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This review describes a wide variety of analytical approaches for the assessment of human exposure to organic chemicals associated with plastic additives, focusing on works published in the last decade on plasticizers, bisphenols, flame retardants and antioxidants. Physiologically based extraction tests serve as preliminary in-vitro assays to determine the bioaccessibility of these compounds from micro/nanoplastics in body fluids of the gastrointestinal tract, skin, or lung. Whenever plastic-laden compounds become bioavailable, human metabolism is to be monitored through the assessment of phase I and II metabolites. In this regard, analytical methods based on chromatography and mass spectrometry for human biomonitoring of parent compounds and their metabolites in biological samples (mostly urine and plasma) are discussed in depth. This review also covers the role of wastewater-based epidemiology in determining the overall human exposure of a given population to plastic-related species.

Suspect and non-target screening (SNTS) methods are being promoted in order to decode the human exposome since a wide chemical space can be analysed in a diversity of human biofluids. However, SNTS approaches in the exposomics field are infra-studied in comparison to environmental or food monitoring studies. In this work, a comprehensive suspect screening workflow was developed to annotate exposome-related xenobiotics and phase II metabolites in diverse human biofluids. Precisely, human urine, breast milk, saliva and ovarian follicular fluid were employed as samples and analysed by means of ultra-high performance liquid chromatography coupled with high resolution tandem mass spectrometry (UHPLC-HRMS/MS). To automate the workflow, the “peak rating” parameter implemented in Compound Discoverer 3.3.2 was optimized to avoid time-consuming manual revision of chromatographic peaks. In addition, the presence of endogenous molecules that might interfere with the annotation of xenobiotics was carefully studied as the employment of inclusion and exclusion suspect lists. To evaluate the workflow, limits of identification (LOIs) and type I and II errors (i.e., false positives and negatives, respectively) were calculated in both standard solutions and spiked biofluids using 161 xenobiotics and 22 metabolites. For 80.3 % of the suspects, LOIs below 15 ng/mL were achieved. In terms of type I errors, only two cases were identified in standards and spiked samples. Regarding type II errors, the 7.7 % errors accounted in standards increased to 17.4 % in real samples. Lastly, the use of an inclusion list for endogens was favoured since it avoided 18.7 % of potential type I errors, while the exclusion list caused 7.2 % of type II errors despite making the annotation workflow less time-consuming.

Persistent, mobile and toxic substances have drawn attention nowadays due to their particular properties, but they are overlooked in human monitorization works, limiting the knowledge of the human exposome. In that sense, human urine is an interesting matrix since not only parent compounds are eliminated, but also their phase II metabolites that could act as biomarkers. In this work, 11 sample preparation procedures involving preconcentration were tested to ensure maximum analytical coverage in human urine using mixed-mode liquid chromatography coupled with high-resolution tandem mass spectrometry. The optimized procedure consisted of a combination of solid-phase extraction and salt-assisted liquid-liquid extraction and it was employed for suspect screening. Additionally, a non-discriminatory dilute-and-shoot approach was also evaluated. After evaluating the workflow in terms of limits of identification and type II errors (i.e., false negatives), a pooled urine sample was analysed. From a list of 1450 suspects and in-silico simulated 1568 phase II metabolites (i.e. sulphates, glucuronides, and glycines), 44 and 14 substances were annotated, respectively. Most of the screened suspects were diverse industrial chemicals, but biocides, natural products and pharmaceuticals were also detected. Lastly, the complementarity of the sample preparation procedures, columns, and analysis conditions was assessed. As a result, dilute-and-shoot and the Acclaim Trinity P1 column at pH =3 (positive ionization) and pH =7 (negative ionization) allowed the maximum coverage since almost 70 % of the total suspects could be screened using those conditions.

In this work, a comprehensive method for the simultaneous determination of 33 diverse persistent and mobile organic compounds (PMOCs) in human urine was developed by dilute-and-shoot (DS) followed by mixed-mode liquid chromatography coupled with tandem mass spectrometry (MMLC-MS/MS). In the sample preparation step, DS was chosen since it allowed the quantification of all targets in comparison to lyophilization. For the chromatographic separation, Acclaim Trinity P1 and P2 trimodal columns provided greater capacity for retaining PMOCs than reverse phase and hydrophilic interaction liquid chromatography. Therefore, DS was validated at 5 and 50 ng/mL in urine with both mixed mode columns at pH = 3 and 7. Regarding figures of merit, linear calibration curves (r2 > 0.999) built between instrumental quantification limits (mostly below 5 ng/mL) and 500 ng/mL were achieved. Despite only 60% of the targets were recovered at 5 ng/mL because of the dilution, all PMOCs were quantified at 50 ng/mL. Using surrogate correction, apparent recoveries in the 70–130% range were obtained for 91% of the targets. To analyse human urine samples, the Acclaim Trinity P1 column at pH = 3 and 7 was selected as a consensus between analytical coverage (i.e. 94% of the targets) and chromatographic runs. In a pooled urine sample, industrial chemicals (acrylamide and bisphenol S), biocides and their metabolites (2-methyl-4-isothiazolin-3-one, dimethyl phosphate, 6-chloropyridine-3-carboxylic acid, and ammonium glufosinate) and an artificial sweetener (aspartame) were determined at ng/mL levels. The outcomes of this work showed that humans are also exposed to PMOCs due to their persistence and mobility, and therefore, further human risk assessment is needed.

The use of suspect and non-target screening (SNTS) for the characterization of the chemical exposome employing human biofluids is gaining attention. Among the biofluids, urine is one of the preferred matrices since organic xenobiotics are excreted through it after metabolization. However, achieving a consensus between selectivity (i.e. preserving as many compounds as possible) and sensitivity (i.e. minimizing matrix effects by removing interferences) at the sample preparation step is challenging. Within this context, several sample preparation approaches, including solid-phase extraction (SPE), liquid-liquid extraction (LLE), salt-assisted LLE (SALLE) and dilute-and-shoot (DS) were tested to screen not only exogenous compounds in human urine but also their phase II metabolites using liquid-chromatography coupled to high-resolution tandem mass spectrometry (LC-HRMS/MS). Additionally, enzymatic hydrolysis of phase II metabolites was evaluated. Under optimal conditions, SPE resulted in the best sample preparation approach in terms of the number of detected xenobiotics and metabolites since 97.1% of the total annotated suspects were present in samples extracted by SPE. In LLE and SALLE, pure ethyl acetate turned out to be the best extractant but fewer suspects than with SPE (80.7%) were screened. Lastly, only 52.5% of the suspects were annotated in the DS approach, showing that it could only be used to detect compounds at high concentration levels. Using pure standards, the presence of diverse xenobiotics such as parabens, industrial chemicals (benzophenone-3, caprolactam and mono-2-ethyl-5-hydroxyhexyl phthalate) and chemicals related to daily habits (caffeine, cotinine or triclosan) was confirmed. Regarding enzymatic hydrolysis, only 10 parent compounds of the 44 glucuronides were successfully annotated in the hydrolysed samples. Therefore, the screening of metabolites in non-hydrolysed samples through SNTS is the most suitable approach for exposome characterization.

Micropollutants monitoring in wastewater can serve as a picture of what is consuming society and how it can impact the aquatic environment. In this work, a suspect screening approach was used to detect the known and unknown contaminants in wastewater samples collected from two wastewater treatment plants (WWTPs) located in the Basque Country (Crispijana in Alava, and Galindo in Vizcaya) during two weekly sampling campaigns, which included the months from April to July 2020, part of the confinement period caused by COVID-19. To that aim, high-resolution mass spectrometry was used to collect full-scan data-dependent tandem mass spectra from the water samples using a suspect database containing >40,000 chemical substances. The presence of > 80 contaminants was confirmed (level 1) and quantified in both WWTP samples, while at least 47 compounds were tentatively identified (2a). Among the contaminants of concern, an increase in the occurrence of some compounds used for COVID-19 disease treatment, such as lopinavir and hydroxychloroquine, was observed during the lockdown. A prioritization strategy for environmental risk assessment was carried out considering only the compounds quantified in the effluents of Crispijana and Galindo WWTPs. The compounds were scored based on the removal efficiency, estimated persistency, bioconcentration factor, mobility, toxicity potential and frequency of detection in the samples. With this approach, 33 compounds (e.g. amantadine, clozapine or lopinavir) were found to be considered key contaminants in the analyzed samples based on their concentration, occurrence and potential toxicity. Additionally, antimicrobial (RQ-AR) and antiviral (EDRP) risk of certain compounds was evaluated, where ciprofloxacin and fluconazole represented medium risk for antibiotic resistance (1 > RQ-AR > 0.1) in the aquatic ecosystems. Regarding mixture toxicity, the computed sum of toxic unit values of the different effluents (> 1) suggest that interactions between

The increasing number of contaminants in the environment has pushed water monitoring programs to find out the most hazardous known and unknown chemicals in the environment. Sample treatment-simplification methods and non-target screening approaches can help researchers to not overlook potential chemicals present in complex aqueous samples. In this work, an effect-directed analysis (EDA) protocol using the sea urchin embryo test (SET) as a toxicological in vivo bioassay was used as simplified strategy to identify potential unknown chemicals present in a very complex aqueous matrix such as hospital effluent. The SET bioassay was used for the first time here to evaluate potential toxic fractions in hospital effluent, which were obtained after a two-step fractionation using C18 and aminopropyl chromatographic semi-preparative columns. The unknown compounds present in the toxic fractions were identified by means of liquid chromatography coupled to a Q Exactive Orbitrap high-resolution mass spectrometer (LC-HRMS) and using a suspect analysis approach. The results were complemented by gas chromatography-mass spectrometry analysis (GC-MS) in order to identify the widest range of chemical compounds present in the sample and the toxic fractions. Using EDA as sample treatment simplification method, the number of unknown chemicals (>446 features) detected in the raw sample was narrowed down to 94 potential toxic candidates identified in the significantly toxic fractions. Among them, the presence of 25 compounds was confirmed with available chemical standards including 14 pharmaceuticals, a personal care product, six pesticides and four industrial products. The observations found in this work emphasize the difficulties in identifying potential toxicity drivers in complex water samples, as in the case of hospital wastewater.

Since wastewater treatment plants (WWTPs) were not originally designed to eliminate contaminants of emerging concern (CECs), alternative strategies like membrane bioreactor (MBR) technology are gaining importance in achieving effective CEC removal and minimising their environmental impact. In this study, composite wastewater samples were collected from the biggest WWTP in the Basque Country (Galindo, Biscay) and the performance of two secondary treatments (i.e. conventional activated sludge treatment, CAS, and MBR) was assessed. The combination of a suspect screening approach using liquid chromatography tandem high-resolution mass spectrometry (LC-HRMS) and multitarget analysis by gas chromatography-mass spectrometry (GC-MS) allowed the detection of approximately 200 compounds in the WWTP effluents. The estimated removal efficiencies (REs) revealed that only 16 micropollutants exhibited enhanced removal by MBR treatment (RE >70% or 40 – 60%). The environmental risk posed by the non-eliminated compounds after both treatments remained similar, being anthracene, clarithromycin, bis(2-ethylhexyl) phthalate (DEHP) and dilantin the most concerning pollutants (RQ >1). The Microtox® bioassay confirmed the MBR’s efficiency in removing baseline toxicity, while suggesting a similar performance of CAS treatment. These minimal differences between treatments call into question the worthiness of MBR treatment and emphasise the need to seek more efficient alternative treatment methods.

The concept of exposome covers all the exposures an individual suffers from conception to death, which can be partially assessed through the monitoring of human biofluids. In there, target ana- lytical approaches tend to focus on a limited set of xenobiotics, whereas exposomic studies need broad scopes in search of a full understanding. Given the issue, suspect and non-target screen- ing are feasible alternatives. However, adequate sample preparation procedures should minimize interferences without significantly reducing the number of xenobiotics. Within this context, the present article aims to describe comprehensive sample preparation procedures for suspect or non- target screening of organic xenobiotics in several human biofluids, all coupled to unified separa- tion and detection conditions based on ultra-high performance liquid chromatography-high res- olution tandem mass spectrometry (UHPLC–HRMS/MS)

This work describes the development of a robust analytical methodology for the simultaneous determination of 50 semi-volatile organic compounds (SVOCs) in wastewater effluent samples by solid-phase extraction (SPE) followed by gas chromatography coupled to mass spectrometry (GC–MS) analysis. In this work, we studied extensively whether the validated SPE method used for the analysis of polar compounds in wastewaters could be extended to the analysis of non-polar compounds in the same analytical run. To that aim, the effect of different organic solvents in the SPE process (i.e., sample conditioning prior to SPE, elution solvent and evaporation steps) was evaluated. In this sense, the addition of methanol to wastewater samples before the extraction, the use of hexane:toluene (4:1, v/v) mixture for the quantitative elution of target compounds, and the addition of isooctane during the evaporation were required to minimize analyte losses during SPE and enhance extraction yields. Overall, the developed methodology showed a good performance for the determination of 50 SVOCs, and was further applied to the analysis of real wastewater effluent samples.

A collaborative trial involving 16 participants from nine European countries was conducted within the NORMAN network in efforts to harmonise suspect and non-target screening of environmental contaminants in whole fish samples of bream (Abramis brama). Participants were provided with freeze-dried, homogenised fish samples from a contaminated and a reference site, extracts (spiked and non-spiked) and reference sample preparation protocols for liquid chromatography (LC) and gas chromatography (GC) coupled to high resolution mass spectrometry (HRMS). Participants extracted fish samples using their in-house sample preparation method and/or the protocol provided. Participants correctly identified 9–69 % of spiked compounds using LC-HRMS and 20–60 % of spiked compounds using GC-HRMS. From the contaminated site, suspect screening with participants’ own suspect lists led to putative identification of on average ~145 and ~20 unique features per participant using LC-HRMS and GC-HRMS, respectively, while non-target screening identified on average ~42 and ~56 unique features per participant using LC-HRMS and GC-HRMS, respectively. Within the same sub-group of sample preparation method, only a few features were identified by at least two participants in suspect screening (16 features using LC-HRMS, 0 features using GC-HRMS) and non-target screening (0 features using LC-HRMS, 2 features using GC-HRMS). The compounds identified had log octanol/water partition coefficient (KOW) values from − 9.9 to 16 and mass-to-charge ratios (m/z) of 68 to 761 (LC-HRMS and GC-HRMS). A significant linear trend was found between log KOW and m/z for the GC-HRMS data. Overall, these findings indicate that differences in screening results are mainly due to the data analysis workflows used by different participants. Further work is needed to harmonise the results obtained when applying suspect and non-target screening approaches to environmental biota samples.

The interest in contaminants of emerging concern (CECs) has increased lately due to their continued emission and potential ecotoxicological hazards. Wastewater treatment plants (WWTPs) are generally not capable of eliminating them and are considered the main pathway for CECs to the aquatic environment. The number of CECs in WWTPs effluents is often so large that complementary approaches to the conventional target analysis need to be implemented. Within this context, multitarget quantitative analysis (162 compounds) and a suspect screening (>40,000 suspects) approaches were applied to characterize the CEC fingerprint in effluents of five WWTPs in the Henares River basin (central Spain) during two sampling campaigns (summer and autumn). The results indicated that 76% of the compounds quantified corresponded to pharmaceuticals, 21% to pesticides and 3% to industrial chemicals. Apart from the 82 compounds quantified, suspect screening increased the list to 297 annotated compounds. Significant differences in the CEC fingerprint were observed between summer and autumn campaigns and between the WWTPs, being those serving the city of Alcala de Henares the ones with the largest number of compounds and concentrations. Finally, a risk prioritization approach was applied based on risk quotients (RQs) for algae, invertebrates, and fish. Azithromycin, diuron, chlortoluron, clarithromycin, sertraline and sulfamethoxazole were identified as having the largest risks to algae. As for invertebrates, the compounds having the largest RQs were carbendazim, fenoxycarb and eprosartan, and for fish acetaminophen, DEET, carbendazim, caffeine, fluconazole, and azithromycin. The two WWTPs showing higher calculated Risk Indexes had tertiary treatments, which points towards the need of increasing the removal efficiency in urban WWTPs. Furthermore, considering the complex mixtures emitted into the environment and the low dilution capacity of Mediterranean rivers, we recommend the development of d

[EN] In the present work, a target analysis method for simultaneously determining 24 diverse endocrine-disrupting compounds (EDCs) in urine (benzophenones, bisphenols, parabens, phthalates and antibacterials) was developed. The target analysis approach (including enzymatic hydrolysis, clean-up by solid-phase extraction and analysis by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS)) was optimized, validated and applied to volunteers' samples, in which 67% of the target EDCs were quantified. For instance, benzophenone-3 (0.2-13 ng g(-1)), bisphenol A (7.7-13.7 ng g(-1)), methyl 3,5-dihydroxybenzoate (8-254 ng g(-1)), mono butyl phthalate (2-17 ng g(-1)) and triclosan (0.3-9 ng g(-1)) were found at the highest concentrations, but the presence of other analogues was detected as well. The developed target method was further extended to suspect and non-target screening (SNTS) by means of LC coupled to high-resolution MS/MS. First, well-defined workflows for SNTS were validated by applying the previously developed method to an extended list of compounds (83), and then, to the same real urine samples. From a list of approximately 4000 suspects, 33 were annotated at levels from 1 to 3, with food additives/ingredients and personal care products being the most abundant ones. In the non-target approach, the search was limited to molecules containing S, Cl and/or Br atoms, annotating 4 pharmaceuticals. The results from this study showed that the combination of the lower limits of detection of MS/MS and the identification power of high-resolution MS/MS is still compulsory for a more accurate definition of human exposome in urine samples.

An effect-directed analysis (EDA) approach was used to identify the compounds responsible for endocrine disruption in a hospital effluent (Basque Country). In order to facilitate the identification of the potentially toxic substances, a sample was collected using an automated onsite large volume solid phase extraction (LV-SPE) system. Then, it was fractionated with a two-step orthogonal chromatographic separation and tested for estrogenic effects with a recombinant yeast (A-YES) in-vitro bioassay. The fractionation method was optimized and validated for 184 compounds, and its application to the hospital effluent sample allowed reducing the number of unknowns from 292 in the raw sample to 35 after suspect analysis of the bioactive fractions. Among those, 7 of them were confirmed with chemical standards. In addition, target analysis of the raw sample confirmed the presence of mestranol, estrone and dodemorph in the fractions showing estrogenic activity. Predictive estrogenic activity modelling using quantitative structure-activity relationships indicated that the hormones mestranol (5840 ng/L) and estrone (128 ng/L), the plasticiser bisphenol A (9219 ng/L) and the preservative butylparaben (1224 ng/L) were the main contributors of the potential toxicity. Derived bioanalytical equivalents (BEQs) pointed mestranol and estrone as the main contributors (56 % and 43 %, respectively) of the 50 % of the sample's explained total estrogenic activity.

[EN]Amitriptyline (AMI) is a commonly tricyclic antidepressant to treat depression, anxiety, and other conditions. Like many other pharmaceuticals, AMI and its by-products are incompletely removed during wastewater treatment and therefore they are released to rivers, estuaries and coastal waters. The presence of this kind of compounds in the water environment may involve a negative impact on non-target aquatic organisms at relatively low concentrations. However, the knowledge of AMI effects on aquatic organisms in the environment is scarce. Thus, the objective of this work is to determine the effects of environmentally-relevant concentrations of AMI on biological responses at biochemical and cellular levels in marine teleost. Gilt-head seabream (S. aurata) were exposed to AMI for 7 days at 0.2 mu g/L in an open flow system and a battery of biomarkers were investigated: acetylcholinesterase, catalase, superoxide dismutase, glutathione S-transferase, cytochrome C oxidase, P450 CYP1A1 ethoxyresorufin (O) dealkylation, and lysosomal biomarkers. Biomarkers were integrated as IBR/n (biological response index). Overall, it can be concluded that AMI exposure at environmentally-relevant concentration induces significant biological responses to stress in marine teleost, especially in lysosomal biomarkers. However, further research is needed about the effects of AMI and other pharmaceuticals on biomarkers in nontargeted species, to raise the knowledge about the toxicity of this type of emerging pollutants.

The development of suspect or non-target screening methods to detect xenobiotics in biological fluids is essential to properly understand the exposome and assess its adverse health effects on humans. In order to fulfil that aim, the biomonitorization of human fluids is compulsory. However, these methods are not yet extensively developed, especially for polar organic xenobiotics in biofluids such as milk, as most works are only focused on certain analytes of interest. In this work, a multi-target analysis method to determine 245 diverse xenobiotics in milk by means of Ultra High Performance Liquid Chromatography (UHPLC)-qOrbitrap was developed. Under optimal conditions, liquid milk samples were extracted with acetonitrile in the presence of anhydrous Na2SO4 and NaCl, and the extracts were cleaned-up by protein precipitation at low temperature and Captiva Non-Drip (ND)—Lipids filters. The optimized method was validated at two concentration-levels (10 ng/g and 40 ng/g) obtaining satisfactory figures of merit for more than 200 compounds. The validated multi-target method was applied to several milk samples, including commercial and breast milk, provided by 4 healthy volunteers. Moreover, the method was extended to perform suspect analysis of more than 17,000 xenobiotics. All in all, several diverse xenobiotics were detected, highlighting food additives (benzothiazole) or phytoestrogens (genistein and genistin) in commercial milk samples, and stimulants (caffeine), plasticizers (phthalates), UV filters (benzophenone), or pharmaceuticals (orlistat) in breast milk samples.

The efects of hydrophobic microcontaminants such as alkylphenols, organophosphorus compounds, organochloride pesticides, phthalates and musk fragances were studied in mussels. The proposed analytical strategy is based on the combination of passive sampling studies, bioconcentration measurements of micropollutants in mussels, environmental NMR metabolomics of two tissues (gonad, muscle) and hemolymph of mussels and histological analysis. By means of this work, it was verified the feasibility of this strategy in controlled conditions with intent to use it in future environmental studies. The micropollutants mixture was responsible of early spawning in mussels. In fact, the most significant metabolic changes were observed in the same day that spawning took place.; Lan honetan, ingurumen analisirako metodologia planteamendu berri bat proposatu da. Horretarako, kimikariek eta biologoek baldintza kontrolatuetako esposizioa egiteko elkarlanean jardun genuen. Esperimentu honetan, muskuiluak eta lagin-biltze pasiboko tresnak hainbat mikrokutsatzaile hidrofoboren eraginpean jarri ziren. Batetik, kutsatzaileen kontzentrazioak neurtu ziren, lagin-biltze puntualen zein lagin-biltze pasiboen bitartez. Bestetik, muskuiluetan kutsatzaileen kontzentrazioak neurtu ziren. Biologoek, euren aldetik, muskuiluen azterketa histopatologikoa egin zuten. Azkenik, NMR-n oinarritutako metabolomika erabili zen muskuiluek kutsatzaileen aurrean ematen zuten erantzuna aztertzeko. Lau estrategien konbinazioarekin, kausa (kokteleko mikrokutsatzaileen kontzentrazioak eta muskuiluek metatutakoa) eta eragindako efektuak (histologia azterketetan behatutakoak) hobeto uler ditzakegu. Kutsatzaileek eragiten dituzten aldaketak ulertzeko eta ondorioak azaltzeko metabolomika baliabide erabilgarria dela ondorioztatu genuen. Kutsatzaileen koktelak errute goiztiarra eragin zien muskuiluei; izan ere, NMR metabolomika erabiliz, aldaketa metaboliko nabarienak errute-egunean ikusi ziren.

Background In this study, an alternative and complementary method to those approaches currently used to estimate alcohol consumption by the population is described. This method, known as wastewater-based epidemiology (WBE), allows back-calculating the alcohol consumption rate in a given population from the concentrations of a selected biomarker measured in wastewater. Methods Composite (24-h) wastewater samples were collected at the inlet of 17 wastewater treatment plants located in 13 Spanish cities for seven consecutive days in 2018. The sampled area covered 12.8% of the Spanish population. Wastewater samples were analyzed to determine the concentration of ethyl sulfate, the biomarker used to back-calculate alcohol consumption. Results Alcohol consumption ranged from 4.5 to 46 mL/day/inhabitant. Differences in consumption were statistically significant among the investigated cities and between weekdays and weekends. WBE-derived estimates of alcohol consumption were comparable to those reported by its corresponding region in the Spanish National Health Survey in most cases. At the national level, comparable results were obtained between the WBE-derived annual consumption rate (5.7 ± 1.2 L ethanol per capita (aged 15+)) and that reported by the National Health Survey (4.7 L ethanol per capita (aged 15+)). Conclusions This is the largest WBE study carried out to date in Spain to estimate alcohol consumption rates. It confirms that this approach is useful for establishing spatial and temporal patterns of alcohol consumption, which could contribute to the development of health care management plans and policies. Contrary to established methods, it allows obtaining information in a fast and relatively economical way

370 p., Doktorego-tesi honetan farmakoek eta zaintza pertsonalerako produktuek ur-ekosistemetan dituzten albo-ondorioak ikertzeko hurbilketa holistikoa garatu da. Alde batetik, masa-espektrometriari akoplatutako likido-kromatografia erabilita metodo analitiko sendoak eta fidagarriak optimizatu dira farmakoak eta zaintza pertsonalerako produktuak ingurumeneko matrize desberdinetan determinatzeko. Bestalde, urraburu arrainekin esposizio-esperimentuak burutu dira farmako eta zaintza pertsonalerako produktu desberdinen biometatzea eta ehunen arteko banaketa ebaluatzeko. Horrez gain, kutsatzaile horien biotransformazioa aztertu eta degradazio-produktuak karakterizatu dira bereizmen altuko masa- espektrometriaren bidez. Azkenik, metabolomikako hurbilketa bideratuak eta ez-bideratuak erabilita organismo urtarretan farmako eta zaintza pertsonalerako produktu desberdinek eragin ditzaketen maila molekularreko aldaketak ikertu dira. Oro har, doktorego-tesi honetako emaitzek egiaztatzen dute amitriptilina antidepresiboa, ciprofloxacin antibiotikoa eta oxibenzona ultramore iragazkia arrainetan metatu daitezkeela, eta kutsatzaile horiek plasmako, burmuineko eta gibeleko metaboloman organismo mailara heda daitezkeen albo-ondorioak sortzen dituztela. Gainera, garatutako hurbilketa analitiko hauek beste kutsatzaile edota beste espezie batzuen joerak ikertzeko ere erabili daitezke, eta modu horretan, neurri arautzaile berriak ezartzea bermatuko duen ingurumeneko arriskuen ebaluaziorako funtsezko informazioa biltzea posible izango da.

Nowadays, due to the wide range of applications, the presence of per- and polyfluoroalkyl substances is increasing in the environment. Aquatic organisms are very useful bioindicators in order to assess the health of the aquatic environment. Within this objective, grey mullet (Chelon Labrosus) livers and oysters (Ostrea edulis)of the French, Basque, Spanish and Portuguese coasts were analysed. In the case of the liver, perfluorooctane sulfonic acid (PFOS), perfluorodecanoic acid (PFDA) and per-fluorooctane sulfonamide (PFOSA) were the detected target analytes in all the sam-pling points. Surprisingly high concentrations of PFOS (443-1,214 ng/g) were detected in the river of Gernika, which is placed in the Natural Reserve of Urdaibai, highlighting the effect of the wastewater treatment plant (WWTP) and/or the industry. In the case of oysters, PFOS and PFOSA were detected at levels lower than those found in live; Egun, konposatu per- eta polifluoratuek (PFAS-ek) gure eguneroko bizitzan dituzten erabilera anitzak direla eta, ingurunean gero eta nabariagoa da euren presentzia. Ur-ekosistemen egoera aztertzea helburu, organismo itsastarrak kutsaduraren adierazle ezin hobeak dira. Ildo horretan, lan honetan Frantziako, Euskal Herriko, Espainiako eta Portugaleko kostaldeetako lazunen (Chelon labrosus-en) gibelak eta ostrak (Ostrea edulis) aztertu dira. Gibelen kasuan, azido perfluorooktanosulfonikoa (PFOS), azido perfluorodekanoikoa (PFDA) eta perfluorooktanosulfonamida (PFOSA) izan dira laginak biltzeko puntu guztietan detektatutako PFAS-ak. Aipatzekoa da Urdaibaiko Erreserba Naturalean kokatuta dagoen Gernikako itsasadarrean aurkitutako PFOS-aren kontzentrazioak (443-1214 ng/g), araztegiaren edota industriaren eragina nabarmenduz. Ostren kasuan, PFOS eta PFOSA izan dira detektatutako kutsatzaileak, betiere gibelean lortutako kontzentrazioak baino baxuagoak.

288 p., Azken urteotan, konposatu fluoratuenganako kezka handituz joan da gizartearen eta zientzialarien artean. Izan ere, kutsatzaile hauek gure eguneroko bizitzan erabiltzen diren material eta tresna ugaritan aurki ditzakegu euren egiturak ematen dizkien propietate bereziei esker, hala nola, alfonbretan, kirol-arropetan, jakiak ontziratzeko materialetan eta sukaldeko tresnetan aurki daitezke. Tesi honen helburu nagusiak bi izan dira; alde batetik, konposatu fluoratuak determinatzeko metodo analitikoen garapena eta, bestetik, metodo horien aplikazioa ikerketa kasu errealetara.Metodo analitikoei dagokienez, hiru metodo desberdin garatu dira konposatu hauen kuantifikazioa barazki eta lurretan, arrainetan eta ontziratze materialetan burutzeko. Laginaren prestaketa-urratsean ultrasoinu fokatuen bidezko erauzketa erabili den bitartean, analisia likido kromatografia-tandem masa espektrometria teknikaren bitartez burutu da, bereizmen baxua kuantifikatzeko eta bereizmen altua konposatuen identifikaziorako.Behin metodo analitikoak garatuta, ikerketa lan desberdinetan aplikatu dira. Alde batetik, hainbat herrialdetan debekatuta egon arren oraindik nekazaritza arloan erabiltzen den Sulfluramida pestizidaren degradazioa aztertu da lurrean 81 egunetan zehar. Ikerketa honetan hainbat degradazio produktu determinatzeaz gain, degradazioaren eragina barazki baten (azenarioa) presentzian aztertu da. Emaitzen arabera, Sulfluramida lurrean toxikotasun handia duten konposatu fluoratuetara (azido perfluorooktanoikora, PFOSera, besteak beste) degrada daiteke barazkien presentziak degradazio hau bizkortzen duelarik.Bestalde, Espainiako, Frantziako eta Portugaleko kostetan bildutako, ostra, muskuilu eta arrain gibelen monitorizazioa burutu da gure kostaldetako konposatu fluoratuen maila aztertzeko. Ildo berean, arrainetan detektatu den eta industrian erabilera ugaria duen 8:2 diPAP konposatu fluoratua aukeratu da Plentziako Itsas Estazioan (PIE, UPV-EHU) arrainen esposaketa bat egiteko. Esposaketa

256 p., Two unavoidable residues from wastewater treatment plants (WWTPs) are effluent water and sewage sludge. The latter, isconsidered one of the largest pollutant sink because it contains a broad range of microorganisms and organic and inorganicpollutants. Although, prior to its disposal, it is submitted to different chemical and physical treatments. However, due to the lack ofeffectiveness of these treatments in removing pollutants, concern about its use in agriculture as soil fertiliser is increasing. In thissense, it is important to study the behaviour of pollutants by plants cultivated in sewage or compost-amended soils.Two main objectives were defined in the present PhD thesis. On the one hand, a great effort was made in the development of robust,selective, accurate, precise and sensitive analytical procedures for the determination of several organic pollutants, includingpolybrominated diphenyl ethers (PBDEs), perfluoroalkyl substances (PFASs), hormones, triclosan (TCS), bisphenol A (BPA),musk fragrances and alkyl phenols (APs), in solid matrices, such as compost-amended soil, carrot and lettuce in order to achievereliable data. For this purpose, focused ultrasound solid-liquid (FUSLE) extraction combined with different clean-up strategies,such as traditional solid-phase extraction (SPE), dispersive solid-phase extraction (dSPE) or enrichment on cheap polymericmaterial were optimised.Once the analytical methodologies were validated, the second objective was related with the uptake of some organic pollutants(PBDEs, PFASs, BPA and musk fragrances) by carrot and lettuce crops cultivated in fortified compost-amended soils.Regarding the observed behaviour of the pollutants, it was concluded that pollutant properties, crop type and soil characteristicsexert an important influence in the chemical translocation through the plant. In general, the higher the soil organic carbon contentwas, the lower the calculated bioconcentration factors. Concerning target analyte properties

Hydrogen is the only atom for which the Schr odinger equation is solvable. Consisting only of a proton and an electron, hydrogen is the lightest element and, nevertheless, is far from being simple. Under ambient conditions, it forms diatomic molecules H2 in gas phase, but di erent temperature and pressures lead to a complex phase diagram, which is not completely known yet. Solid hydrogen was rst documented in 1899 [1] and was found to be isolating. At higher pressures, however, hydrogen can be metallized. In 1935 Wigner and Huntington predicted that the metallization pressure would be 25 GPa [2], where molecules would disociate to form a monoatomic metal, as alkali metals that lie below hydrogen in the periodic table. The prediction of the metallization pressure turned out to be wrong: metallic hydrogen has not been found yet, even under a pressure as high as 320 GPa. Nevertheless, extrapolations based on optical measurements suggest that a metallic phase may be attained at 450 GPa [3]. The interest of material scientist in metallic hydrogen can be attributed, at least to a great extent, to Ashcroft, who in 1968 suggested that such a system could be a hightemperature superconductor [4]. The temperature at which this material would exhibit a transition from a superconducting to a non-superconducting state (Tc) was estimated to be around room temperature. The implications of such a statement are very interesting in the eld of astrophysics: in planets that contain a big quantity of hydrogen and whose temperature is below Tc, superconducting hydrogen may be found, specially at the center, where the gravitational pressure is high. This might be the case of Jupiter, whose proportion of hydrogen is about 90%. There are also speculations suggesting that the high magnetic eld of Jupiter is due to persistent currents related to the superconducting phase [5]. Metallization and superconductivity of hydrogen has puzzled scientists for decades, and the community is trying to answ

Duración (en horas): De 21 a 30 horas. Destinatario: Estudiante, En este recurso didáctico se presenta la metodología en base a proyectos utilizada en el proceso de enseñanza-aprendizaje de la asignatura optativa "Cromatografía y Técnicas Afines" que se imparte en el segundo ciclo de la Licenciatura de Química. El proyecto, que lleva como título "¿Son fiables los productos que encontramos en los supermercados?", permite al alumno aprender los distintos métodos analíticos para el analisis de contaminantes en los productos alimenticios, pero a su vez comprender todos aquellos aspectos teórico-prácticos de la cromatografía y las técnicas afines. En este sentido, cada vez es mayor la información y las noticias que nos llegan sobre la contaminación de los productos alimenticios. Podemos encontrar un amplio número de ejemplos en la última década como la contaminación de pollos con dioxinas en Bélgica y Alemania, la contaminación de leche para niños con melanina en China, etc. Estos casos suscitan una gran preocupación en la sociedad sobre la calidad de los productos alimenticios así como el interés de plantear reglamentación sobre los alimentos que garanticen el control de la calidad de los mismos. Este proyecto, por lo tanto, irá encaminado al desarrollo de determinados métodos analíticos que pueden ser aplicados en el departamento de la unidad de análisis de alimentos que garanticen su calidad y el bienestar del consumidor, como son, por ejemplo: a) Objetivos marcados por el responsable del laboratorio de cromatografía de gases: análisis de bifenilos policlorados en peces, la elección de un inyector adecuado para el análisis de furano en café, y el análisis de melanina en leche en polvo. b) Con lo que respecta al laboratorio de Cromatografía de Líquidos los objetivos marcados son: determinación de clenbuterol, salbutamol y cimateol en carne y la detección de determinados problemas analíticos detectados en distintos métodos analíticos y su resolución.