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Introduction: Benzophenones (BPs) are used in various branches of industry as ultraviolet radiation filters, but they pollute the natural environment, penetrate living organisms, and disrupt endocrine balance. Knowledge of the exposure of domestic animals to these substances is extremely scant. The aim of the study was to investigate long-term exposure of companion dogs to BPs and relate this to environmental factors. Material and Methods: Hair samples taken from 50 dogs and 50 bitches from under 2 to over 10 years old were analysed for BP content with liquid chromatography–tandem mass spectrometry. Results: The results revealed that dogs are most often exposed to 2-hydroxy-4-methoxybenzophenone (BP-3) and 4-dihydroxybenzophenone (BP-1). Concentration levels of BP-3 above the method quantification limit (MQL) were noted in 100% of the samples and fluctuated from 4.75 ng/g to 1,765 ng/g. In turn, concentration levels of BP-1 above the MQL were noted in 37% of the samples and ranged from <0.50 ng/g to 666 ng/g. Various factors (such as the use of hygiene and care products and the dog’s diet) were found to affect BP concentration levels. Higher levels of BP-3 were observed in castrated/spayed animals and in animals that required veterinary intervention more often. Conclusion: The results obtained show that the analysis of hair samples may be a useful matrix for biomonitoring BPs in dogs, and that these substances may be toxic to them.

The persistent appearance of antibiotic residues in the aquatic ecosystem is considered an issue of great concern. This study examined the adsorptive efficiency of a novel bionanocomposite (L-methionine/stevensite, MET/ST) for promising decontamination of nine antibiotics. Results revealed that MET/ST allows an excellent antibiotic removal efficiency, from 87% for trimethoprim (TMP) to almost 100% for the eight remaining antibiotics, at neutral pH, an adsorbent dose of 2 g/L, and 1.5 mg/L of the antibiotics mixture. Equilibrium was achieved in less than 1 min, except for TMP (30 min), and the kinetics was consistent with the pseudo-second order model (R² > 0.927). The isotherm data were fitted with the Langmuir and Freundlich models (R² > 0.960) (qmax from 21.48 to 28168 mg/g for TMP and chlortetracycline, respectively). The high surface area (170.49 m²/g) and pore volume (0.16 cm³/g) of MET/ST, together with electrostatic and hydrogen bonding interactions, played a dominant role in antibiotic adsorption. TMP was the only antibiotic affected by temperature (from 61% to 85% at 5 and 45ºC) and salinity (from 87% to 37% at 0 and 4% w/v of NaCl). The MET/ST was used consecutively for at least four adsorption–desorption cycles after being regenerated with a capacity > 97% in the last cycle for 7 out of 9 antibiotics. In addition to its adsorption capacity, reusability and low-cost features, the material demonstrated an excellent efficiency (up to 69% for TMP and 100% for other antibiotics) in wastewater and surface water samples denoting a great application for water purification.

Microplastic (MP) contamination is in the spotlight today, yet knowledge of their interaction with other organic contaminants in the soil environment is limited. Concerns extend to endocrine disrupting chemicals (EDCs), known for their potential to interfere with the hormonal systems of organisms and for their persistence and widespread presence in the environment. In this study, the most frequently occurring EDCs were monitored both in alluvial soil and in soil contaminated with different MPs commonly found in soil media, polyethylene, polyamide, and polystyrene. Bisphenol A and parabens were the most rapidly dissipating compounds, followed by triclosan and triclocarban, with the latter showing poor degradation. Per- and polyfluoroalkyl substances (PFAS) showed high persistence as concentrations remained nearly constant throughout the experiment. Although they fitted well with first-order dissipation kinetics, most showed biphasic behavior. The co-occurrence of MPs in the soil influenced the kinetic behavior in most cases although the differences were not very marked. MPs could impact sorption-desorption processes, affecting contaminant mobility and bioavailability to organisms in soil. These findings strengthen evidence for the influence of MPs on the behavior of soil contaminants such as EDCs, not only as vectors or sources of contaminants but by affecting dissipation kinetics.

Benzophenones (BPs) are substances used in the production of sunscreens, cosmetics, and personal care products. However, there is a lack of knowledge of BPs in wild animals. Therefore, the study aimed to assess the concentration of selected BPs commonly used in the cosmetic industry in guano samples collected from 4 colonies of greater mouse-eared bats (Myotis myotis). Liquid chromatography with tandem mass spectrometry (LC-MS/MS) was used to determine guano concentrations of benzophenone 1 (BP-1), benzophenone 2 (BP-2), benzophenone 3 (BP-3) and benzophenone 8 (BP-8). BP-1 levels above the method quantification limit (MQL) were noted in 97.5% of samples and fluctuated from <0.1 ng/g to 259 ng/g (mean 41.50 ng/g, median 34.8). The second most common was BP-3, which fluctuated from <0.1 ng/g to 19 ng/g (mean 6.67 ng/g, median 5.05), and its levels higher than MQL were observed in 40% of samples. BP-2 and BP-8 concentrations did not exceed the method detection limit (0.04 ng/g) in any analyzed sample. There were visible differences in the BP-1 and BP-3 levels among the studied bat colonies. Mean BP-1 concentration fluctuated from 11.23±13.13 ng/g to 76.71±65.51 ng/g and differed significantly between the colonies. Mean BP-3 concentration fluctuated from 5.03±6.03 ng/g to 9.18±7.65 mg/g, but it did not differ significantly between the colonies. The results show that guano is a suitable matrix for the assessment of wildlife exposure to BPs. This could be particularly advantageous in protected species, where not disturbing and stressing the animals are crucial.

Microplastics (MP) and antibiotics coexist in the environment and their combined exposure represents a source of increasing concern. MP may act as carriers of antibiotics because of their sorption capacity. Knowledge of the interactions between them may help improve understanding of their migration and transformation. In this work, the adsorption behaviour of a group of sulfonamides and their acetylated metabolites on different sizes of polyamide (PA) and polystyrene (PS) MP were investigated and compared. Sulfonamides were adsorbed on both MP (qmax up to 0.699 and 0.184 mg/g, for PA and PS, respectively) fitting to a linear isotherm model (R2 > 0.835). A low particle size and an acidic and salinity medium significantly enhances the adsorption capacity of sulfonamides (i.e. removal of sulfamethoxazole increased from 8 % onto 3 mm PA pellets to 80 % onto 50 mm of PA pellets). According to characterization results, adsorption mechanism is explained by pore filling and hydrogen bonds (for PA) and hydrophobic interactions (for PS). After adsorption, surface area was increased in both MP as result of a potential ageing of the particles and the intensity of XRD peaks was higher denoting a MP structure more amorphized. Metabolites were adsorbed more efficiently than their parent compounds on PS while the opposite effect was observed on PA explained by the acetylation of the amine group and, subsequently the reduction of hydrogen bond interactions. Although the dissolved organic matter inhibits sulfonamides adsorption, removal up to 65.2 % in effluent wastewater and up to 72.1 % in surface water were observed in experiments using real matrices denoting the role of MP as vectors of sulfonamide antibiotics in aquatic media.

Microplastics (MPs) and antibiotics are emerging pollutants widely found in aquatic environments, potentially causing environmental harm. MPs may act as carriers for antibiotics, affecting their environmental distribution. This study investigates the adsorption of four macrolide antibiotics and a metabolite onto two types of MPs: polyethylene terephthalate (PET) and polyethylene (PE). Results revealed a linear isotherm adsorption model, with higher adsorption to PET than to PE (R² > 0.936 for PE and R² > 0.910 for PET). Hydrophobic interactions and hydrogen bonding could be the main adsorption mechanisms, with pore filling potentially involved. Reduced particle size enhances adsorption due to the increase of active adsorption sites. This increasement is more pronounced in PE than in PET, leading to an 11.6% increase in the average adsorption of all macrolides to PE, compared to only 5.1% to PET. Dissolved organic matter inhibits adsorption (azithromycin adsorption to PE was reduced from 12% to 5.1%), while salinity enhances it just until 1% salinity. pH slightly influences adsorption, with maximal adsorption at neutral pH. Results in real samples showed that complexity of the matrix decreased adsorption. Overall, these findings indicate that PE and PET MPs can be a vector of macrolides in aquatic environments.

The presence of pharmaceuticals and personal care products (PPCPs) in the environment has aroused considerable interest in the last few years. However, the occurrence and fate of parent compounds and their metabolites and/or transformation products in soils have been scarcely evaluated to date. In this work, the dissipation kinetics of PPCPs, which are most frequently detected in the environment, and their main metabolites, is evaluated in soil amended with digested and composted sludge. The studied compounds were monitored for 60 days after digested or compost application to the soil. Several kinetic models were used to evaluate the dissipation kinetics of the processes. Parabens and their metabolites were the compounds with the fastest dissipation rates, while the antiepileptic carbamazepine and its metabolites were the poorest degraded compounds studied. Most of the compounds showed a single first-order dissipation kinetics. The application of biphasic kinetic models can improve the knowledge about the dissipation behavior of some of them. For instance, whereas compounds such as carbamazepine showed a high persistence showing a lag phase in its dissipation, resulting in an approximately constant concentration for the first days of batch experiments, others, such as sulfamethoxazole and diclofenac, followed a dissipation kinetics in two phases: a fast dissipation attributed to the amount of compound associated to the soil-water solution and a slow dissipation that could be due to the amount of the compound adsorbed onto the soil particle. For most of the compounds, the dissipation was faster in sludge-amended soil than in soil without organic amendment. This fact could be due to the influence of microbial activity and organic matter on their dissipation.

There is increasing evidence that the presence of certain pharmaceuticals in the environment leads to biota exposure and constitute a potential risk for ecosystems. Bioaccumulation is an essential focus of risk assessment to evaluate at what degree emerging contaminants are a hazard both to the environment and the individuals that inhabit it. The main goals of the present review are 1) to summarize and describe the research and factors that should be taken into account in the evaluation of bioaccumulation of pharmaceuticals in aquatic organisms; and 2) to provide a database and a critical review of the bioaccumulation/bioconcentration factors (BAF or BCF) of these compounds in organisms of different trophic levels. Most studies fall into one of two categories: laboratory-scale absorption and purification tests or field studies and, to a lesser extent, large-scale, semi-natural system tests. Although in the last 5 years there has been considerable progress in this field, especially in species of fish and molluscs, research is still limited on other aquatic species like crustaceans or algae. This revision includes >230 bioconcentration factors (BCF) and >530 bioaccumulation factors (BAF), determined for 113 pharmaceuticals. The most commonly studied is the antidepressant group, followed by diclofenac and carbamazepine. There is currently no reported accumulation data on certain compounds, such as anti-cancer drugs. BCFs are highly influenced by experimental factors (notably the exposure level, time or temperature). Field BAFs are superior to laboratory BCFs, highlighting the importance of field studies for reliable assessments and in true environmental conditions. BAF data appears to be organ, species and compound-specific. The potential impact on food web transfer is also considered. Among different aquatic species, lower trophic levels and benthic organisms exhibit relatively higher uptake of these compounds.

Fluoroquinolones are antibiotics of significant environmental concern their extended use not only in human medicine but also in veterinary medicine and not only as therapeutic agents but also to promote livestock growth and in aquaculture. Some fluoroquinolones and their metabolites are chiral compounds. Therefore, for a proper environmental risk assessment, enantioselective analytical methods are required. In this work, an analytical method has been developed and validated for the first time automatised enantioselective determination of environmental significant fluoroquinolones and their metabolites in wastewater and surface water samples. Target fluoroquinolones were selected by considering their extended use in human (ciprofloxacin and ofloxacin) and veterinary (flumequine) medicine. The analytical method was based on on-line solid-phase extraction-chiral liquid chromatography-tandem mass spectrometry. Analysis, including sample extraction and chiral LC-MS/MS determination, was carried out in just 14 min. The method was validated for its application to surface water and effluent and influent wastewater. Accuracy values were in the range from 61.4 to 122 % in wastewater and from 73.4 to 119 % in surface water. Precision, expressed as relative standard deviation, was lower than 13.6 % for all the compounds and sample matrices. Method quantification limits were in the range from 0.2 to 50 ng/L for all the compounds in wastewater and surface water. Method application to wastewater and surface water samples revealed the enantioselective transformation of LEV into (R)-OFL in surface water and the prevalence of OH-FLU D2 with respect to OH-FLU D1 in influent wastewater.

The adsorption–desorption processes of organic pollutants into the soil are one of the main factors influencing their potential environmental risks and distribution in the environment. In the present work, the adsorption–desorption behavior of an antibiotic, trimethoprim (TMP), and two of its main metabolites, 3-desmethyltrimethoprim (DM-TMP) and 4-hydroxytrimethoprim (OH-TMP), were assessed in three Mediterranean agricultural soils with different physicochemical characteristics. Results showed that the adsorption kinetic is performed in two steps: external sorption and intraparticle diffusion. The adsorptions of the studied compounds in soils were similar and fitted to the three models but were better fitted to a linear model. In the case of DM-TMP and OH-TMP, their adsorptions were positively correlated with the soil organic matter. In addition, desorption was higher in less organic matter soil (from 1.3 to 30.9%). Furthermore, the desorptions measured for the TMP metabolites were lower than those measured in the case of TMP (from 2.0 and 4.0% for OH-TMP and DM-TMP, respectively, to 9.0% for TMP).

Emerging pollutants have been ubiquitously found in environmental compartments, while there is scarce information about these substances and their effects on health status in wild terrestrial mammals. Bat species are very sensitive animals to any changes in the environment and are considered one of the best bioindicators of the quality of the environment to terrestrial wildlife. To acquire a better knowledge of the environmental exposure to these animals, a multiclass method is proposed to determine 20 emerging pollutants (six perfluoroalkyl substances (PFAS), four parabens (PB), four benzophenones (BP), a plasticizer (BPA), and five surfactants (four linear alkylbenzene sulfonates (LAS) and nonylphenol (NP)) in bats using a non-invasive approach based on guano matrix. Sample treatment involved ultrasonic solvent extraction and dispersive solid phase extraction prior to analysis in a single run with liquid chromatography-tandem mass spectrometry. The main variables affecting the extraction and clean-up steps were evaluated using single and multivariate strategies. Under the optimized conditions, satisfactory analytical characteristics in terms of linearity, recoveries (>80 %), precision (RSD < 24 %) and method quantification limits (from 0.01 to 64 ng/g dry weight) were obtained. Furthermore, and as a proof of concept, guano samples from a bat reference population were collected from a colony located in Brenna village, in south Poland. The results confirm the exposure of wild bats to emerging pollutants (LAS, PFAS, and PB compounds were frequently detected in the samples) and the suitability of the bat guano matrix for understanding the environmental exposure in terrestrial mammals.

In this paper, a method is proposed for the determination of antibiotics classified by the World Health Organization as critically important (four macrolides and three quinolones) and highly important (one tetracycline, one diaminopyridine, and three sulfonamides) and eight of their metabolites. The method is based on ultrasound-assisted extraction, dispersive solid-phase extraction clean-up, and analytical determination by liquid chromatography–tandem mass spectrometry. Variables affecting each stage of the analytical method were thoroughly optimised. The method was validated for its application to sewage sludge from different treatment stages (non-treated sludge: primary and secondary sludge; and treated sludge: digested sludge and compost) and to agricultural soil. Limits of quantification were in the range of 0.03–7.50 ng g−1 dry weight (dw) for most of the compounds. Accuracy values were in the range of 70–102%. Precision was below 17%. The application of the method to real samples revealed that macrolides and fluoroquinolones were the antibiotic classes at the highest concentrations in all types of samples. The lowest concentrations of antibiotics were measured in compost (highest concentration: 27 ng g−1 dw, corresponding to norfloxacin) and soil samples (highest concentration: 93 ng g−1 dw, corresponding to a metabolite of clarithromycin). The proposed method is the first developed to date for the determination of multiclass antibiotics and their main metabolites in sludge from different treatment stages. The method can provide a useful tool for obtaining information about antibiotics in sewage sludge prior to its application to agricultural soils and in agricultural soils.

Due to the importance of the authentication of the botanical and geographical origin of honey, this document is focused on the use of phenols as potential chemical markers in an attempt to distinguish and characterize one of the non-floral honey types, oak (Quercus sp.) honey, from other honeydew honeys produced in other regions. The development and validation of ultra-high-performance liquid chromatography with mass spectrometry detection enables the identification of 23 phenolic compounds in 58 Spanish oak honeydew honey samples. The proposed compounds, above all salicylic acid (mean = 24.31 mg 100 g−1), but also p-coumaric acid, p-hydroxybenzoic acid, syringic acid, naringenin, and galangin could further contribute as a helpful tool in the quality control of this non-floral honey, and therefore distinguish it from European honeydew honey and those from other regions. Furthermore, many positive correlations between phenolic compounds, CIELAB color parameters, and antioxidant activity are established. This research presents a complete phenolic composition and the largest sampling of one of the most appreciated honeydew honey varieties. This is also one of the singular studies that have successfully linked individual phenolic acids and flavonoids with physicochemical parameters within the same unifloral honey.

Perfluoroalkyl substances (PFASs) are substances commonly used in the production of various everyday objects, including among others kitchen dishes, cosmetics, or clothes. They penetrate to the environment and living organisms causing disturbances in the functioning of many internal organs and systems. Due to environmental pollution, wildlife is also exposed to PFASs, but the knowledge about this issue is rather limited. The aim of this study was to evaluate the exposure of wild greater mouse-eared bats (Myotis myotis), living in Poland, to six selected PFASs: five perfluoroalkyl carboxylic acids (perfluorobutanoic acid—PFBuA, perfluoropentanoic acid—PFPeA, perfluorohexanoic acid—PFHxA, perfluoroheptanoic acid—PFHpA, perfluorooctanoic acid—PFOA) and perfluorooctane sulfonic acid (PFOS) through the analysis of guano samples with liquid chromatography with tandem mass spectrometry (LC–MS–MS) method. To our knowledge this is the first study concerning the PFASs levels in bats, as well as using guano samples to evaluate the exposure of wild mammals to these substances. A total of 40 guano samples were collected from 4 bats summer (nursery) colonies located in various parts of Poland. The presence of PFASs mentioned were detected in all colonies studied, and concentration levels of these substances were sampling dependent. The highest concentration levels were observed in the case of PFPeA [1.34 and 3060 ng/g dry weight (dw)] and PFHxA (8.30–314 ng/g dw). This study confirms the exposure of wild bats to PFASs.

Parabens and bisphenol A are synthetic compounds found in many everyday objects, including bottles, food containers, personal care products, cosmetics and medicines. These substances may penetrate the environment and living organisms, on which they have a negative impact. Till now, numerous studies have described parabens and BPA in humans, but knowledge about terrestrial wild mammals’ exposure to these compounds is very limited. Therefore, during this study, the most common concentration levels of BPA and parabens were selected (such as methyl paraben—MeP, ethyl paraben—EtP, propyl paraben—PrP and butyl paraben—BuP) and analyzed in guano samples collected in summer (nursery) colonies of greater mouse-eared bats (Myotis myotis) using liquid chromatography with the tandem mass spectrometry (LC-MS-MS) method. MeP has been found in all guano samples and its median concentration levels amounted to 39.6 ng/g. Other parabens were present in smaller number of samples (from 5% for BuP to 62.5% for EtP) and in lower concentrations. Median concentration levels of these substances achieved 0.95 ng/g, 1.45 ng/g and 15.56 ng/g for EtP, PrP and BuP, respectively. BPA concentration levels did not exceed the method quantification limit (5 ng/g dw) in any sample. The present study has shown that wild bats are exposed to parabens and BPA, and guano samples are a suitable matrix for studies on wild animal exposure to these substances.

Antibiotics are widely used drugs in human and veterinary medicine, which has attracted great attention in relation to the development of bacterial resistance, currently a problem of great concern for governments and states, as it is related to the resurgence of infectious diseases already eradicated. Understanding the bioaccumulation of antibiotics in aquatic organisms is an important key to understanding their risk assessment. The present study was designed to study the bioaccumulation of target antibiotics in relevant organisms inhabiting benthic marine environments. The uptake and elimination of ciprofloxacin (CIP), sulfamethoxazole (SMX) and trimethoprim (TMP) were investigated in sea cucumbers (Holothuria tubulosa), snakelock anemone (Anemonia sulcata) and beadlet anemone (Actinia equina) under controlled laboratory conditions. The results show that antibiotics have a particular trend over time during all periods of absorption and depuration. The tissue distribution of antibiotics in sea cucumber is strongly influenced by the structure of the compounds, while CIP is concentrated in the body wall; TMP is concentrated in the digestive tract. Two different approaches were used to estimate bioconcentration factors (BCFs) in different animal models, based on toxicokinetic data and measured steady-state concentrations. The BCF ranges were 456–2731 L/kg, 6–511 L/kg and 9–100 L/kg for TMP, CIP and SMX, respectively. The estimated BCF values obtained classify TMP as cumulative in A. equina and H. tubulosa, underlining the potential bioconcentration in these marine organisms. A correlation was observed between the BCFs of the target antibiotics and the octanol-water distribution coefficient (Dow) (r² > 0.7). The animal-specific BCF followed the order of beadlet anemone > sea cucumber > snakelock anemone.

The main difficulties when analyzing pharmaceutically active compounds (PhACs) in solid environmental samples is the complexity of the samples and the low concentration levels of such pollutants. Most efforts are focused in achieving good analytical performance parameters such as high recoveries or low detection limits without considering if the methods are environmentally friendly. In this work, the main tools proposed for assessing the greenness of analytical methodologies (Analytical Eco-scale, Green Analytical Procedure Index (GAPI), and Analytical GREEnness metric (AGREE)) have been applied to nine analytical procedures that include recent important analytical tendencies. The three metrics identified the paper spray ionization method as the greenest procedure since it used untreated samples for direct mass spectrometry analysis. Using Analytical Eco-scale, most of the evaluated procedures were rated as “acceptable green”. However, the use of internal standards resulted key in the environmental impact of the method which provided contradictory results versus other metrics. GAPI found greenness similarities between most of selected methods, hindering a greenness classification. AGREE allowed the weighting of each evaluation criterion providing a greenness ranking. The application of each metric detecting their weaknesses and strengths was discussed. The incorporation of validation analytical features in greenness metrics was a gap revealed.

Water contaminated by cytostatic drugs has many negative impacts on the ecosystems. In this work, cross-linked adsorbent beads based on alginate and a geopolymer (prepared from an illito-kaolinitic clay) were developed for a promising decontamination of the 5-fluorouracil (5-FU) cytostatic drug from water samples. The characterization of the prepared geopolymer and its hybrid derivative was performed by scanning electron microscopy, X-ray diffraction, Fourier transform infrared and termogravimetric analysis. Batch adsorption experiments indicated that alginate/geopolymer hybrid beads (AGHB) allow an excellent 5-FU removal efficiency of up to 80% for a dosage adsorbent/water of 0.002 g/mL and a concentration of 5-FU of 2.5 mg/L. The adsorption isotherms data follow well the Langmuir model. The kinetics data favor the pseudo-second-order model. The maximum adsorption capacity (qmax) was 6.2 mg/g. The optimal adsorption pH was 4. Besides pore filling sorption process, the carboxyl and hydroxyl groups from alginate immobilized onto the geopolymer matrix favored the retention of 5-FU ions by hydrogen bonds. Common competitors, such as dissolved organic matter, do not significantly affected the adsorption. In addition, this material has not only eco-friendly and cost-effective advantages but also excellent efficiency when applied to real environmental samples such as wastewater and surface water. This fact suggests that it could have a great application in the purification of contaminated water.

The present work assess the bioconcentration kinetics of atenolol (ATN) and carbamazepine (CBZ) in common marine organisms including Holothuria tubulosa, Anemonia sulcata and Actinia equina under controlled laboratory conditions. CBZ exhibited higher uptake and excretion rates resulting higher bioconcentration factor (BCF) (41–537 L/kg for CBZ vs 7–50 L/kg for ATN) although both are below the limits established by the European Union (EU). The measured BCF using kinetic data showed some differences with those predicted using the concentrations measured at the steady-state, probably explained because the steady state was not ready reached. The animal-specific BCF followed the order of Holothuria tubulosa > Actinia equina > Anemonia sulcata for ATN while was the opposite for CBZ. The study highlighted between-tissues differences in the digestive tract and the body wall of the Holothuria tubulosa. The work presented is the first to model bioconcentration of ATN and CBZ in holothurian and anemone animal models.

Pharmaceutical residues in water and wastewater have become a worldwide problem with environmental and public health consequences. Antibiotics are of special importance because of the emergence of antibiotic-resistant genes. This study evaluates the adsorptive removal of four common fluoroquinolone antibiotics by using natural colemanite as an alternative adsorbent for the first time. Batch adsorption experiments were conducted for the mixture of fluoroquinolones as well as for individual compounds during the isotherm studies. Adsorption kinetic results indicated that the process followed the pseudo-second-order (PSO) model, while the Langmuir model described the sorption isotherms. The effects of pH and temperature on adsorption performance were determined, and the results indicated that the adsorption was endothermic and spontaneous, with increasing randomness at the solid–liquid interface. The effects of real water and wastewater matrices were tested by using tap water, surface water, and wastewater samples. Reusability experiments based on five adsorption–desorption cycles indicated that the adsorption performance was mostly retained after five cycles. The adsorption mechanism was elucidated based the material characterization before and after adsorption. The results indicate that colemanite can be used as an effective and reusable adsorbent for fluoroquinolone antibiotics as well as for other pollutants with similar physicochemical properties.

Bisphenol A (BPA) is an organic substance widely used in the plastics industry. It penetrates food and environment and, as an endocrine disruptor, has detrimental effects on human organisms. Pet animals, which live in the immediate vicinity of humans, are also exposed to BPA; however, knowledge regarding the exposure of dogs to this substance is extremely scarce. This is the first study in which hair analysis has been used to biomonitor BPA in 30 dogs using liquid chromatography and tandem mass spectrometry techniques. The presence of BPA in concentration levels above the method detection limit (1.25 ng/g) was noted in 93.33% of samples. BPA concentration levels were found to range from 7.05 ng/g to 436 ng/g (mean 81.30 ng/g). Statistically significant differences in BPA concentration levels were found between animals with physiological weight and animals with abnormal weight (skinny and obese). In turn, differences between males and females, as well as between young, middle-aged and old dogs, were not statistically significant. The obtained results have clearly shown that hair analysis is a useful method to evaluate the exposure of dogs to BPA. This study also confirmed that dogs are exposed to BPA to a large extent, and this substance may play a role as a pathological factor in this animal species. However, many aspects connected to the influence of BPA on canine health status are unclear and need further study.

Composting is an important waste management strategy, providing an economical and environment-friendly approach to sanitizing and stabilizing biosolids for land soil amendment. However, the resulting product can contain a large number of organic pollutants that may have adverse effects on the ecosystem. This paper presents the occurrence of eight widely used organic pollutants (four linear alkylbenzene sulfonates (LAS C10-C13), nonylphenol and its mono- and di-ethoxylates (NPE) and a di(2-ethylhexyl)phthalate (DEHP)) in full-scale composting processes. LAS homologues were detected at the highest concentrations (range of ∑LAS: 2068–9375 mg kg−1 dm), exceeding the limit fixed in the EU Directive draft. The concentration levels of the NPE and DEHP were significantly lower (up to 27.5 and 156.8 mg kg−1 dm, respectively) and did not exceed their fixed limits in the EU Directive draft. Ecotoxicological risk assessment for when compost is amended onto soils has also been evaluated. The concentrations measured represented a medium-low risk for most compounds, although it was not enough in the case of LAS C11 and C13 and NP.

The widespread occurrence of antibiotics in the environment may exert a negative impact on wild organisms. In addition, they can become environmental reservoirs, through the ingestion of food or contaminated water, and vectors for antibiotic-resistant bacteria. This fact is even more important in migratory birds that can promote their dissemination across continents. In this work, a multiresidue analytical method suitable for the determination of five families of antibiotics and their main metabolites in waterbird faeces has been developed and validated. The target compounds include environmentally significant sulfonamides, macrolides, fluoroquinolones, tetracyclines and antifolates. Sample treatment involves ultrasound-assisted extraction with methanol and dispersive solid-phase extraction clean-up with C18. Analytical determination was carried out by liquid chromatography–tandem mass spectrometry. The most significant parameters affecting sample extraction and extract clean-up were optimised by means of experimental designs. Good linearity (R2 > 0.994), accuracy (from 41 to 127%), precision (relative standard deviation lower than 24%) and limits of quantification (lower than 2 ng g−1 (dry weight, dw)) were obtained for most of the compounds. The method was applied to the determination of the selected compounds in 27 faeces samples from three common migratory waterbird species. Nine antibiotics and three of their metabolites were detected in the analysed samples. Fluoroquinolones and macrolides were the antibiotics most frequently detected. The highest concentrations corresponded to norfloxacin (up to 199 ng g−1 dw).

Parabens are widely used in the food, cosmetics and pharmaceutical industry and are widespread in the environment. As endocrine disruptors, parabens have adverse effects on living organisms. However, knowledge of the exposure of domestic animals to parabens is extremely scarce. Therefore, this study assessed the exposure level of dogs to three parabens commonly used in industry (i.e. methylparaben - MeP, ethylparaben - EtP and propylparaben - PrP) using fur sample analysis in liquid chromatography-tandem mass spectrometry. The presence of parabens has been noted in the samples collected from all dogs included in the study (n = 30). Mean concentrations of MeP, EtP and PrP in the fur of dogs were 176 (relative standard deviation – RSD = 127.48%) ng/g dry weight (dw), 48.4 (RSD = 163.64%) ng/g dw and 79.8 ng/g dw (RSD = 151.89%), respectively. The highest concentrations were found for MeP (up to 1023 ng/g dw). Concentrations of MeP and EtP in males were statistically higher than those in females (p < 0.05). Statistically significantly higher concentration levels of PrP in young animals (up to three years old) were also found. This is the first study concerning the use of fur samples to evaluate the exposure of domestic animals to parabens. The results indicate that an analysis of the fur may be a useful tool of paraben biomonitoring in dogs. The presence of parabens in the canine fur also suggests that these substances may play a role in veterinary toxicology. However, many aspects connected with this issue are not clear and require further study.

Non-steroidal anti-inflammatory drugs (NSAIDs) have been reported to be the main pharmaceutical class accumulated in seafood. Among them, ibuprofen (IBU) is of special concern as it is used worldwide to treat common pain, does not require a medical prescription, it is often taken in a high daily dose, and has been reported to cause potential adverse effects on aquatic organisms. IBU is highly transformed into hydroxy- and carboxy-metabolites and/or degradation products generated not only after its administration but also during wastewater treatment or in the environment. These compounds can be present in the environment at higher concentrations than IBU and present higher toxicity. In this work, a low-cost and affordable routine analytical method was developed and validated for the first-time determination of IBU and its main metabolites in mussels. The method is based on ultrasound-assisted extraction (UAE), clean-up by dispersive solid-phase extraction (d-SPE) and analytical determination by liquid chromatography-tandem mass spectrometry. Box-Behnken experimental design was used for method optimisation to better evaluate the influence and interactions of UAE and d-SPE variables. Extraction recoveries were in the range from 81 to 115%. Precision, expressed as relative standard deviation, was lower than 7%. Method detection limits were in the range from 0.1 to 1.9 ng g−1 dry weight. The method was successfully applied to wild mussels.

Platinum-based cytostatic drugs are one of the most widely used cancer treatments. They are excreted via the urinary tract and can reach the environment through wastewater, posing a risk to human health due to their side effects. Four identification and quantification techniques, including liquid chromatography (LC) separation coupled to (i) a diode array ultraviolet (UV(DAD)) (ii), mass spectrometer in single ion monitoring mode (LC-MS) and (iii) multiple reaction monitoring mode (LC-MS/MS) and (iv) derivatization with diethyldithiocarbamate prior to LC-MS/MS analysis, have been optimized and compared for the multiresidue determination of main platinized cytostatic drugs (cisplatin, carboplatin, and oxaliplatin) in urine samples. Parameters that affect the efficiency of the chromatographic separation and analytical determination of different methods (column, mobile phase, wavelength, precursor ions, fragmentor, and product ions) were optimized. Analytical features, such as matrix effect, sensitivity, precision, selectivity, and linearity, were calculated. In terms of selectivity, the derivatization technique was discarded since it was only applicable to the platinated sum. A high dilution of the sample with LC-UV(DAD) was needed to reduce the matrix effect. Overall, the LC-MS/MS method presented the best analytical features (% RSD ≤ 12.8%, R2 ≥ 0.991, or method-detection limits between 0.01–1 µg mL⁻¹). The selected method was applied to the quantification of platinized cytostatic drugs in hospital urine samples from oncologic patients.

Microplastics (MPs) and other emerging pollutants exist together in the environment and their co-exposure represents a source of increasing concern as MPs have been reported to act as carriers of pollutants due to their high sorption capacity. The ingestion of contaminated MPs by organisms can enhance the desorption of pollutants, increasing their bioavailability and toxicity. This review examines the role of MPs as vectors of environmental emerging contaminants. First, the main tools used to identify and characterise MPs and the analytical methods used for the determination of associated emerging contaminants are discussed. Insightful explanations of the sorption interaction between several groups of emerging pollutants and MPs are provided. MP type (polarity, crystallinity, size) and aging process together with the environmental conditions and pollutant properties (hydrophobicity and dissociated forms) are key factors influencing the sorption process. The literature review showed that polyethylene and polystyrene were the most commonly studied polymers. Antibiotics, perfluoroalkyl compounds and triclosan showed high sorption capacities onto MPs. Finally, the effect of co- exposure to MPs-emerging pollutants and bioaccumulation in aquatic and terrestrial organisms is discussed. The combined exposure may impact the toxic effects in different ways, through synergistic or antagonic in- teractions. Examples of different scenarios are provided, but in general the research conducted on terrestrial systems is scarce. The results revealed a lack of standardization in laboratory studies and in the testing conditions that reflect actual environmental exposure.

Nonylphenol (NP) is an anthropogenic pollutant frequently found in sewage sludge due to the insufficient degrading effectiveness of conventional WWTPs and has attracted attention as an endocrine disruptor. The aim of this study was to isolate specific NP-degrading bacteria from sewage sludge to be used in the degradation of this contaminant through bioaugmentation processes in aqueous solution and sewage sludge. Up to eight different bacterial strains were isolated, six of them not previously described as NP degraders. Bacillus safensis CN12 presented the best NP degradation in solution, and glucose used as an external carbon source increased its effect, reaching DT50 degradation values (time to decline to half the initial concentration of the pollutant) of only 0.9 days and a complete degradation in <7 days. Four NP metabolites were identified throughout the biodegradation process, showing higher toxicity than the parent contaminant. In sewage sludge suspensions, the endogenous microbiota was capable of partially degrading NP, but a part remained adsorbed as bound residue. Bioaugmentation was used for the first time to remove NP from sewage sludge to obtain more environmentally friendly biosolids. However, B. safensis CN12 was not able to degrade NP due to its high adsorption on sludge, but the use of a cyclodextrin (HPBCD) as availability enhancer allowed us to extract NP and degrade it in solution. The addition of glucose as an external carbon source gave the best results since the metabolism of the sludge microbiota was activated, and HPBCD was able to remove NP from sewage sludge to the solution to be degraded by B. safensis CN12. These results indicate that B. safensis CN12 can be used to degrade NP in water and sewage sludge, but the method must be improved using consortia of B. safensis CN12 with other bacterial strains able to degrade the toxic metabolites produced.

There is increasing scientific evidence that some pharmaceuticals are present in the marine ecosystems at concentrations that may cause adverse effects on the organisms that inhabit them. At present, there is still very little scientific literature on the (bio)accumulation of these compounds in different species, let alone on the relationship between the presence of these compounds and the adverse effects they produce. However, attempts have been made to optimize and validate analytical methods for the determination of residues of pharmaceuticals in marine biota by studying the stages of sample treatment, sample clean-up and subsequent analysis. The proposed bibliographic review includes a summary of the most commonly techniques, and its analytical features, proposed to determine pharmaceutical compounds in aquatic organisms at different levels of the trophic chain in the last 10 years.

La presencia y distribución de contaminantes emergentes en compartimentos ambientales ha sido abordada intensamente en la literatura científica de los últimos años. Los avances en las técnicas y métodos analíticos empleados, el conocimiento de los rangos de concentración de algunos compuestos en determinados escenarios y sus potenciales efectos ecotoxicológicos, entre otros, han sido objeto de un interesante debate científico que ha trascendido a otros ámbitos como el de la legislación ambiental. La mayoría de estos estudios se han centrado en los compuestos tal y como son utilizados en el ámbito doméstico, industrial o agropecuario, pero aún siguen siendo muy escasos los dedicados a los productos de degradación o metabolitos (“los emergentes de los emergentes”) en los que los compuestos originales en sus diferentes vías de introducción en el medio ambiente son transformados. De acuerdo con estos antecedentes, el objetivo global planteado en la presente tesis doctoral ha sido doble. Por un lado, el desarrollo de nuevos métodos analíticos, fiables y accesibles, para la determinación conjunta de contaminantes emergentes y metabolitos representativos en diferentes matrices ambientales atendiendo a las carencias advertidas en la literatura científica. Por otro lado, la aplicación de esos métodos, optimizados y validados, en la resolución de casos específicos de interés medioambiental. La tesis se ha estructurado en 5 capítulos. El capítulo 1, antecedentes, incluye una extensa revisión crítica del estado del arte sobre metabolitos de contaminantes emergentes en el medio ambiente. En él se abordan los mecanismos de metabolización de principios activos farmacéuticos y de productos de cuidado personal, las vías de entrada de estos compuestos y sus productos de degradación en el medio ambiente y los potenciales riesgos asociados, y las técnicas de tratamiento y determinación más empleadas en el análisis de estas sustancias en diferentes matrices, finalizando con un apartado, The presence and distribution of emerging pollutants in environmental compartments has been intensively addressed in the scientific literature of recent years. The advances in the techniques and analytical methods used, the knowledge of the concentration ranges of some compounds in certain scenarios and their potential ecotoxicological effects, among other related topics, have been the subject of an interesting scientific debate that has transcended to other areas such as environmental legislation. Most of these studies are mainly based on the compounds just as they are used in the domestic, industrial or agricultural environment, but there are still very few studies devoted to degradation products or metabolites (the compounds ¨emerging¨ from emerging compounds) into which the original compounds are transformed in their different introduction routes into the environment. In accordance with these precedents, the global objective proposed in this PhD thesis has been twofold. On the one hand, the development of new, reliable and accessible analytical methods for the joint determination of emerging pollutants and representative metabolites in different environmental matrices, considering the shortcomings noted in the scientific literature. On the other hand, the application of these methods, optimized and validated, in the resolution of specific cases of environmental interest. The thesis has been structured in 5 chapters. Chapter 1, background, includes an extensive critical examination of the state-of-art in metabolites of emerging pollutants in the environment. It addresses the mechanisms of metabolization in pharmaceuticals and personal care products; the entry routes of these compounds and their degradation products into the environment and the potential associated risks, and the most widely used treatment and classification techniques in the analysis of these substances in different matrices, ending with a section on future perspectives in this study area. Chapte

Chirality is a relevant topic in pharmaceutical, food and agrochemical fields because enantiomers, in spite of their similar physical-chemical properties, can exhibit different dynamics, kinetics and effects. Their enantiomeric determination implies a significant analytical challenge because of their identical physical-chemical properties, except light rotation. This review provides a state-of-the-art overview of analytical methods reported from 2010 to the date for the determination of chiral pollutants, including pharmaceuticals, pesticides, musk fragrances, perfluorinated compounds (PFCs), brominated flame retardants (BFRs) and polychlorinated biphenyls (PCBs), in environmental samples and biota. Recent reviews in this topic, mainly focused on pharmaceuticals and pesticides, have been also included. Special attention has been focused on analytical techniques most commonly applied for such determination. Finally, future trends and mainly challenges to be overcome are stated.

Poly- and perfluoroalkyl substances (PFASs) are a large group of chemicals commonly used in various branches of industry, which may adversely affect the living organisms. The aim of this study were to evaluate exposure of dogs to six selected PFASs: five perfluoroalkyl carboxylic acids (perfluorobutanoic acid - PFBuA, perfluoropentanoic acid - PFPeA, perfluorohexanoic acid - PFHxA, perfluoroheptanoic acid - PFHpA, perfluorooctanoic acid – PFOA) and perfluorooctane sulfonic acid (PFOS) through the analysis of fur samples. To our knowledge this is the first study concerning the use of fur samples to evaluation of exposure of domestic animals to PFASs. Relationship between PFASs concentration and age, gender and body weight of animals was also evaluated. Fur samples were collected from 30 dogs living in Olsztyn (Poland). All PFASs studied were detected in the canine fur samples. The highest concentrations were observed in the case of PFOA and PFBuA, detected at concentrations in the range between 1.51 and 66.7 ng/g and 0.98–26.6 ng/g, respectively. During the present study generally no statistically significant differences dependent on gender, age and body weight of animals were found. This study confirms the suitability of fur samples for biomonitoring of exposure to PFASs in domestic animals, what may be important in veterinary toxicology.

Polycyclic aromatic hydrocarbons (PAHs) are of major scientific concern owing to their widespread presence in environmental compartments and their potential toxicological effects on humans and biota. In this study, the adsorption capacity of natural (montmorillonite (Mt)), synthetic (Na-Mica-4), and modified (with octadecylamine and octadecyltrimethylamine (ODA-Mt, ODA-Mica-4, and ODTMA-Mt and ODTMA-Mica-4)) clays were assessed and compared for the removal of 16 PAHs. Materials were synthesized and characterized by X-Ray diffraction, Zeta potential, and Fourier-transform infrared spectroscopy. The results showed its correct preparation and the incorporation of PAHs in the structure of the clays after the adsorption tests. The proposed materials were effective PAH adsorbents, with adsorption percentages close to 100%, in particular those using Mt. Mt and Na-Mica-4 presented a better adsorption capacity than their organofunctionalized derivatives, indicating that the adsorption of PAHs may occur both in the surface part and in the interlayer. The proposed adsorbents take the advantage of being a low cost and highly effective. They can be an interesting alternative for wastewater treatment and soil remediation to prevent PAH contamination.

This work evaluated the availability and sorption behaviour of four pharmaceuticals and eight of their metabolites in sewage sludge and sludge-amended soil. Digested sludge and compost were evaluated. The highest levels found in digested sludge corresponded to caffeine (up to 115 ng g−1 dm), ibuprofen (45 ng g−1 dm) and carbamazepine (9.3 ng g−1 dm). The concentrations measured in compost were even lower than in digested sludge. No compound was detected in sludge-amended soils. This fact could be due to the dilution effect after sludge application to soil. Different adsorption capacities in sludge–soil mixtures were measured for the studied compounds at the same spike concentration. In general, except for paraxanthine and 3-hydroxycarbamazepine, the metabolite concentrations measured in the mixtures were almost two-fold lower than those of their parent compounds, which can be explained by their mobility and lixiviation tendency. The log Kd ranged from −1.55 to 1.71 in sludge samples and from −0.29 to 1.18 in soil–sludge mixtures. The log Kd values calculated for compost were higher than those calculated for digested sludge. The obtained results implied that the higher organic carbon content of compost could influence soil contamination when it is applied to soil.

El desarrollo de nuevos productos de consumo ha dado lugar a la llegada al medioambiente de nuevas sustancias contaminantes. Muchas de ellas clasificadas como disruptores endocrinos, y cuyo control requiere de herramientas analíticas sensibles y fiables para su correcta determinación. Es de especial interés la monitorización de este tipo de contaminación en suelos agrícolas y vegetales de consumo humano ya que ello permite evaluar, no solo el grado de contaminación de los suelos enmendados con lodos de depuradora, sino además, la incorporación de estos contaminantes a los cultivos y, por tanto, la exposición humana a través de su consumo. De acuerdo con estos antecedentes, en el presente trabajo se han desarrollado tres nuevos métodos analíticos para la determinación de un grupo representativo de disruptores endocrinos, de origen industrial y urbano, dos para su determinación en vegetales de consumo humano y un tercero para su determinación en lodo de depuradora y suelo. Para el desarrollo de las metodologías se seleccionaron métodos de extracción sencillos, rápidos y de bajo coste. Éstos, una vez validados, se aplicaron en la evaluación de la distribución de estos contaminantes en diferentes procesos de tratamiento de lodos de depuradora y en el sistema suelo-planta. Se analizaron muestras de lodos procedentes de distintas tecnologías de estabilización y en las diferentes etapas de dichos tratamientos. Se evaluó la asimilación y translocación de los contaminantes en un cultivo de rábanos realizado en condiciones controladas en una mezcla lodo compostado-suelo. Se analizó así mismo la evolución de los contaminantes en la mezcla lodo-suelo y en el suelo en contacto con la raíz al finalizar el experimento. Los resultados obtenidos, a grandes rasgos, pusieron de manifiesto: i) la adecuación de las metodologías analíticas desarrolladas para el propósito de la monitorización de los disruptores endocrinos seleccionados, ii) la presencia y distribución de los disruptores e