Suspected-screening assessment of the occurrence of organic compounds in sewage sludge.

The profiling of emerging organic pollutants present in sludge and generated during wastewater treatment is much more limited than in water. This is mainly due to the difficulty of sludge analysis because of its high content of organic matter and interfering compounds. In this study, a generic extraction method using a mixture of buffered water (pH 4.1) and solid phase extraction (SPE) clean-up was applied to samples of sludge obtained in different treatment plants. This extraction was followed by determination of the contaminants by ultra-high performance liquid chromatography coupled to high resolution mass spectrometry (UHPLC-HRMS), using suspected screening to detect the most relevant organic compounds that access the environment through sludge application. This screening (including >3000 substances, such as, pharmaceuticals, pesticides, metabolites and industrial chemicals) tentatively identified 122 compound and assigned most probable structure to 39. The set of compounds assigned to a probable structure was increased in 14 compounds by searching in a free database of metabolites. Fifteen compounds were unequivocally confirmed against the analytical standard. Pharmaceuticals and personal care products (PPCPs), with 31 substances identified and 8 confirmed were the main group of compounds. Compounds frequently detected in all sludge samples include nucleotides such as adenosine triphosphate, amino acids such as phenylalanine, or peptides such as leu-phe. Altogether, the results of this work highlight the interest of HRMS to draw the profile of organic compounds in complex matrices.

Postflood Monitoring in a Subtropical Estuary and Benchmarking with PFASs Allows Measurement of Chemical Persistence on the Scale of Months.

Measurements of chemical persistence in natural environments can provide insight into behavior not easily replicated in laboratory studies. However, it is difficult to find environmental situations suitable for such measurements, particularly for substances with half-lives exceeding several weeks. The objective of this study was to demonstrate that a strategic postflood monitoring campaign can be used to quantify transformation half-lives on the scale of months in a real aquatic system. Water samples were collected in the upper Brisbane River estuary on 36 occasions over 37 weeks and analyzed for 127 pharmaceuticals and personal care products (PPCPs), pesticides, and perfluoroalkyl substances (PFASs). High quality time trend data were obtained for 41 substances. For many of these, data on the input of a wastewater treatment plant to the upper estuary were also obtained. A mass balance model of the estuary stretch was formulated and parametrized using PFASs as persistent benchmarking chemicals. Transformation half-life estimates were obtained for 10 PPCPs and 7 pesticides ranging from 18 to 260 days. Furthermore, insight was obtained into dominant transformation processes as well as the magnitude of chemical inputs to the estuary and their sources. The approach developed shows that under certain conditions, estuaries can be used to quantify the persistence of organic contaminants with half-lives of the order of several months.

Development of multi-residue extraction procedures using QuEChERS and liquid chromatography tandem mass spectrometry for the determination of different types of organic pollutants in mussel.

This study aimed to develop multi-residue methods for the extraction of organic pollutants in mussels (Mytilus galloprovincialis), including 11 pharmaceuticals, 5 pesticides, 5 perfluoroalkyl substances (PFASs) and 2 illicit drugs. The combination of 4 different QuEChERS methods and 12 clean-ups (a total of 44 combinations) was tested. QuEChERS included acidified (AQ), non-acidified (SQ) and their miniaturized versions. The clean-ups included 6 different conventional dispersive solid phase extraction (dSPE) plus 2 enhanced matrix removal (EMR-Lipid) and 4 SPE procedures (including sorbents focused on phospholipid removal and polymer-based). After sample analysis via HPLC-MS/MS, the three methods that provided the best results were validated in terms of linearity, accuracy, precision, sensitivity and matrix effect. The methods selected were the combination of (i) SQ and EMR-Lipid, (ii) AQ and Z-sep+ bulk-based dSPE and (iii) AQ and graphitized carbon black (GCB)-based dSPE. Recoveries at two concentration levels (50 and 500 ng/g) ranged 54-124%, 59-124% and 60-127%, respectively, and limits of quantification (LOQs) were < 30 ng/g for most analytes using any of the methods. The three methods were tested in non-spiked mussel samples purchased in local markets, but organic pollutants were not detected in any sample. However, the methods probed to successfully extract a wide range of organic pollutants families in mussel samples from the market and from bioaccumulation trials.

Multi-residue extraction to determine organic pollutants in mussel hemolymph.

This study assesses the extraction of eleven pharmaceuticals, five pesticides, five perfluoroalkyl substances, and two illicit drugs in hemolymph from (Mytilus Galloprovincialis). Four extraction procedures using Phree™ Phospholipid Removal cartridges were tested using different volumes of methanol (400 and 600 µL) and acetonitrile (300 and 450 µL). The pollutants were determined by high-performance liquid chromatography-tandem mass spectrometry. The use of methanol gave several problems during the extraction procedure, such as longer times and sample loss. Three methods (acetonitrile 300 and 450 µL; and methanol 600 µL) were validated. Recoveries at three concentration levels (5, 50, and 100 ng/mL) ranged 35.1-129.0 and 29.3-133.0% for acetonitrile 300 and 450 µL, respectively, while recoveries for methanol 600 µL ranged 52.2-166.0%. Limits of detection were < 10 ng/mL for most analytes using any of the methods. Methanol 600 µL was the only method capable to extract the illicit drug 4-methoxyphencyclidine and provided a better peak shape and higher signal-noise ratio. When applied to non-spiked samples from local markets salicylic acid and diclofenac were detected at 33.50-97.79 and 28.30-30.31 ng/mL respectively. To our knowledge, there are no methods to determine organic contaminants in hemolymph and this is the first application of Phree™ cartridges for mussel hemolymph extraction.

Systematic assessment of extraction of pharmaceuticals and personal care products in water and sediment followed by liquid chromatography-tandem mass spectrometry.

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.

Analysis of ibuprofen and its main metabolites in roots, shoots, and seeds of cowpea (Vigna unguiculata L. Walp) using liquid chromatography-quadrupole time-of-flight mass spectrometry: uptake, metabolism, and translocation.

A liquid chromatography quadruple time-of-flight mass spectrometry (LC-QqTOF-MS/MS) method was developed for simultaneous quantitative analysis of ibuprofen (IBU), 1- and 2-hydroxyibuprofen (1-OH IBU and 2-OH IBU), and carboxyibuprofen (CBX IBU) while preserving the ability of the instrument to get precursor and product ion mass spectra of non-target compounds. The trigger was the precursor ions reaching 100 cps intensity. Sample preparation was carried out by ultrasound solid-liquid extraction with methanol as extraction solvent at pH < 2 followed by solid-phase extraction (SPE) clean-up using STRATA-X cartridges and methanol as an eluent. Linearity was obtained in the range 50-10,000 ng mL-1 for IBU, each OH IBU and CBX IBU (r ≥ 0.99). The proposed method was satisfactorily validated showing absolute recoveries of > 70% for all target analytes at low and high concentration levels. The lowest limit of quantification was < 50 ng g-1 in plant. This method was applied to investigate IBP behavior in cowpea (Vigna unguiculata (L.) Walp) treated at high IBU concentrations and its presence in vegetables irrigated with treated water. Up to 46 metabolites, mostly hydroxylated metabolites and conjugates with hexosides and amino acids, were identified. The most abundant metabolites were also identified in an eggplant sample. Graphical Abstract ᅟ Ibuprofen metabolite identification.

Determination of organic contaminants in L'Albufera Natural Park using microporous polyethylene tube passive samplers: An environmental risk assessment.

L'Albufera Natural Park (Valencia, Spain) is a protected wetland of international significance that provides critical habitats to endemic and threatened bird and plant species. This study aims to use multiple cross-validation techniques to generate an accurate estimation of the environmental risk of organic contaminants (OCs) in an internationally important coastal wetland, to identify compounds of concern and their potential sources and risk factors. Microporous polyethylene tube (MPT) passive samplers were deployed at 12 locations across L'Albufera Natural Park with concurrent grab samples collected. A subset of MPT samplers were also analysed by an additional laboratory in Australia to widen the range of contaminants and assess interlaboratory reproducibility of results. Forty-three pesticides, 20 pharmaceuticals and personal care products (PPCPs), 20 per-and polyfluoroalkyl substances (PFAS) and 4 organophosphorus flame retardants (OPFRs) were detected in the MPT samplers. The fungicides tebuconazole and difenoconazole were detected at the highest concentrations in passive samplers (maximum concentrations, 153 ng sampler-1 and 106 ng sampler-1, respectively). Several other pesticides were detected in all locations (mean concentrations >1 ng sampler-1). The compounds fenamiphos, propyzamide, difenoconazole, propiconazole, metsulfuron methyl, sodium bis (perfluorohexyl) phosphinate (6:6 PFPiA), 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), 6:2 fluorotelomersulfonate (6:2 FTS), citalopram desmethyl and citalopram were reported in the wetland for the first time. Spatial distribution analysis revealed higher pesticide concentrations in the North of L'Albufera. A risk quotient (RQ) analysis showed that ibuprofen is of concern in the area. Overall, the MPT sampling approach is promising as a risk assessment tool for better understanding the transport and fate of OCs in protected areas.

Determination of organic pollutants in Anguilla anguilla by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS).

One of the aspects considered about the presence of contaminants in the aquatic ecosystems is their possible effect on critically endangered species, as the case of European eel, Anguilla anguilla. However, there is a lack of analytical methods to determine these contaminants due to the complexity of eel matrix (contains 5-20 % of lipids and 5-15 % of proteins). Thus, a multi-residue method using QuEChERS extraction a clean-up based on new specific sorbents (to eliminate lipids) and liquid chromatography tandem mass spectrometry (LC-MS/MS) was developed to determine a mix of 21 contaminants. Compared to the previously reported methods (Degani et al., 1986), which were developed for mussels, in this study, one of the proposed extraction methods were adapted to different fish tissues of higher complexity, such as liver and muscle of A. anguilla.•The effectivity of dispersive solid phase extraction (dSPE) using new specific Enhanced Matrix Removal (EMR-lipid) as clean-up for lipid removal was tested.•Clean extracts of matrices with high protein (5-15 %) and lipid (5-20 %) content were obtained ensuring robustness and durability of the analytical systems.•Emerging contaminants extractable by this procedure comprise four different families (pesticides, perfluoroalkyl substances (PFASs), pharmaceuticals and drugs of abuse). Then, it could be further applied to wide scope screening strategies.

Bioaccumulation of emerging contaminants in mussel (Mytilus galloprovincialis): Influence of microplastics.

Coastal environments are heavily influenced by human activities. Chemical substances considered as emerging contaminants (ECs) are one of the most important indicators of the anthropic influence on the environment, and they have recently shown to interact with microplastics (MPs). Mussels are suitable for in-lab bioacumulation studies providing insight about the occurrence and fate of contaminants in the organisms. In this study, bioacummulation of 20 chemical substances catalogued as ECs, including pharmaceuticals and personal care products (PPCPs), pesticides, and perfluoroalkyl substances (PFASs) in Mytilus galloprovincialis was assessed, with or without the influence of the presence of MPs. Mussels were distributed in three groups: control (B), exposed to ECs (C) and exposed to ECs and polyethylene MPs (C+M). The study was carried out for 58 days separated in two stages (i) exposure during days 0-28, and (ii) depuration during days 29-58. Visceral mass and haemolymph of the mussels were extracted separately, using QuEChERS and solid phase extraction (SPE), respectively. Then, extracts were analysed via UHPLC-MS/MS. Results showed that 3 PPCPs, 4 pesticides and 3 PFASs accumulated in visceral mass with bioconcentration factors (BCFs) ranging 6.7-15000 L/kg/d. In addition, 2 PPCPs, 2 pesticides and PFPeA were detected in haemolymph showing BCFs ranging 0.9-3.3 L/kg/d. When comparing C and C+M, MPs worked as a vector for the accumulation of the PFASs: PFOA, PFOS, PFDA and PFPeA; showing higher BCFs in the presence of MPs. Furthermore, the elimination of PFDA and PFOS was slower in the mussels exposed to MPs. On the other hand, the pesticides terbuthylazine and chlorpyrifos showed lower BCFs and more rapid elimination in the mussels exposed to MPs.

Dataset of pesticides, pharmaceuticals and personal care products occurrence in wetlands of Saudi Arabia.

The data set presents the occurrence of 59 currently used pesticides (CUPs) and 33 pharmaceuticals and personal care products (PPCPs), from wetland areas, in Saudi Arabia, impacted by wastewater discharge. Wetlands are valuable ecosystems, but are very fragile and easily affected by anthropogenic pressure [1], [2], [3], [4], [5], [6]. The occurrence of organic contaminants provides understanding about their fate and possible risk for humans and environment. Up to our knowledge, this is the first report on the occurrence of the mentioned organic pollutants in shallow lakes in Saudi Arabia, and the first time these compounds are analyzed in wild flora. Samples of water, sediment, soil and plants were extracted via ultrasound assisted extraction (UAE) and solid phase extraction (SPE). The compounds determination was performed using ultra-high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). Interpretation and discussion of the present dataset can be found in the article entitled "Pharmaceuticals, pesticides, personal care products and microplastics contamination assessment of Al-Hassa irrigation network (Saudi Arabia) and its shallow lakes"[1].

Pharmaceuticals, pesticides, personal care products and microplastics contamination assessment of Al-Hassa irrigation network (Saudi Arabia) and its shallow lakes.

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-1), caffeine (up to 20,663 ng L-1), diclofenac (up to 1390 ng L-1) and paracetamol (up to 3069 ng L-1) 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-1 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.

Sequential window acquisition of all theoretical fragments versus information dependent acquisition for suspected-screening of pharmaceuticals in sediments and mussels by ultra-high pressure liquid chromatography-quadrupole time-of-flight-mass spectrometry.

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.

Uptake and accumulation of emerging contaminants in soil and plant treated with wastewater under real-world environmental conditions in the Al Hayer area (Saudi Arabia).

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.

Simultaneous determination of traditional and emerging illicit drugs in sediments, sludges and particulate matter.

An analytical method for determining traditional and emerging drugs of abuse in particulate matter, sewage sludge and sediment has been developed and validated. A total of 41 drugs of abuse and metabolites including cocainics, tryptamines, amphetamines, arylcyclohexylamines, cathinones, morphine derivatives, pyrrolidifenones derivatives, entactogens, piperazines and other psychostimulants were selected. Samples were ultrasound extracted with McIlvaine buffer and methanol, and the extracts were cleaned up by solid phase extraction (SPE) using Strata-X cartridges. Drugs were eluted using methanol and methanol-dichloromethane and determined by liquid chromatography tandem mass spectrometry. The optimum solid-liquid extraction (SLE) conditions were: weight 1g of sample and ultrasound assisted extraction (UAE) with 10mL of methanol-McIlvain buffer (1:1, v/v, pH 4.5) for 10min. Recoveries for all compounds were ≥50% in the three matrices with the exception of ephedrine (EPHE), 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), ecgonine methyester (ECME), heroin (HER), 3,4-methylendioxyamphetamine (MDA) and 4-acetoxy N,N'-dimethyltryptamine (4-AcO-DIPT) and methadone (MET). Data acquisition was done by selective reaction monitoring (SRM), and the two most abundant product ions were used for confirmation. Limits of detection were lower than 1.32ngg(-1) dry weight (d.w.) and limits of quantification were between 0.12 and 3.96ngg(-1) (d.w.). The method was applied to the analysis of particulate matter, where cocaine (COC), benzoylecgonine (BECG), ecgoninemethylester (ECME), cocaethylene (COCET), methadone (MET) and codeine (COD) were mostly detected. In the case of dehydrated sludge, opioids are at higher concentration than cocainics and some emerging drugs such as 4-methoxyamphetamine (PMA), ketamine (KET) and bufotenine (BUF) were detected. In sediment COC, 4-methoxyphencyclidine (4-MeO-PCP), MET and BECG were most relevant compounds.