gdansk (Southern Baltic). The key abiotic factor influencing BPA, OP and NP accumulation in mussels is their hydrophilicity/lipophilicity, which affects their main assimilation routes - by digestive tract for the more lipophilic OP and NP, and additionally by the gills for the less lipophilic BPA. As a result, high condition index (i.e. higher soft tissue weight) is more often correlated with high concentrations of OP and NP in mussels than with BPA. Furthermore, alkylphenols have 6-8 times greater accumulative potential than BPA. Concentration of the studied compounds was lower in females than in males following spawning, and the effect lasted longer for BPA than for alkylphenols. The influence of season and hydrological conditions on BPA, OP, NP in the mussel was more pronounced than the proximity of external sources of these compounds. An increase in water temperature in summer probably stimulated the solubility of BPA, the least lipophilic of the studied compounds, and led to increased assimilation of this compound from water (through gills). On the other hand, high OP and NP concentrations in mussels occurred in spring, which was caused by increased surface run-off and sediments resuspension.

Changes of concentrations and possibility of accumulation of bisphenol A and alkylphenols, depending on biomass and composition, in zooplankton of the Southern Baltic (Gulf of Gdansk).

The focus of the present study was to find the relationship between concentrations of bisphenol A (BPA), 4-tert-octylphenol (OP) and 4-nonylphenol (NP) in zooplankton and seasonal changes in the composition and biomass of particular zooplankton taxa in the Gulf of Gdansk (Southern Baltic) in the years 2011-2012. Assays of BPA, OP and NP in water and zooplankton samples were performed using the HPLC/FL system. High mean concentrations of the studied compounds, determined in spring (405.9 (BPA); 25.7 (OP); 111.2 (NP) ng g(-1) dw), can be linked to the high proportion of meroplankton in that season. Rotifera also had an influence on the rise in concentrations of the studied compounds but to a lesser degree, while the lowest concentrations (determined in summer) can be associated with the high participation of Copepoda and Cladocera in zooplankton biomass. It was also observed that juvenile forms can be more susceptible to accumulating endocrine disrupting compounds (EDCs). This is indicated by the positive correlation between BPA concentration in zooplankton and the proportion of Copepoda nauplii biomass in spring (r = 0.90; p < 0.05). In most cases, greater zooplankton biomass accumulated higher concentrations and loads of the studied compounds. With biomass growth (to 123.32 µg m(-3)), the bioconcentration factor also rose (to max 46.1·10(3)), demonstrating that unlike typical hydrophobic compounds the studied EDCs do not become "diluted" in zooplankton biomass. The highest BPA concentrations from all compounds may be connected with anthropogenic sources located in the coastal zone.

The fate of bisphenol A, 4-tert-octylphenol and 4-nonylphenol leached from plastic debris into marine water--experimental studies on biodegradation and sorption on suspended particulate matter and nano-TiO2.

Experiments were carried out, the aim of which was to determine the leaching rates for bisphenol A (4,4'-(propane-2,2-diyl)diphenol - BPA), 4-tert-octylphenol (OP), 4-nonylphenol (NP) from polycarbonate and recycled tyre granules into the seawater. Additionally biodegradation, sorption on marine suspended particulate matter and sorption on various types of nano-TiO2 of BPA, OP, NP were studied. Experiments were carried out on plastics at various stages of degradation. The conducted experiment confirmed the flux of BPA, OP and NP from the studied plastics into seawater. The initial photodegradation of the plastic had a significant influence on the amount of the studied components released into water. During the first days of the experiment leaching was weaker from aged materials. After 60 days leaching of BPA and OP was higher for aged plastic compared to unaged. On average, suspension adsorbed OP, BPA and NP from seawater at respective levels of 37%, 75% and 100%. On the other hand, during biodegradation on average 25%, 9% and 2% of OP, BPA and NP respectively are removed from water. Nano-TiO2 of 21 nm pore size diameter adsorbed all the compounds more strongly than nano-TiO2 of 15 nm pores sized coated with Al and stearic acid. The strongest sorption (100%) on different types of nano-TiO2 was that of the most hydrophobic and more linear structured NP with just one phenol group. The weakest sorption was observed in the case of BPA, which is the least hydrophobic, and characterized by higher compared to NP and OP steric hindrance and electrostatic repulsion.

The role of phytoplankton composition, biomass and cell volume in accumulation and transfer of endocrine disrupting compounds in the Southern Baltic Sea (The Gulf of Gdansk).

Endocrine disrupting compounds (EDCs) like bisphenol A (BPA), 4-tert-octylphenol (OP) and 4-nonylphenol (NP) are introduced to the trophic webs through among others phytoplankton. This paper describes BPA, OP and NP concentrations in phytoplankton in the Gulf of Gdansk (Southern Baltic Sea) in the years 2011-2012. The assays of BPA, OP and NP in samples were performed using HPLC with fluorescence detection. The concentrations of BPA, the most commonly used of the three compounds, were over ten times higher than OP and NP concentrations. The concentrations of the studied EDCs in phytoplankton from the Gulf of Gdansk depended on anthropogenic factors and on phytoplankton properties (species composition, biomass, volume). An increase in phytoplankton biomass did not always result in an increase of BPA, OP and NP concentrations. However, the load of the studied EDCs accumulated in phytoplankton biomass increase with a rise of biomass. An increase in BPA, OP and NP concentrations was effected by biomass growth and the proportions ofciliates, dinoflagellates, diatoms and green algae. A strong positive correlation between OP and NP concentrations and negative correlation between BPA concentrations and biomass of organisms with cells measuring <1000 µm(3) in volume results from the differing properties of these compounds.