Search

Wastewater-based epidemiology (WBE) estimates collective consumption or exposure to chemicals or pathogens by monitoring the substances excreted in the population’s wastewater. Advances in mass spectrometry (MS) and the application of some clinical diagnostic tools and proteomics to wastewater fingerprinting have been linked to the discovery of new biomarkers and indicators of population health and are broadening the scope of WBE that nowadays cover not only small molecule biomarkers but also genetic biomarkers, large molecules, viruses, infection diseases, resistance, etc. This mini-review highlights recent WBE advances using MS and how this progress can create a fingerprint of a city’s health hazards, habits, and lifestyle, which is gaining in public health emphasis.

Recent advances in gas chromatography-mass spectrometry (GC-MS) (ionization sources at atmospheric pressure, fast GC, GCxGC, high resolution mass spectrometry, etc.) have significantly improved the capabilities of this technique, traditionally used to determine pesticides. Although liquid chromatography mass spectrometry (LC-MS/MS) is nowadays preferred, pyrethroids and organochlorine pesticides are more sensitive by GC-MS and a significant number of other pesticides work well by both techniques. Here, we critically review the development, instrumentation, approaches and applications of GC-MS, focusing on the analysis of pesticide residues published between 2000 and 2019 along with outstanding pioneer contributions, with special emphasis on those published after 2010. This review attempts to fill a void of information on the state-of-art of GC-MS for pesticide residue determination, describing the pros and cons of the different approaches, and the main applications.

Two solid-phase extraction methods were systematically studied to determine 32 pharmaceuticals and personal care products in water and sediments by ultrahigh-performance liquid chromatography–tandem mass spectrometry. One involves HLB cartridges activated with sodium dodecyl sulfate before the passage of the sample to form an ion pair with cationic analytes, and the other uses mixed HLB–cation exchange cartridges. The accuracy of the sodium dodecyl sulfate method was good for most compounds (recoveries of 61–120% with relative standard deviation less than 23%). However, the recoveries for atorvastatin, codeine, paracetamol, flufenamic acid, and salicylic acid were approximately 50% and for omeprazole and triclocarban were even lower (from 0 to 12%). The detection limits were 1.65–25 ng L-1 in water and 0.33–4.00 ng g-1 (dry weight) in sediment. The recoveries for the mixed-mode cartridge (Strata-X-CW) method ranged from 57% to 120% with relative standard deviation less than 21%, with the exception of codeine [25% (water)], metformin [11% (sediment)], paracetamol [48% (sediment)], and salicylic acid [32% (sediment)]. The detection limits were 1.65–38.35 ng L-1 in water and 0.33–10 ng g-1 (dry weight) in sediment. Both methods followed the same pattern when applied to water. For sediments, the recoveries, which offer good performance, were not very high, although 60% of the compounds had recoveries greater 80%. The methods were applied to the analysis of surface water and sediments from the Albufera Natural Park (Spain). Twenty-seven of 32 analytes were detected in the samples analyzed.

This paper describes a procedure for the isolation of 20 organic micro-pollutants among pesticides, drugs, recreational drugs, flame retardants from river sediments. After a solid-liquid extraction with a methanol:water (50:50, v/v) solution, the supernatant was diluted with water and cleaned up by stir-disc solid-phase extraction (SPE). The disc was made of buckypaper, a self-supporting entangled assembly of carbon nanotubes, which was used as a highly porous, two-sided, sorbent membrane. In the preliminary activation step, the membrane was oxidised for 2-hours with nitric acid to extend its extraction capability also to more polar compounds. All extracts were analysed by ultra-high-performance liquid chromatography-tandem mass spectrometry. A comparative investigation with commercial Strata-X Polymeric Reversed Phase SPE cartridges proved the effectiveness of the lab-made device. On the average, the analytes were recovered with yields around 69% (low spike level) and 80% (medium and high spike level), while only a couple of analytes exhibited values less than 50%. The relative standard deviation was always less than 20%. Limits of detections were in the range 0.02–9.9 ng g−1. The validated method was then applied for the analysis of sediment samples from different sites of the River Turia basin in the area of Valencia (Spain), finding tris(2-chloroisopropyl)-phosphate in all sediments at a level ranging from 6.9 to 387.9 ng g−1. Other compounds, such as pesticides and pharmaceuticals were more sporadically in these samples.

The coupling of chromatography to mass spectrometry has been a very important step in environmental science that has changed routine workflows opening a horizon of new and impressive possibilities. This hyphenated technique benefits from coupling as chromatography offers great separation power and comprises various techniques and mechanisms. In turn, chromatography exploits the identification capability of mass spectrometry and is able to provide nominal or exact mass charge ration (m/z) not only of the intact molecule but also of several characteristic fragments. The sensitivity, selectivity, specificity, and rapidity in chromatography–mass spectrometry make this technology highly powerful in environmental science, especially in the detection of contaminants at trace levels and also in the environmental application of omics techniques and the profiling and fingerprinting of different samples. This review highlights how chromatography coupled to mass spectrometry has created a new paradigm in environmental science.

Water bodies cover approximately 70 % of the earth s surface, making them ecosystems with a high environmental value and the habitat for numerous species of flora and fauna. Emerging pollutants (EPs) are ubiquitous anthropogenic compounds of environmental concern that can be found at different concentration levels in matrices such as sediment, water and aquatic biota. In addition, EPs can be bioaccumulated and biomagnified, inducing adverse effects on biota, and posing a risk to humans when contaminated biota is consumed. Unlike abiotic matrices, the occurrence of EPs in aquatic biota has not been widely studied. This is probably because their complexity, due to the presence of lipids, proteins and other organic compounds, makes the extraction and analysis of EPs difficult. This review gathers the most relevant analytical methods published between 2014 and 2019, comparing them and evaluating their strengths and weaknesses. It is intended to provide a better understanding of the development of new and improved methods, and to be a reference for researchers who are looking for the best methodology for their studies

This study assess the presence of pharmaceutical and personal care products (PPCPs) and pesticides in different environmental compartments and microplastics in water of a characteristic lagoon wetland in Saudi Arabia to establish the transport, accumulation and fate of these pollutants in a water-stressed area under high anthropogenic pressure. In water, diazinon (up to 1016 ng L), caffeine (up to 20,663 ng L), diclofenac (up to 1390 ng L) and paracetamol (up to 3069 ng L) were at the highest concentrations. The substances with the highest frequency of detection were carbendazim, atorvastatin, caffeine, etoricoxib, lorazepam, metformin, ofloxacin, paracetamol, salicylic acid and tramadol. Considerably less pesticides and PPCPs at concentrations ranging from 0.01 to 126 ng g dry weight (d.w.) were detected in the other matrices (sediment ≫ soil > plants). The concentration of microplastics in water ranged from 0.7 to 7.8 items/L in the Al-Asfar lake and from 1.1 to 9.0 items/L in the Al-Hubail lake. Risk assessment [using hazards quotients (HQ)] was used to highlight pesticides and PPCPs of major ecological concern that should be closely monitored to avoid adverse effects.

Detecting ENP/NM/MNs in water is a demanding task not only because of the extremely small size of the particles and their potential sequestration and agglomeration, but also because of their unique physical and chemical characteristics. The aim of this chapter is to critically review the state-of-art of ENP/NM/MN detection in the environment, highlighting the advances that have taken place in the last five years (up to 2018). The available analytical techniques used for the detection and characterization of nanoparticles in water including particle size analysis, particle fraction concentration counts, surface area analysis, morphology and particle chemical composition analysis will be outlined and critically analyzed to describe advantages and pitfalls. Sample preparation aspects, imaging techniques (electron microscopy, scanning electron microscopy or X-ray microscopy), separation methods (flow field fractionation, liquid chromatography, hydrodynamic chromatography) and detection/characterization techniques (e.g. single particle inductive coupled plasma, mass spectrometry) have been discussed in depth. This chapter also introduces the established workflows to increase the knowledge on the fate, behaviour, disposition and toxicity of these ENP/NM/MNs in the environment.

This field study assesses the occurrence of emerging contaminants (EC) of the Albufera Natural Park. This protected wetland has as an area of 21120 hectares and it is located 10 km to the South of Valencia City (Spain). It consists of a highly eutrophic coastal lagoon surrounded mainly by rice fields that occupy the primitive marshland. The Turia River, to the north, the Jucar River, to the South, and a network of irrigation channels bring fresh water to the Albufera system. The study was focus on about 30 compounds including Personal Care Products and Pharmaceutical Compounds, including acid, basic and neutral. The interest in detecting environmental contaminants in different matrices (mostly water, soil and sediment) is increasing in the last years. This for their relevant impact on the global ecosystem. The selected compounds, in this study, constitute an important block of organic contaminants frequently found for many reasons(2). The results evidenced the presence of many of the selected EC both in water and sediment. The most abundant ones are analgesic and anti-inflammatory drugs (salicylic acid, diclofenac), antihypertensive (furosemide), anticoagulant (warfarin), stimulants (caffeine) and preservatives (parabens). The relation-ship between the presence of these compounds and the anthropic pressure in the area was carefully analysed

Wastewater-based epidemiology (WBE) has become a promising approach to provide anonymous information in almost real time about consumption or use of certain substances by the human being, exposition to external agents, and/or evaluation of health and disease state of a population. Daughton in 2001 theoretically developed the concept of WBE that four years later Zuccato et al. put into practice for illicit drugs

Pest control in agriculture is mainly based on the application of insecticides, which may impact nontarget beneficial organisms leading to undesirable ecological effects. Neonicotinoids are among the most widely used insecticides. However, they have important negative side effects, especially for pollinators and other beneficial insects feeding on nectar. Here, we identify a more accessible exposure route: Neonicotinoids reach and kill beneficial insects that feed on the most abundant carbohydrate source for insects in agroecosystems, honeydew. Honeydew is the excretion product of phloem-feeding hemipteran insects such as aphids, mealybugs, whiteflies, and psyllids. We allowed parasitic wasps and pollinating hoverflies to feed on honeydew from hemipterans feeding on trees treated with thiamethoxam or imidacloprid, the most commonly used neonicotinoids. LC-MS/MS analyses demonstrated that both neonicotinoids were present in honeydew. Honeydew with thiamethoxam was highly toxic to both species of beneficial insects, and honeydew with imidacloprid was moderately toxic to hoverflies. Collectively, our data provide strong evidence for honeydew as a route of insecticide exposure that may cause acute or chronic deleterious effects on nontarget organisms. This route should be considered in future environmental risk assessments of neonicotinoid applications.

During the last 60 years the development programs in various fields of Saudi Arabia, especially in the last two decades, have left clear marks on the country landscape. Moreover, there is an increase in treated sewage water which had adverse affects on the marine and terrestrial resources. In many Arid and semi arid regions, reuse of this water is a necessity for crop irrigation. The presence of organic emerging contaminants (ECs) in this water and their translocation to plants may represent a risk of human exposure. Nevertheless, information available about real field crops is scarce and focused on a limited number of compounds. The novelty of this work relays in the large number of ECs covered and the variety of crops (cabbage, barley, green beans, eggplants, chili, tomato and zucchini) analyzed. Extraction procedure developed provided an appropriate extraction yield (up to 50% of the compounds were recovered within a 70–120% range), with good repeatability (relative standard deviations below 20% in most cases) and sensitivity (LOQ b 25 ng g−1) for the model compounds. Determination by liquid chromatography quadrupole time-of-flight (LCQqTOF-MS) is able to identify N2000 contaminants. Sixty-four ECs were identified in wastewater among which, six pharmaceuticals (atenolol, caffeine, carbamazepine and its metabolites 10,11- epoxycarbamazepine, gemfibrozil, and naproxen) and seven pesticides (acetamiprid, atrazine deethyl, azoxystrobin, bupirimate, diazinon, malathion, pirimicarb and some of their metabolites) were detected in plants also. Furthermore, one metabolite of the ibuprofen (not detected in water or soil), the ibuprofen hexoside was also found in plants. Up to our knowledge, this study demonstrates for the first time the accumulation of ECs in crops irrigated with treated wastewater under real non-controlled environmental conditions.

Wastewater-based epidemiology (WBE) has been consolidated as a tool to provide real-time information on consumption of legal and illegal drugs of abuse by the population. However, WBE is expected to achieve more ambitious objectives such as establishing exposure to certain agents (pesticides, personal care products, persistent organic pollutants, and pathogens), incidence of specific diseases (diabetes, allergies, oxidative stress, and cancer), and determination of some lifestyle consequences (exposure to personal care products, consumption of doping substances or products for the treatment of erectile dysfunction) or environmental factors (increase in temperature) in populations. Herein, we outlined the state-of-the-art applications of WBE including its advantages and disadvantages as well as the prospects for achieving a broader assessment of the habits and health of populations. WBE needs to be further strengthened to help epidemiologists and health authorities to correctly assess fingerprints of human activities in wastewater.

The >Anthropocene> as new geological area view as the period during which human activity has been the dominant influence on climate and the environment gains defenders year after year. An important anthropogenic hazard is the environmental contamination due to the release of chemical substances affecting ecosystems that is growing parallel to the increase of population. One of the most representative contaminant related to the human impact are the contaminants of emerging concern (CECs), particularly, pharmaceuticals and personal care products. The work focused on determination of 35 Pharmaceuticals and Personal Care Products in water and sediment samples of 33 sampling stations located in Albufera Natural Park (an area of 21 thousand hectares, it is located in Valencia, Spain). The extraction was based on solid-phase extraction (SPE) using Strata X cartridges treated with sodium dodecyl sulfate (SDS) or mixed mode weak anion exchange cartridges. The determination was carried out by liquid chromatography-tandem mass spectrometry (LC-MS/MS) with a triple-quad using two precursor ¿ product ion transitions for each compound with the exception of ibuprofen that only gave one product ion in the multiple selected reaction monitoring mode (MRM).

A single workflow based on three approaches (target, suspected and non-target screening) using liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (LC-QTOF-MS) in data independent acquisition mode (DIA) was developed to assess the presence of emerging pollutants (EPs) in water and sediments from a Mediterranean River Basin. Identification of potential contaminants was based on mass accuracy, isotopic ratio pattern, theoretical fragmentation, and retention time using Waters UNIFI software. In the suspect screening against a library containing 2200 components, 68 contaminants were tentatively identified, 6 of which were confirmed and quantified with analytical standards. Non-target screening (NTS) required additional manual processing and the aid of an on-line database (ChemSpider) to tentatively identify compounds. Eprosartan, an antihypertensive drug not included in the library used for suspected screening, was confirmed and semi-quantified. The identification of Eprosartan proved the workflow to be functional for NTS. Target screening of 171 pesticides and 33 pharmaceuticals and personal care products (PPCPs) including the compounds confirmed using suspect and non target screening achieved monitoring of the most abundant contaminants from the head to the mouth of the Turia basin to establish their spatial distribution. QTOF-MS screening versatility with its high-resolution capability allows for a comprehensive assessment of EPs in the aquatic environment.

Pesticide residues in beebread, live and dead honey bees, together with honey bee death rate were monitored from June 2016 to June 2018 in three apiaries, located near agricultural settings and in wildlands. Dead honey bees were only collected and analyzed when significant mortality episodes occurred and pesticide content in beeswax of each experimental apiary was evaluated at the beginning of the study. Samples were extracted by a modified QuEChERS procedure and screened for pesticides residues by liquid chromatography mass spectrometry (LC-MS/MS). Pesticide hazard in the samples was evaluated through the hazard quotient approach (HQ). Beebread was widely contaminated with coumaphos and amitraz degradate 2, 4-dimethylphenylformamide (DMF), miticides detected in 94 and 97% of samples respectively. However, insecticides sprayed during citrus bloom like chlorpyrifos (up to 167 ng g )and dimethoate (up to 34 ng g )were the main responsible of the relevant pesticide hazard in this matrix. Pesticide levels in live bees were mostly residual, and pesticide hazard was low. Beeswax of the apiaries, contaminated by miticides, revealed a low pesticide hazard to honey bee colonies. Acute mortality episodes occurred only in the two apiaries located near agricultural settings. Dead bees collected during these episodes revealed high levels (up to 2700 ng g )of chlorpyrifos, dimethoate, omethoate and imidacloprid. HQ calculated in dead bees exceeded up to 37 times the threshold value considered as elevated hazard to honey bee health.

We set out to test if the methodology used to clean sheep wool wax (Lanolin) from pesticides could be used to clean beeswax as well. We first made an aggregate sample of brood comb wax from three different US beekeepers. Sub-samples of these aggregate wax samples were analyzed for pesticide contamination. The remaining wax, was then dissolved into hexane solution and run through four N, N-Dimethylformamide (DMF) washes. During these extractions, the pesticides partitioned into the DMF, and so were removed from the beeswax. Following the solvent extractions, the beeswax was tested again for pesticides. An average of 95% of the pesticide contamination was removed by the chemical wash procedure. • Beeswax is the beekeeping matrix with the highest pesticide content. • This study developed methodology for solvent-based removal of pesticides from beeswax (>95%). • Of 24 pesticides detected in beeswax samples before to the solvent extraction, only 3 pesticides were detected after the extraction with DMF.

The aquatic ecosystems are dynamic environments often affected directly or indirectly by a myriad of anthropogenic contaminants that need to be properly identified. In this study, liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-QqTOF-MS) suspected-screening was applied to mussels and riverine sediment both, non-spiked and spiked with a mixture of 32 pharmaceuticals. Three data acquisition methods –sequential window acquisition of all theoretical fragment-ion spectra (SWATH), in fix (FSWATH) and variable (VSWATH) window modes and Information Dependent Acquisition (IDA)– were compared to determine the most suitable acquisition technique. The results obtained in the spiked samples showed that the two SWATH modes enable to obtain the MS/MS spectrum of a higher number of compounds (up to 27 with FSWATH and 25 with VSWATH) than IDA (up to 19) in sediment and mussel. The different data acquisition modes were also tested in non-spiked samples to verify the results obtained in the spiked ones. Importantly, all the methods are able to detect the MS/MS spectrum of several contaminants in the samples when analysed against a database of >600 compounds. Up to 7 contaminants were tentatively detected with IDA, 15 with FSWATH and 17 with VSWATH. Most pollutants were pesticides and pharmaceuticals, being of particular interest the presence of ibuprofen and acetaminophen in mussels.

Pressurized liquid extraction (PLE) is a tool able to provide green extraction methods to further determine contaminants in food and the environment. The aim of this review is to offer a critical overview of the recent developments within this field and can be considered as an update of the previous that we published in 2015. Trends regarding sample treatment, solvents, in-cell clean-up approaches used in the extraction of organic contaminants are addressed. Special attention deserve those methods that include on-line clean up in the extraction cell. Comparison with other green techniques is also presented. The final objective of this review is to clearly define the role that this technique plays in the analysis of organic pollutants, their strengths and weaknesses, as well as the updated spectrum of applications for which PLE is an essential tool.

Honey bees visit sprayed crops with pesticides during pollen and nectar collecting process. Pesticides are transported inside the hive, where both, agrochemicals from agriculture and compounds used in-hive against varroosis by beekeepers are accumulated in wax, pollen and honey bees. In order to study the distribution of pesticide residues in beekeeping matrices, 166 samples of beeswax, fresh stored pollen and live in-hive honey bees were collected in June and July during 2016-2017 from 45 apiaries in 39 locations in Spain that covered a wide range of landscapes, from intensive farming areas to grasslands, holm oak woodlands, mountainous and urban surroundings. The samples were extracted by a slightly modified QuEChERS procedure and screened for 63 pesticides and its degradation products by liquid chromatography mass spectrometry (LC-MS/MS). Beeswax revealed high levels of miticides used in beekeeping such as coumaphos, chlorfenvinphos, fluvalinate and acrinathrin, which were detected in more than 75% of samples. Beeswax is the most contaminated hive compartment regarding quantities of pesticides detected, whereas pollen samples revealed the highest number of different pesticide residues detected in the samples. Pollen was predominantly contaminated by miticides but also by insecticides used in agriculture such as chlorpyrifos and acetamiprid, which showed concentrations significantly higher in apiaries located in intensive farming contexts. Pesticides residues were less frequent and at lower concentrations in live honey bees. However, it should be taken into account that the study was based in the sampling of apparently healthy bees. So residues found in honey bees analyzed in the present work are not reliable nor representative of the full exposure of bees to pesticides. Assessing pesticides content in these three different apicultural matrices at the same time is a useful tool to understand the magnitude of honey bee colonies exposure to toxic compounds, which is

This study investigated the occurrence of 135 contaminants of emerging concern (CECs) – pharmaceuticals, pesticides, a set of endocrine disrupting compounds (EDCs) (parabens, bisphenols, hormones, triazoles, organophosphorus flame retardants and triclosan), UV-filters, perfluoroalkyl substances (PFASs) and halogenated flame retardants (HFRs) – in 59 fish samples, collected in 2010 in 4 Spanish Rivers (Guadalquivir, Júcar, Ebro and Llobregat). Of the 135 CECs, 76 including 8 pharmaceuticals, 25 pesticides, 10 EDCs, 5 UV-filters, 15 PFASs and 13 HFRs were detected. Pharmaceuticals were the less frequently found and at lower concentrations. Pesticides, EDCs, UV-filters, PFASs and HFRs were detected more frequently (>50% of the samples). The maximum concentrations were 15 ng/g dry weight (dw) for pharmaceuticals (diclofenac), 840 ng/g dw for pesticides (chlorpyrifos), 224 ng/g dw for EDCs (bisphenol A), 242 ng/g dw for UV-filters (EHMC), 1738 ng/g dw for PFASs (PFHxA) and 64 ng/g dw for HFRs (Dec 602). The contaminants detected in fish are commonly detected also in sediments. In light of current knowledge, the risk assessment revealed that there was no risk for humans related to the exposure to CECs via freshwater fish consumption. However, results provide detailed information on the mixtures of CECs accumulated that would be very useful to identify their effects on aquatic biota.

In arid and semi-arid areas the use of treated wastewater for crop irrigation and other agricultural practices, such as the use of pesticides, increase the number of emerging contaminants (ECs) in crops. Hazards of these practices to human being are largely unknown since there are few studies yet covering a short range of compounds and most of them under non-realistic conditions. This study aims at assessing this problem that will become global soon in an area of Saudi Arabia heavily affected by the reuse of treated wastewater and pesticide in order to ascertain its scale. The novelty of the study relays in the large number of ECs covered and the variety of crops (cabbage, barley, green beans, eggplants, chili, tomato and zucchini) analysed. Extraction procedure developed provided an appropriate extraction yield (up to 50% of the compounds were recovered within a 70–120% range), with good repeatability (relative standard deviations below 20% in most cases) and sensitivity (LOQ < 25 ng g−1) for the model compounds. Determination by liquid chromatography quadrupole time-of-flight (LC-QqTOF-MS) is able to identify >2000 contaminants. Sixty-four ECs were identified in wastewater but of the sixty-four compounds, six pharmaceuticals (atenolol, caffeine, carbamazepine and its metabolites 10,11-epoxycarbamazepine, gemfibrozil, and naproxen) and seven pesticides (acetamiprid, atrazine deethyl, azoxystrobin, bupirimate, diazinon, malathion, pirimicarb and some of their metabolites) were detected in plants. Furhermore, one metabolite of the ibuprofen (not detected in water or soil), the ibuprofen hexoside was also found in plants. Up to our knowledge, this study demonstrate for the first time the accumulation of ECs in crops irrigated with treated wastewater under real non-controlled environmental conditions.

The analysis of perfluoroalkyl substances (PFASs) and organophosphate flame retardants (PFRs) in the different environmental compartments of a characteristic coastal wetland, the Albufera Natural Park (Valencia, Spain), is required for understanding the transport, accumulation and fate of these pollutants in an area under high anthropogenic pressure. Samples included 13 wastewater treatment plant influents, 13 effluents, 12 surface water, 19 sediment samples and 10 fish individuals from the Albufera Natural Park and the surrounding area. Tris(2-chloroisopropyl) phosphate (TCIPP) and perfluorooctane sulfonate (PFOS) were at the highest concentrations in water, 330.2 ng L−1 and 47.8 ng L−1, respectively. In fish and sediment PFOS was also the most detected while perfluorooctanoic acid (PFOA) was in all types of water. Higher levels of target compounds (mainly PFASs) in wastewater effluents compared to influent suggested both, formation from precursors during treatment and poor removal efficiency. Mean levels of PFOS in water and fish were higher than the environmental quality standards (EQS) established by the European Union Directive 2013/39/EU. The influence of the metropolitan area of Valencia and its surrounding industrial belt could explain the significantly higher levels reported in the northern part (influenced by the Turia River).

Much progress has been made in the past few decades in understanding the sources, transport, fate, and biological effects of contaminants of emerging concern (CECs) in aquatic ecosystems. Despite these advancements, significant obstacles still prevent comprehensive assessments of the environmental risks associated with the presence of CECs. Many of these obstacles center around the extrapolation of effects of single chemicals observed in the laboratory or effects found in individual organisms or species in the field to impacts of multiple stressors on aquatic food webs. In the present review, we identify 5 challenges that must be addressed to promote studies of CECs from singular exposure events to multispecies aquatic food web interactions. There needs to be: 1) more detailed information on the complexity of mixtures of CECs in the aquatic environment, 2) a greater understanding of the sublethal effects of CECs on a wide range of aquatic organisms, 3) an ascertaining of the biological consequences of variable duration CEC exposures within and across generations in aquatic species, 4) a linkage of multiple stressors with CEC exposure in aquatic systems, and 5) a documenting of the trophic consequences of CEC exposure across aquatic food webs. We examine the current literature to show how these challenges can be addressed to fill knowledge gaps. Environ Toxicol Chem 2019;38:46–60

Sprayed crops with pesticides are visited by honey bees during pollen and nectar collecting process. Pesticides are transported inside the hive, where both, agrochemicals from agriculture and compounds used in-hive against varroosis by beekeepers are accumulated in wax, pollen and honey bees. Samples of honey bees (45), wax (43) and pollen (45) were obtained from 45 different apiaries located in Spain. The samples were extracted by a slightly modified QuEChERS procedure depending on the matrix, and then screened for 58 pesticides and its degradation products by liquid chromatography mass spectrometry (LC-MS/MS). The target analytes were chosen based on their potential toxicity to honey bees and their widespread use in plant protection or in the beehive agains varroa mite. Wax and pollen were the most contaminated matrices and exhibited a wide contamination by pyrethroids and organophosphates. Beeswax lipophilic nature and its lowest replacement rate in the hive are responsible of its highest pesticide content. Acaricides used in beekeeping such as coumaphos, chlorfenvinphos, amitraz and fluvalinate were the most frequently detected pesticides in wax. Some pesticides used in crops as organophosphate chlorpyrifos were detected in lower frequencies and concentrations. Pollen contamination pattern was similar to wax matrix.Acaricides applied in beekeeping were the most frequent and with the highest concentrations. Neonicotinoid acetamiprid and organophosphates chlorpyrifos and dimethoate were detected in pollen samples. Both insecticides are sprayed in crops and deposited on the pollen grains, which are transported to the hive during the foraging activity of the honey bees. Honey bee samples were less contaminated, although some acaricides and insecticides were found in this matrix.Given the concentrations detected in the matrices analyzed, honey bee colonies health could be compromised. Assessing pesticides content in these three different apicultural matrices at the s

Los contaminantes emergentes son compuestos que se encuentran a niveles de trazas en el medio ambiente, y cuya presencia no es necesariamente nueva, pero sí la preocupación por sus posibles efectos nocivos. El objetivo de este estudio ha sido realizar un screening de 19 contaminantes emergentes de carácter ácido en el Parque Natural de L'Albufera. La técnica utilizada para determinar esos analitos está basada principalmente en la extracción en fase sólida (SPE) donde los analitos son absorbidos en el soporte sólido y luego eluidos con metanol. Se utilizó la cromatografía líquida de ultra alta resolución acoplada a un espectrómetro de masas con un sistema híbrido de triple cuadrupolo (UHPLC-QqQ-MS/MS) en muestras de suelo, sedimentos y agua en zonas cercanas a La Albufera de Valencia y dentro de la misma. Entre los resultados obtenidos destaca que, en las muestras de suelo el contaminante con mayor concentración (µg/kg) es el Ácido Acetil Salicílico con una media de 95,44 µg/kg, por otro lado, en las muestras de agua es el Tiamfenicol con 1855,85 µg/L. Para las muestras de sedimentos se utilizaron dos cartuchos diferentes, uno con fase polimérica más SDS y otro con fase catiónica, obteniendo que los contaminantes con mayor concentración son Ibuprofeno con 29,81 µg/kg con fase polimérica más SDS y Ácido Acetil Salicílico con 22,76 µg/kg con fase catiónica. Para estas muestras de sedimentos también se calculó el RSD, obteniendo resultados menores a 20 en la mayoría de los compuestos a excepción de Bisfenol A (27,04), Ibuprofeno (40,68), Tiamfenicol (61,71) y Triclocarban (25,47).

El interés por la presencia de contaminantes emergentes en los distintos compartimentos ambientales ha crecido exponencialmente en las últimas décadas. Estos contaminantes se definen como sustancias químicas que pueden haber estado presentes en el medio ambiente desde hace tiempo, pero solo han sido identificadas recientemente gracias al desarrollo de técnicas analíticas más sensibles. Por tanto, la mayor parte no se encuentran reguladas y sus efectos en el medio ambiente y la salud humana a gran escala son desconocidos (Mandaric et al., 2016). El destino final para la mayoría de los contaminantes emergentes es el agua o los ecosistemas acuáticos, a los que pueden llegar por distintas vías: eliminación de forma incorrecta, liberación a través de los sistemas de aguas residuales domésticos, mediante la agricultura y la industria o tras su paso por estaciones depuradoras de aguas residuales (WWTP, por sus siglas en inglés) que no los eliminan eficazmente (Campo et al., 2014). Las investigaciones sobre la incidencia y distribución de contaminantes emergentes en los ecosistemas acuáticos son recientes. La mayoría de estos estudios se basan en los de uso doméstico o agrícola, tales como fármacos (Carmona et al., 2014), drogas (Andrés-Costa et al., 2017) o insecticidas (Ccanccapa et al., 2016), dejando de lado otros de origen industrial que, sin embargo, son más persistentes y, por tanto, susceptibles de acumularse en el medio ambiente, como son los compuestos en los que mayoritariamente se centra esta tesis: sustancias perfluoroalquiladas y retardantes de llama. Los estudios realizados sobre los ecosistemas acuáticos y la evaluación del riesgo se han centrado en aspectos concretos y limitados.

The potential for pharmaceutical to influence plants ¿including those used for food¿ is becoming increasingly relevant, particularly as waste management systems are unable to remove many compounds from the sewage. Drugs for human use make their way into soil through a number of routes, including the use of sewage sludge as fertilizer and wastewater for irrigation. The general objective of this study looked at the impacts of the ibuprofen (IBU) ¿non-steroidal anti-inflammatory drug (NSAID)¿ on the edible crops cowpea. This study required the development and validation of a liquid chromatography¿high resolution-tandem mass spectrometric (LC¿HR¿MS/MS) method for determining IBU, 1 hydroxyIBU, 2-hydroxyIBU and carboxyIBU in plants. Then, the metabolism, uptake, and translocation of IBU in cowpea (Vigna unguiculata) was studied. To our knowledge, this is the first study on the identification of IBU and its main metabolites in roots, shoot, and seeds of cowpea This plant is well-adapted to the drier regions of the tropics, where other food legumes do not perform well, then, the study has also an unquestionable interest from a food safety point of view.

Este trabajo está basado en un estudio previo que informó acerca de la presencia de dos drogas de abuso, bufotenina (BUF) y 4-metoxifenciclidina (4-MeO-PCP) en el agua del río Turia. De este modo, se ha estudiado el comportamiento y la evolución de la exposición de estas dos drogas durante 16 días en diferentes microcosmos creados para imitar cuatro posibles condiciones del agua presente en la Albufera: LAR (condiciones de luz y medio abiótico), LBR (condiciones de luz y medio biótico), DAR (condiciones de oscuridad y medio abiótico) y DBR (condiciones de oscuridad y medio biótico). Bajo estas condiciones, se abordaron dos estudios dentro de cada microcosmo: el estudio de la variación de los parámetros físico-químicos del agua, para lo cual se ha empleado el Instrumento Multiparamétrico Eutech CyberScan PCD 650; y el cálculo de las concentraciones obtenidas de cada droga durante los días de muestreo o recuperaciones, para lo que se requirió el método de extracción en fase sólida (SPE) y un equipo de cromatografía líquida de alto rendimiento con espectrómetro de masas en tándem (UHPLC-MS/MS). Las recuperaciones mostraron resultados dispares, puesto que la BUF fue prácticamente indetectable en los 4 microcosmos mientras que la 4-MeO-PCP se halló en todos ellos, pero mostrando diferentes comportamientos: la droga sufre degradación sólo en los microcosmos a los que se les aplicó luz (LAR y LBR). Por otro lado, también se evaluó el potencial toxicológico que producen ambas drogas administradas de forma individual y conjunta en una población de Daphnias mediante el kit comercial DaphtoxkitTM. Como resultado, se obtuvo que la administración de la BUF posee el potencial tóxico más alto (mayor IC50 a las 48 horas) en comparación con las otras dos exposiciones ambientales estudiadas, y que la muerte de al menos la mitad de la población ocurre entre el primer y el segundo día de exposición a las drogas.

In arid zones, the use of treated wastewater for crop irrigation and the recurrent applications of pesticides to fight against pest increase the number of emerging contaminants (ECs) in crops (Pico et al. 2019). The consequences of these practices are still unknown due to the scarcity of studies, most of them performed under laboratory conditions at high concentrations (Pico et al. 2019). This study aims at assessing the problem of environmental contamination due to the use of non-conventional water resources that will get worldwide dimension soon in two areas of Saudi Arabia heavily affected by the reuse of treated wastewater and pesticide in order to ascertain its scale. The novelty of the study relays in the large number of ECs covered and the variety of crops (cabbage, barley, green beans, eggplants, chili, tomato and zucchini) analysed in the Al Hayer and Al-Asfar.

The wastewater generated by the human activity contains several anthropogenic contaminants, including emerging pollutants. Sewage sludge is generated during the depuration process in the wastewater treatment plants (WWTPs). The study of emerging pollutants present in this sludge are far limited comparing with the water, mainly because of the challenge that involve their high content in organic matter making difficult their handling, storage and analysis. In Spain, the 80% of this sludge is used in the agriculture sector as fertilizer, and the presence of pollutants could affect to the surrounding ecosystems. The sludge samples were from different treatment plants next to the Natural Park of the Albufera in Valencia, an area surrounded by 14000 hectares devoted to rice crops. Samples were extracted by liquid phase extraction (LPE) with mixture of EDTA-McIlvaine buffer (pH 4.1) and methanol, assisted by ultrasound. Then, supernatant was cleaned up by the solid phase extraction (SPE) with StrataTMX cartridges and analytes were eluted with methanol at gravity flow. Once extracted, the analytes were identified by liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-QqTOF-MS). As a result 50 compounds were identified, being the pharmaceuticals the main group of pollutants with 31 compounds. Human metabolites were the most relevant, present in all samples, including nucleotides (adenosine triphosphate), amino acids (phenylalanine) or peptides (leucine-phenylalanine). On the other hand, several compounds were tentative identified and are pending of confirmation. The results of this study demonstrate the interest of high resolution mass spectrometry to draw the profile of contaminants in solid complex matrices. Furthermore, the data obtained provides information about the potential risk of use the sewage sludge for agriculture. Continue researching is needed to assess the real environmental risk related to this sludge and their possible effects in the surrou

Los residuos de fármacos, drogas de abuso y productos cosméticos se detectan en la naturaleza debido a su elevado consumo, vertidos no controlados y falta de técnicas para la eliminación total de estas sustancias. Estos compuestos forman parte de un grupo de contaminantes llamados contaminantes emergentes, dado que no se monitorizan normalmente o su presencia en el medioambiente no está regulada y pueden llegar a causar un daño ecológico o incluso para la salud humana. Durante los pasados años, el número de estudios para tratar de desarrollar métodos analíticos robustos y sensibles, así como tratar de monitorizar estos compuestos en los ecosistemas acuáticos, ha ido en aumento. Los métodos analíticos existentes se han desarrollado para un número reducido de compuestos principalmente en aguas, siendo otros compartimientos medioambientales como suelos y biota más difíciles de analizar. La presente Tesis Doctoral se focaliza en el desarrollo de métodos de análisis que abarque fármacos, drogas de abuso, productos cosméticos y otros contaminantes emergentes de diferente naturaleza, en aguas superficiales, residuales y de consumo, suelos, sedimentos y peces que pueda ser usado con diferentes métodos cromatográficos. Estos métodos se aplican al estudio del ecosistema del rio Turia, fuertemente afectado por el cambio global que se está produciendo, con objeto de establecer la presencia, transporte y degradación de estos compuestos, y arrojar luz sobre su dinámica en los ecosistemas frágiles. Es por ello que se puso a punto un método de identificación y determinación, selectivo, sensible y robusto para fármacos, drogas de abuso, productos cosméticos y otros contaminantes emergentes basado en la cromatografía líquida de alta resolución acoplada a espectrometría de masas, además se desarrolló un método de extracción para matrices sólidas rápido, eficiente y que mejora las recuperaciones de los métodos tradicionales y no requiere la utilización de equipamiento costosos y sofist

Many of the compounds generated by the anthropic activities like agriculture, industry or health care access to the environment, most of these contaminants are of recent concern, thus classified as emerging contaminants (ECs). ECs include chemical compounds of different groups (pharmaceuticals, pesticides, drugs of abuse and perfluorinated compounds, among others). The main sources of their release to the environment are wastewater treatment plants (WWTPs) that remove only part of the ECs. Compounds (or metabolites) can enter through the effluents to aquatic systems or through the dry sludges to soil. Produced sewage sludge is called biosolids if meet regulatory requirements for land application and surface disposal. This product has interest in soils and farming, due to their percentages of nutrients (until 50%) that could restore overworking soils or promote growth of plants. The determination of ECs in sludges is complicated due to the high organic content of sludges as well as to the complex associations of the ECs with the sludge matrix. Recently, the non-target methods, have been developed showing good prospects to ascertain the contamination profile of these matrices (Schymansky et al, 2015). This non-target approach enables to obtain high quality data of every compound in the sample, allowing a better evaluation of the possible environmental risk related to the use of the sewage sludge. Studies that apply this type of analysis in samples of wastewater, or in the effluents of WWTP, have been increasingly reported (Bader et al, 2016). However, studies in solid matrices like sediments, soils or sludge are fewer (Álvarez-Ruiz et al, 2015). There is a complexity by the presence of humic acids and biomolecules that interfere with the extraction or in the separation and identification of compounds. Because of that, HMRS combined with time-of-flight and orbitrap (TOF) is challenging for this type of analysis due to its high resolution power, mass accuracy and sensit

La importancia de este estudio reside en que aporta herramientas para el estudio de la bioacumulación de microplásticos y otros contaminantes emergentes en la biota acuática. Se pondrán a punto dos métodos de extracción de microplásticos, uno para sedimentos del rio Turia y otro para mejillones expuestos. Se utilizan un método basado en la diferencia de densidad y flotabilidad de los plásticos y otro basado en una digestión de la materia orgánica mediante KOH y posterior observación en lupa en ambos casos. El trabajo también aborda el estudio de un método sencillo capaz de extraer contaminantes emergentes de mejillones expuestos mediante QuEChERS. Los contaminantes emergentes se cuantifican mediante HPLC acoplado a un espectrómetro de masa con detector de triple cuádruplo. Los resultados obtenidos muestran una buena extracción de los microplásticos en el caso de la digestión con KOH gracias a la eliminación del pie del mejillón. En sedimentos los resultados deberían mejorarse ya que se arrastra mucha muestra que impide su visualización. En cuanto a los contaminantes emergentes la extracción de las muestras expuestas da buenos resultados, aunque se debe intentar minimizar el efecto matriz para obtener una mejor cuantificación.

The human activity generate anthropogenic compounds that end up in the wastewater treatment plants (WWTPs). In these plants, part of them could be retained in the sewage sludge. The study of the presence of contaminants in this sludge involve a great challenge due to its high organic matter content. This is the reason why this sample has not been as widely study as the influent and effluent water of the WWTP. However, in Spain, similarly to other European countries, the 80% of the sewage sludge is used as a fertilizer for the crops, being of great interest to know the different compounds present in them and asses the environmental risk of their utilization. The sludge samples are from 8 WWTPs next to the natural park of the Albufera in Valencia. Samples were extracted using a Methanol-McIlvaine Buffer (4.1) mixture and assisted by ultrasound, the supernatant was cleaned up by the solid phase extraction (SPE) using StrataTMX cartridges and then the analytes were eluted with methanol at gravity flow. Samples were analyzed using a suspected screening workflow with a liquid chromatography triple quadrupole time-of-flight (LC-QqTOF), providing high quality information about the different compounds present in the sludge. As overall results, 50 different compounds were identified with high degree of confidence. Pharmaceuticals were the most relevant group with 31 compounds identified. Furthermore, human metabolites were present all the samples, including, nucleotides (adenosine triphosphate), amino acids (phenylalanine) or peptides (leucine-phenylalanine). Other compounds were tentative identify by the accurate mass, but are pending of confirmation by the product ion mass spectrum. Further study is still needed to obtained more data about them. In conclusion, this method is suitable to identify emerging contaminants in sewage sludge, and the non-target techniques provide information of their potential environmental risk in the areas where they are utilized

Pollution by new and traditional drugs of abuse, at very low concentrations, appears to be broad in environmental compartments near populated areas. Data on their occurrence and toxicity for the aquatic biota will help to a sustainable management of the problem. In this study, 42 drugs of abuse and metabolites were analyzed in surface waters of the Turia River Basin (East of Spain), collected in 2012 and 2013. The most frequent compound was benzoylecgonine in 9 sampling points (average concentration 25.4 ng/L) in 2012 and 8 (average concentration 14.02 ng/L) in 2013. Codeine reached the maximum concentration (101 ng/L) in 2013. Analysis by Geographical Information Systems (GIS) shows the spatial incidence of drugs of abuse along the River basin appearing the highest concentrations and frequency of drugs of abuse in the points with the highest population density. A toxicity assessment through the risk quotient (RQ) predicted that no short-term environmental risk might be expected. However, most of toxicity data are not experimental. Further research included was performed with the two new drugs of abuse detected (bufotenine and 4-methoxyphencyclidine), which environmental behavior was still unknown. Degradation in microcosms that imitate four possible conditions of the water present in River basin was studed: LAR (light and abiotic conditions), LBR (light and biotic conditions), DAR (dark and abiotic conditions) and DBR (dark and biotic conditions). Bufotenine was practically undetectable in the 4 microcosms while 4-methoxyphencyclidine showed degradation only in light microcosms (LAR and LBR). Several degradation products of 4-methoxyphencyclidine were identified using liquid chromatography-high resolution mass spectrometry. These degradation products were further detected in River water. On the other hand, the toxic damage produced by both drugs, administered individually and jointly in a Daphnia magna population, was also assessed using DaphtoxkitTM. As a result

The screening of emerging persistent organic pollutants (ePOPs) in coastal wetlands as the Albufera Natural Park (Valencia, Spain) is crucial to understand their transport, accumulation and fate in susceptible area. This area is severely threatened by water pollution, disturbances of the water regime, industrial pressures and high population density. The concern about the occurrence and distribution of ePOPs is rising since they are one of the factors adversely affecting fragile aquatic ecosystems, including their biota. The results of this study show the presence of perfluoroalkyl substances (PFASs) and organophosphate flame retardants (PFRs) in different environmental matrices of the wetland area. Sixty-seven samples including surface water, sediment, fish and influents and effluents from wastewater treatment plants (WWTPs) nearby were collected. WWTPs were identified as one of the main point sources of these ePOPs to the environment. High levels of target compounds (mainly PFASs) in wastewater effluents suggest the presence of precursors in water and their ineffective elimination through the treatments of WWTPs. Perfluorooctane sulfonate (PFOS) and tris(2-chloroisopropyl) phosphate (TCIPP) were the most abundant compounds in all water samples. PFOS was also the most detected compound in sediment and fish samples. In biota, the environmental quality standard (EQS) established by Directive 2013/39 of the European Union for PFOS concentration, was exceeded by 50% of fish samples in the Albufera lake and, specifically, in 71% of eels. In sediment, the maximum allowable concentration values of EQS were not exceeded. However, considering the annual average level of PFOS established by this Directive (0.65 ng l-1) and the mean values obtained in the Albufera (31.6 ng l-1), it would be convenient to perform periodic samplings to determine the annual average of PFOS.

New psychoactive substances (NPS) include those that were not listed in the 1961 United Nations Single Convention on Narcotic Drugs or in the 1971, United Nations Convention on Psychotropic Substances and that are not controlled by legislation yet. The phenomenon of NPS is dynamic because the uncontrolled recreational drugs proliferating in number and variety. A total of 100 NPS were officially notified for the first time in the EU in 2015 through the EWS (Early Warning System), enlarging the total number of NPS monitored by EMCDDA to 560 – more than twice the number of drugs controlled under the international drug control conventions (EMCDDA, 2016). NPS are an unknown threat to the environmental since nothing is now about their (bio)degradation or the nature and hazard of these degradation products. This study was aimed at determining the potential for aerobic biodegradation as well as the main transformation products of bufotenine and 4-methoxyphencyclidine in a coastal wetland system. The specific objectives of this study were (i) to apply developed methodologies in water analysis (surface water), (ii) to estimate the bio- and photodegradation and transformation of the stereoisomers of selected NPS in surface water, and (iii) to evaluate the toxicity of these NPS at different trophic levels by in-silico and in-vivo studies. The two selected NPS were previously detected in Turia River basin (Andrés-Costa et al., 2017). The surface water sample was collected from l’Albufera Natural Park that is a coastal lagoon feed by this river. The applied analytical methodology was developed in previous studies (Andrés-Costa et al., 2017). L’Albufera water microcosm experiments were conducted in the light (L) and dark (D) conditions (to study photochemical processes) and biotic (B) or abiotic (A) conditions with or without sodium azide, respectively (as an inhibitor to microbiological processes). Light conditions were simulated with an Osram 400 W HQI BT daylight lamp during 8

The aquatic ecosystems are dynamic environments that are frequently affected directly or indirectly by anthropogenic discharge of contaminants. A large number of contaminants can be present in their different compartments and the application of a non-target screening approach provides the opportunity to expand the knowledge on the occurrence of any type of low-molecular-weight organic pollutants and a deep insight into the state of pollution. In this study, detailed liquid chromatography-quadrupole time-of-flight mass spectrometry (LCQqTOF-MS) non-target screening analyses have been applied to mussels (Mytilus Galloprovincialis) and riverine sediment of the Turia River Basin, in Eastern Spain. This river passes across the metropolitan area of Valencia being exposed to different contaminants. The extraction of the sediments was carried out using a mixture of McIlvaine buffer (pH 5.4) and methanol by ultrasound-assisted extraction (UAE). Then, extracts were cleaned up by the solid phase extraction (SPE) with StrataTMX cartridges and analytes were eluted using methanol-dichloromethane at gravity flow. In the case of the mussel samples, were extracted using the QuEChERS method, with a mixture of Acetonitrile, water, MgSO4, NaCl, 2Na2C6H6O7 and C6H9Na3O9, then shaken and centrifuged to obtain the supernatant. Sensitive and selective liquid chromatography–mass spectrometry (LC–MS) analysis is a powerful and essential tool for contaminant identification in environmental studies. An MS (or tandem, MS/MS) mass spectrum is acquired from the fragmentation of a precursor ion by multiple methods including information-dependent acquisition (IDA) and sequential window acquisition of all theoretical fragment-ion spectra (SWATH). To determine different efficiency between this two techniques their capabilities to produce comprehensive MS2 data by assessing both contaminant MS2 acquisition hit rate and the quality of MS2 spectra were compared. The SWATH method is able to identify a hi

The aim of this study establishes the influence and the effects of the human pressure in a typical Mediterranean River Basin to determine accurately the point sources of contamination through an environmental forensics methodology. A total of 42 drugs of abuse and metabolites were analysed in surface water samples collected from 22 sampling sites in 2012 and 31 in 2013 distributed along the river. Analysis of the target illicit drugs was performed using solid phase extraction and liquid chromatography coupled mass spectrometry (SPE-LC-MS/MS). To determine spatial incidence of drugs of abuse, analytical results of target compounds were georeferenced and integrated into a geographical information systems (GIS). Ecotoxicological risk of drugs of abuse detected in the Turia River was evaluated by calculating risk quotient (RQ). In 2012, 3,4-methylenedioxymethamphetamine (MDMA) and 4-methoxyphencyclidine (4-MeO-PCP) were detected in one sampling point at a concentration of 22.8 and 37.6 ng/L, respectively. In 2013, 4-MeO-PCP was detected in a different sampling point of 2012 at a concentration of 7.55 ng/L and ecgonine methyl ester (ECME) was detected at a concentration of 15.03 ng/L. Bufotenine (BUF), methadone (MET) and p-methoxyamphetamine (PMA) were found out in 3 or 4 sampling points at concentrations < 70 ng/L in 2012. Ephedrine (EPH) and codeine (COD) were detected in 3 sampling points at average concentrations of 11.6 ng/L for EPH and 91.3 ng/L for COD in 2013. The compound detected more frequently along the river was benzoylecgonine (BECG), a cocaine metabolite, with an average concentration of 25.4 (2.91–76.8) ng/L in 2012. In 2013, MDMA was detected in 5 sampling points (mean of 4.67 ng/L, ranged from 2.34 to 7.21 ng/L) and BECG and MET were detected in a total of 8 and 7 sampling points, respectively, each one at a mean concentration of 14.02 (1.83–12.7) ng/L for BECG and 11.4 (2.29–40.1) ng/L for MET. GIS provided the spatial incidence of drugs of abuse alon

The utilization of non-target screening provides the opportunity to expand the knowledge on lowmolecular-weight organic pollutants present in environmental matrices through suspected or nontarget screening. However, one of the pending issues that still remains is the number of compounds properly identified (with some fragment ions). To solve this problem, new instrumental acquisition methods are being developed. In this study, liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QqTOF-MS) using suspected screening have been applied to mussels (Mytilus galloprovincialis) and riverine sediments of the Turia River Basin, in Eastern Spain. The extraction of the sediment was carried out by ultrasound assisted extraction (UAE) with McIlvaine buffer (pH 5.4) and methanol. Then, extracts were cleaned up by solid phase extraction (SPE) with StrataTMX cartridges and retained analytes were eluted using methanoldichloromethane. In the case of mussels QuEChERS was selected as extraction procedure using a mixture of Acetonitrile, water, MgSO4, NaCl, 2Na2C6H6O7 and C6H9Na3O9. After extraction, the supernatant was cleaned up using dispersive solid-phase extraction. A mixture of 36 pharmaceuticals was selected to spike the samples in order to properly evaluated the different working modes- Sensitive and selective liquid chromatography¿mass spectrometry (LC¿MS) analysis is a powerful and essential tool for contaminant identification in environmental studies. An MS2 (or tandem, MS/MS) mass spectrum is acquired from the fragmentation of a precursor ion by information-dependent acquisition (IDA) and MS/MSALL mass spectrum acquired with SWATH (sequential window acquisition of all theoretical fragment-ion spectra). We compared these two techniques in their capabilities to produce comprehensive MS2 data by assessing both contaminant MS2 acquisition hit rate and the quality of MS2 spectra, also the difference between use fix window SWATH (FSWATH) and variable window SWATH (

Emerging contaminants (ECs) have been detected in the soil environment where there is the potential for uptake into crops. Many of the previous plant uptake studies have been done at unrealistic exposure concentrations [1]. This study was aimed to assess the presence of emerging contaminant in soils and crops irrigated with treated wastewater in Saudi Arabia to evaluate the potential of plant uptake of these compounds. Although LC-MS/MS continues to be the best tool for detecting emerging contaminants in water and other environmental matrices, the combined use of hybrid high-resolution mass spectrometry (HRMS) and ultrahigh pressure liquid chromatography (UHPLC) is starting to become a practical tool to study these contaminants [2,3]. Then, to improve performances, a triple quadrupole time-of-flight mass spectrometer (QqTOF), the Triple-TOF (ABSciex, Darmstadt, Germany) with resolving power up to 35, 000 FWHM at m/z 200 was used. Furthermore, the Triple-TOF system combines the TOF with a high-performance quadruple which allows the possibility of precursor ion fragmentation providing high sensitivity and selectivity – in a manner not unlike what can be performed using tandem mass spectrometry. The study was done as ‘suspect screening’ which is based on the identification of emerging contaminants without a preceding selection of the compounds of interest. This technique was used in order to discover pollutants of emerging environmental concern in the water, soil and several vegetables which we might have overlooked until now. The study included suspected screening analysis of water sample for irrigation taken in four different sites before and after the Riyadh wastewater treatment plant. In addition, soil and crops growing in the sourroundings were analysed. Numerous emerging contaminants were found in water, soil and crop samples. These were for instance phenols, antioxidants, and plasticizers of the phthalate-type. Also a fibrates compound (gemfibrozil, CAS: 25812

In the last years, the interest in detecting environmental contaminants in different matrices (mostly sediment, soil and water) is increasing because their more relevant impact on the global ecosystem. In this study, we focused on determination of Pharmaceutical Compounds and Personal Care Products. The study was conducted on about 30 compounds, including acid, basic and neutral. The selected compounds constitute an important block of organic contaminants frequently found for many reasons, such as industrial waste, expired or unused medicinal product not disposed in the right way, and excretion of drugs and their metabolites derived from therapeutic treatments. This field study is intended to propose an analytical methodology to assess and monitor the occurrence of emerging contaminants (EC) of the Albufera Natural Park. Has an area of 21120 hectares and it is located 10 km to the South of Valencia City. It consists of a highly eutrophic coastal lagoon surrounded mainly by rice fields that occupy the primitive marshland. The Turia River, to the north, the Jucar River, to the South, and a network of irrigation channels bring fresh water to the Albufera system. Different analytical methods to determine ca. 30 EC were developed and optimized to obtain the best efficiency and sensitivity. Samples analysed included 35 water samples and 20 sediment samples for L¿Albufera Lake and its surrounding area. Fig. 1 shows the location of the sampling points. The extraction is based on solid-phase extraction (SPE) using two different stationary phases of cartridges Reversed Phase and Polymeric Weak Cation Phase, provided suitable recoveries to extract this compounds from water or to clean up the sediment extracts. The determination was carried out by liquid chromatography-tandem mass spectrometry (LC-MS/MS) with a triple-quad using two precursor ¿ product ion transitions for each compound in the multiple selected reaction monitoring mode (MRM). The results evidenced the presence o

In the last years, the interest in detecting environmental contaminants in different matrices (mostly sediment, soil and water) is increasing because their more relevant impact on the global ecosystem [1]. In this study, we focused on determination of Pharmaceutical Compounds and Personal Care Products. The study was conducted on about 30 compounds, including acid, basic and neutral. The selected compounds constitute an important block of organic contaminants frequently found for many reasons, such as industrial waste, expired or unused medicinal product not disposed in the right way, and excretion of drugs and their metabolites derived from therapeutic treatments [2]. Some of the selected compounds as metformine required a careful optimization of the extraction conditions. The analytical method was based on solvent extraction (if a solid matrix is used) followed by solid-phase extraction (SPE). The chromatographic separation was performed using an Agilent 1260 ultra-high performance liquid chromatography (UHPLC) with a Phenomenex Kinetex C18 column of 1.7 µm of particle size at constant flow rate of 0.2 mL min-1. The mobile phase consisted of deionized water and methanol, both with 0.1% formic acid (for positive mode) and with 0.1% ammonium fluoride (for negative mode), working in gradient mode. The UHPLC was coupled to an Agilent 6410 triple quadrupole mass spectrometer with an electrospray ionization source working both in positive (ES+) and negative mode (ES-). Different steps of the extraction procedure were considered to optimize the recovery of the compounds. Regarding the solid-phase extraction (SPE), 2 different stationary phases of cartridges were tested: Phenomenex Strata-X 33 µm Polymeric Reversed Phase 200 mg/6 mL and Phenomenex Strata-X-CW 33 µm Polymeric Weak Cation 200 mg/6 mL. Moreover the activation of cartridges was considered before the passage of sample with and without the use of a 2mM Sodium Dodecyl Sulfate (SDS) solution. In each test the ext

There is a rising interest for both the conservation and biotechnological application of Sea anemones belonging to Anthozoa Class, (Cnidaria Phylum). Global warming has been recognised as one of the most important hazards for some species but the risk posed by pharmaceuticals and other emergent compounds present in the coastal waters they inhabited have been less studied. Anemonia sulcata and Actinia equina are widely distributed species in the Mediterranean Sea. The objective of this work has been to determine the physiological and biochemical effects of carbamazepine (CBZ) exposure as well as to characterize the degradation routes followed by this compound in water and tissues (biotransformation) of the two anemones species. Anemones provided by Oceanografic of Valencia Aquarium were acclimatized to laboratory conditions for two weeks and exposed to 1 ¿g/L and 100 ¿g/L of CBZ in artificial sea water in a semi-static system. Small portion of the tentacles were taken after two and seven days. Ion transport (measured as NKATPase activity), energetic metabolism (measured as glucose and lactate levels) and nitrogen excretion (measured as ammonia concentration in tissues) were determined. Treated samples of A. sulcata and A. equina were analysed by ultra-high-performance liquid chromatographyhigh-resolution mass spectrometry on a quadrupole-time-of-flight (QqTOF) (TripleTOF®, ABsciex). The structures of metabolites have been proposed using HRMS and HRMS/MS data. In particular, the combination of mass accuracy and the fragmentation patterns of metabolites and parent compound allowed proposing plausible structures for each metabolite. CBZ metabolites originated from aromatic and benzylic hydroxylation and epoxidation. The analysis of the water samples saved from each aquarium pointed out that a small percentage of CBZ can be degraded by hydrolysis and/or oxidation to the hydroxylated metabolites but not to the epoxidized ones. The current work constitutes the first study

According to the Stockholm Convention on persistent organic pollutants, these compounds are resistant to chemical, biological, and photolytic environmental degradation, and could pose significant impact on human health and the environment. The screening of emerging persistent organic pollutants (ePOPs) in soils and sediments is crucial to understand their transport, accumulation and fate. The Jucar and Turia basins (including L¿Albufera Natural Park, Valencia, Spain) are areas severely threatened by land use changes, soil and water pollution, high population density, etc. The concern about the occurrence and distribution of ePOPs is rising since they are one of the factors adversely affecting fragile agricultural systems, dominant in the area. In this study, 98 samples including agricultural soil, sediment, influent and effluent from waste water treatment plants (WWTPs) were collected (2010-2016). Considered ePOPs, 21 perfluoroalkyl substances (PFASs) and 9 organophosphate flame retardants (PFRs), were extracted by solid phase extraction and determined by liquid chromatography triple quadrupole mass spectrometer. PFASs and PFRs were detected in all the matrices. It is remarkable the high occurrence and concentration of short-chain PFASs (C<8), intended to replace the long-chain ones in several industrial applications. Perfluorooctane sulfonate was also detected together with tris(2-chloroisopropyl) phosphate. WWTPs were identified as an important but not unique source. High levels of target compounds (mainly PFASs) in wastewater effluents suggest the presence of precursors and their poor removal through the treatments. Despite concentrations found in this study can be considered low, monitoring of ePOPs in zones under the threat of global change, as the Mediterranean, is required, particularly in the development of Special Action Plans in situations of alert and temporary drought in which contaminant concentrations could be increased.

The aim of this study establishes the influence and the effects of the human pressure in a typical Mediterranean River Basin as Turia River to establish accurately the point sources of contamination and its types, through an environmental forensics methodology. Forty-two phychoactive substances were analysed in surface water samples collected from 35 sampling sites distributed along the river for 2 consequtive years. Analysis of the target drugs was performed following a previously method based on solid phase extraction and liquid chromatography coupled mass spectrometry (SPE-LC-MS/MS). To determine spatial incidence of phychoactive substances, analytical results of target compounds were georeferenced and integrated into a geographical information systems (GIS) together with tabular data, GIS layers and fieldwork. Ecotoxicological risk of drugs of abuse detected in the Turia River was evaluated in this study by calculating risk quotient (RQ). According to their occurrence, phychoactive substances can be clasified in three groups: (i) Drugs detected only in one sampling point. In 2012, 3,4-methylenedioxymethamphetamine (MDMA) and 4-methoxyphencyclidine (4-MeO-PCP) were detected at a concentration of 22.8 and 37.6 ng/L, respectively. In 2013, 4-MeO-PCP was detected in a different sampling point of 2012 at a concentration of 7.55 ng/L and ecgonine methyl ester (ECME) was detected at a concentration of 15.03 ng/L. (ii) Drugs detected only in a few sampling points. Bufotenine (BUF), methadone (MET) and para-methoxyamphetamine (PMA) were found out in 3 or 4 sampling points at concentrations.

Pesticides affect several non-target beneficial insect, such as honeybees, being not only able to kill them but also to contaminate beehive products. This study aimed at developing multiresidue methods for monitoring 62 pesticides and degradation products in honeybees, pollen and beeswax by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Pollen and honeybee samples (5 g) were extracted following a modified QuEChERS protocol using acetonitrile (10 mL) followed by a dispersive solid phase extraction clean up with PSA and C18 (50 mg) to remove sugars, fatty acids and nonpolar interferences [1, 2]. Beeswax samples were also extracted with acetonitrile by melting wax in a water bath at 80 ºC and then, the extract was cool (−18 °C, for at least 2 h) for precipitaaon of the wax. Finally, 25 mg PSA and 25 mg C18 were added for clean-up and pH was adjusted to 5 [3]. The resulted extracts were then analysed by LC-ESIMS/MS in positive mode. Separation was carried out on a Luna C18 column (150 × 2.0 mm, 3 µm) using a gradient elution profile with mobile phase consisting of water-methanol both, 10 mM ammonium formate. The two most intense precursor ion → product ion transiaons were monitored to obtain unambiguous confirmation of the compound identity. The sensitivity of the methods was estimated by establishing the limits of detection (LODs) and quantification (LOQs). In pollen matrix LODs were lower than 2 ng·g-1 and LOQs were below 5 ng·g1 for all pesticides. Honeybees matrix showed LODs from 0.3 to 3 ng·g-1 whereas LOQs ranged from 1 to 10 ng·g-1. In beeswax, LODs were from 0.3 to 4.2 ng·g-1, whereas LOQs ranged from 1 to 12.5 ng·g-1. Precision, expressed as relative standard deviation (RSD), was < 20% in most pesticides analyzed. Matrix effects were mostly suppressive in the three matrices and ranged from -60 to 50% over the response of the standards prepared in solvent. The average recoveries values were 89, 70 and 83% for pollen, honeybees and beeswax, respectiv