An evaluation of dogs' exposure to benzophenones through hair sample analysis.

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.

Implications of polystyrene and polyamide microplastics in the adsorption of sulfonamide antibiotics and their metabolites in water matrices.

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.

Adsorption of Macrolide Antibiotics and a Metabolite onto Polyethylene Terephthalate and Polyethylene Microplastics in Aquatic Environments.

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.

Biomonitoring of benzophenones in guano samples of wild bats in Poland.

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.

Influence of microplastic contamination on the dissipation of endocrine disrupting chemicals in soil environment.

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.

Assessment of perfluoroalkyl substances concentration levels in wild bat guano samples.

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.

Green Assessment of Analytical Procedures for the Determination of Pharmaceuticals in Sewage Sludge and Soil.

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.

Multiresidue method for the determination of critically and highly important classes of antibiotics and their metabolites in agricultural soils and sewage sludge.

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.

Alginate/geopolymer hybrid beads as an innovative adsorbent applied to the removal of 5-fluorouracil from contaminated environmental water.

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.

Bioconcentration of pharmaceuticals in benthic marine organisms (Holothuria tubulosa, Anemonia sulcata and Actinia equina) exposed to environmental contamination by atenolol and carbamazepine.

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.

Accumulation and metabolization of the antidepressant venlafaxine and its main metabolite o-desmethylvenlafaxine in non-target marine organisms Holothuria tubulosa, Anemonia sulcata and Actinia equina.

The assessment of exposure to the antidepressant venlafaxine and its major metabolite o-desmethylvenlafaxine in Holothuria tubulosa, Anemonia sulcata and Actinia equina is proposed. A 28-day exposure experiment (10 µg/L day) followed by a 52-day depuration period was conducted. The accumulation shows a first-order kinetic process reaching an average concentration of 49,125/54342 ng/g dw in H. tubulosa and 64,810/93007 ng/g dw in A. sulcata. Venlafaxine is considered cumulative (BCF > 2000 L/kg dw) in H. tubulosa, A. sulcata and A. equina respectively; and o-desmethylvenlafaxine in A. sulcata. Organism-specific BCF generally followed the order A. sulcata > A. equina > H. tubulosa. The study revealed differences between tissues in metabolizing abilities in H. tubulosa this effect increases significantly with time in the digestive tract while it was negligible in the body wall. The results provide a description of venlafaxine and o-desmethylvenlafaxine accumulation in common and non-target organisms in the marine environment.

Uptake and depuration of three common antibiotics in benthic organisms: Sea cucumber (Holothuria tubulosa), snakelocks anemone (Anemonia sulcata) and beadlet anemone (Actinia equina).

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.

Enantioselective LC-MS/MS determination of antidepressants, ß-blockers and metabolites in agricultural soil, compost and digested sewage sludge.

In this work, an analytical method was optimised and validated for the simultaneous extraction and enantioselective determination of chiral ß-blockers, antidepressants and two of their metabolites in agricultural soils, compost and digested sludge. Sample treatment was based on ultrasound-assisted extraction and extract clean-up by dispersive solid-phase extraction. Analytical determination was carried out by liquid chromatography-tandem mass spectrometry using a chiral column. Enantiomeric resolutions were in the range from 0.71 to 1.36. Accuracy was in the range from 85 to 127% and precision, expressed as relative standard deviation, was lower than 17% for all the compounds. Method quantification limits were below 1.21-52.9 ng g-1 dry weight (dw) in soil, 0.76-35.8 ng g-1 dw in compost and 13.6-90.3 ng g-1 dw in digested sludge. Application to real samples revealed enantiomeric enrichment in the range especially in compost and digested sludge (enantiomeric fractions up to 1).

Adsorption of Fluoroquinolone Antibiotics from Water and Wastewater by Colemanite.

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.

Evaluation of Parabens and Bisphenol A Concentration Levels in Wild Bat Guano Samples.

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.

Thermodynamic and Kinetic Investigation of the Adsorption and Desorption of Trimethoprim and Its Main Metabolites in Mediterranean Crop Soils.

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).

Bioaccumulation/bioconcentration of pharmaceutical active compounds in aquatic organisms: Assessment and factors database.

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.

Adsorption of perfluoroalkyl substances on polyamide microplastics: Effect of sorbent and influence of environmental factors.

Microplastics (MPs) and perfluoroalkyl substances (PFASs) are two types of pollutants coexisting in the environment. Their co-exposure is a source of increasing concern. MPs present in the natural environment suppose an ideal surface for the sorption of hazardous contaminants. This study investigates the adsorption behaviour of six PFASs on polyamide (PA) MPs. Adsorption experiments under various internal (PA and PFASs dosage, PA particle size) and environmental (pH, ionic strength, dissolved organic matter) factors were carried out. Isotherm results (from 0.1 to 25 mg/L of PFASs) showed that the maximum adsorption capacity of the selected PFASs on the PA was as follows: perfluorooctanesulfonic acid (PFOS, 0.873 mg/g) > perfluorooctanoic acid (0.235 mg/g) > perfluoroheptanoic acid (0.231 mg/g) > perfluorohexanoic acid (0.201 mg/g) > perfluoropentanoic acid (0.192 mg/g) > perfluorobutanoic acid (0.188 mg/g) (pH 5.88, 0% salinity and 0% of dissolved organic matter). The PFOS has more tendency to be sorbed onto PA than perfluorocarboxilic acids. The MP characterization by scanning electron microscopy, X ray diffraction and Fourier transform infrared spectroscopy showed changes in the PA surface after adsorption assays. Pore filling, hydrophobic interactions and hydrogen bonds governed sorption process. The sorption capacity of PFASs was crucially affected by the PA size (from 19.6% to 99.9% for 3 mm and 50 µm particle size, respectively). The process was not significantly influenced by salinity while the dissolved organic matter exerted a negative effect (decrease from 100% to 26% for PFOS in presence of 25 mg/L of humic acid). Finally, adsorption rates of PFASs were quantified in real water matrices (influent and effluent wastewater, surface and tap water samples). The results revealed interactions between PA and PFASs and evidenced the role of PA as a vector to transport PFASs in the aquatic environment.

Comparison of Different Techniques for the Determination of Platinized Cytostatic Drugs in Urine Samples.

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.

An Overview of Analytical Methods to Determine Pharmaceutical Active Compounds in Aquatic Organisms.

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.