Search

This study explores the potential application of solar photochemical processes (SPPs) for simultaneous disinfection and decontamination of urban wastewater (UWW) when combined with constructed wetlands (CWs). Two SPPs based on the addition of low concentrations of hydrogen peroxide and peroxymonosulfate (PMS) were evaluated. SPPs were carried out at pilot plant scale using low-cost solar open photoreactors (Raceway Pond Reactor (RPR)) under natural sunlight. The performance of the SPPs was analyzed by monitoring naturally occurring bacteria (Escherichia coli, Enterococcus spp. and Salmonella spp.) and Contaminants of Emerging Concern (CECs), such as pharmaceutical products, pesticides, antibiotics and their metabolites, simultaneously. SPP best operating conditions were determined by testing a wide range of oxidant concentrations (0-5.9 mM, 0-3.0 mM) and liquid depths (5, 10 and 15 cm) in the RPR. SPP treatment efficacy was tested on the actual inlet and outlet of the CW system, showing the high influence of their different physicochemical characteristics on the oxidants' performance. H 2 O 2 /solar SPP in the actual inlet of the CWs showed slightly higher inactivation kinetics when increasing H 2 O 2 concentration at both water depths (5 and 10 cm), while no significant CECs degradation rates were obtained. However, much higher efficacy was obtained with PMS/solar process attaining high bacteria inactivation under dark conditions and 79 % CEC degradation at 3.0 mM after only 10 min of reaction time. SPPs assessment on the outlet of the CWs also showed better efficacy of the PMS as oxidant compared to the H 2 O 2 for the simultaneous CECs removal (95 % at 1.0 mM of PMS, after only 5 min of treatment) and bacteria inactivation (confirming the no-regrown after 24 h). SPPs have demonstrated to be a low-cost and eco-sustainable polishing alternative to regenerate CW effluents complying with the actual European regulation on the minimum water quality requirements for reusing treated UWW in agriculture., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Isabel Oller reports financial support was provided by ENI CBC Mediterranean Sea Basin Program. Isabel Oller reports financial support was provided by Spanish ministry of science and innovation. Isabel Oller reports a relationship with Research Centre for Energy Environment and Technology Energy Department that includes: employment. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Thiabendazole (TBZ), is a persistent fungicide/anthelminthic and a serious environmental threat. We previously enriched a TBZ-degrading bacterial consortium and provided first evidence for a Sphingomonas involvement in TBZ transformation. Here, using a multi-omic approach combined with DNA-stable isotope probing (SIP) we verified the key degrading role of Sphingomonas and identify potential microbial interactions governing consortium functioning. SIP and amplicon sequencing analysis of the heavy and light DNA fraction of cultures grown on 13 C-labelled versus 12 C-TBZ showed that 66% of the 13 C-labelled TBZ was assimilated by Sphingomonas. Metagenomic analysis retrieved 18 metagenome-assembled genomes with the dominant belonging to Sphingomonas, Sinobacteriaceae, Bradyrhizobium, Filimonas and Hydrogenophaga. Meta-transcriptomics/-proteomics and non-target mass spectrometry suggested TBZ transformation by Sphingomonas via initial cleavage by a carbazole dioxygenase (car) to thiazole-4-carboxamidine (terminal compound) and catechol or a cleaved benzyl ring derivative, further transformed through an ortho-cleavage (cat) pathway. Microbial co-occurrence and gene expression networks suggested strong interactions between Sphingomonas and a Hydrogenophaga. The latter activated its cobalamin biosynthetic pathway and Sphingomonas its cobalamin salvage pathway to satisfy its B12 auxotrophy. Our findings indicate microbial interactions aligning with the 'black queen hypothesis' where Sphingomonas (detoxifier, B12 recipient) and Hydrogenophaga (B12 producer, enjoying detoxification) act as both helpers and beneficiaries., (© 2022 Society for Applied Microbiology and John Wiley & Sons Ltd.)

The knowledge about the interaction of nanoplastics with other aquatic pollutants and their combined effects on biota is very scarce. In this work, we studied the interaction between polystyrene nanoplastics (PS NPs) (30 nm) and the micropollutants in a biologically treated wastewater effluent (WW). The capacity of PS NPs to sorb micropollutants was studied as well as their single and combined toxicity towards three freshwater organisms: the recombinant bioluminescent cyanobacterium, Anabaena sp. PCC 7120 CPB4337; the duckweed, Spirodela polyrhiza and the cladoceran, Daphnia magna. The endpoints were the inhibition of bioluminescence, the growth inhibition of the aquatic plant and the immobilization of D. magna after 24, 72 and 48 h of exposure, respectively. Combination Index (CI)-isobologram method was used to quantify mixture toxicity and the nature of interactions. PS NPs sorbed a variety of chemicals present in WW as micropollutants in a range of tens of ng/L to μg/L. It was found that those pollutants with positive charge were the main ones retained onto PS NPs, which was attributed to the electrostatic interaction with the negatively charged PS NPs. Regarding the toxicological effects, single exposure to PS NPs affected the three tested organisms. However, single exposure to WW only had a negative impact on the cyanobacterium and S. polyrhiza with no observed toxicity to D. magna. Regarding PS NPs-WW combined exposure, a reduction of toxicity in comparison with single exposure was observed probably due to the sorption of micropollutants onto PS NPs, which resulted in lower bioavailability of the micropollutants. In addition, the formation of PS NPs-WW heteroaggregates was observed which could result in lower bioavailability of PS NPs and sorbed micropollutants, thus lowering toxicity. This study represents a near-realistic scenario approach to the potential sorption of wastewater pollutants onto nanoplastics that could alter the toxicological effect on the biota., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

In this study, a full cycle of agricultural reuse of agro-food wastewater (synthetic fresh-cut wastewater, SFCWW) at pilot plant scale has been investigated. Treated SFCWW by ozonation and two solar processes (H 2 O 2 /solar, Fe 3+ -EDDHA/H 2 O 2 /solar) was used to irrigate two raw-eaten crops (lettuce and radish) grown in peat. Two foodborne pathogens (E. coli O157:H7 and Salmonella enteritidis) and five organic microcontaminants (OMCs: atrazine, azoxystrobin, buprofezin, procymidone and terbutryn) were monitored along the whole process. The three studied processes showed a high treatment capability (reaching microbial loads < 7 CFU/100 mL and 21-90 % of OMC reduction), robustness (based on 7 or 10 analysed batches for each treatment process) and high suitability for subsequent treated SFCWW safe reuse: non-phytotoxic towards Lactuca sativa and no bacterial regrowth during its storage for a week. The analysis of the harvested crop samples irrigated with treated SFCWW in all the studied processes showed an absence of microbial contamination (< limit of detection, LOD; i.e., < 1 CFU/99 g of lettuce and < 1 CFU/8 g of radish), a significant reduction of OMC uptake (in the range 40-60 % and > 90 % for solar treated and ozonated SFCWW, respectively) and bioaccumulation in both crops in comparison with the results obtained with untreated SFCWW. Moreover, the chlorophyll content in the harvested lettuces irrigated with SFCWW treated by Fe 3+ -EDDHA/H 2 O 2 /solar was twice than that irrigated with SFCWW treated by H 2 O 2 /solar and ozone, indicating the additional advantage of using Fe 3+ -EDDHA as an iron source to reduce the risk of iron chlorosis in crops. Finally, the chemical (dietary risk assessment for the combined exposure of the 5 OMCs) and quantitative microbiological risk assessment (QMRA) of the harvested crops showed the capability of the studied processes to reduce the risk associated with untreated SFCWW reuse by more than 50 % and more than 4 orders of magnitude, respectively., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

This work proposes the evaluation of an aluminized surface on the bottom of open reactors to perform a photo-Fenton process, at circumneutral pH (using Fe III-Ethylenediamine-N,N'-disuccinic acid complex), for elimination of micropollutants (MPs) in real effluents from municipal wastewater treatment plants (EMWWTP). Firstly, the strategy was to initially investigate the real EMWWTP spiked with several MPs (acetaminophen, diclofenac, carbamazepine, caffeine, trimethoprim and sulfamethoxazole) with 20 and 100 μg L -1 in a laboratory scale (evaluated by HPLC-UV) using a solar simulator. Finally, the removal of all MCs present in the real EMWWTP was monitored (evaluated by HPLC-MS) in a pilot-scale (90 L) in a raceway pond reactor (RPR). The treatment time required for degradation above 80% for the investigated MPs was over 30 min, and the predominant effect could be mainly associated with organics present in the real EMWWTP due to the light attenuation and scavenging of radical species. Moreover, the results confirmed that chloride and sulfate would most likely equally not affect the process. The use of an aluminized surface on the bottom of RPRs has been confirmed as a suitable option to improve the photo-Fenton reaction, enabling the use of lower doses of iron. Up to 60 different MPs found in EMWWTP have been successfully degraded using 0.1 mM of Fe at circumneutral pH with a consumption of 30 mg L -1 H 2 O 2 with less than 45 min., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The effect of the UV-C/free chlorine (FC) process on the removal of contaminants of emerging concern (CECs) from real urban wastewater as well as the effect of UV-C radiation on the formation of trihalomethanes (THMs) compared to FC process alone was investigated. Unlike of FC process, UV-C/FC was really effective in the degradation of the target CECs (carbamazepine (CBZ), diclofenac, sulfamethoxazole and imidacloprid) in real wastewater (87% degradation of total CECs within 60 min, Q UVC  = 1.33 kJ L -1 ), being CBZ the most refractory one (49.5%, after 60 min). The UV-C radiation significantly affected the formation of THMs. THMs concentration (mainly chloroform) was lower in UV-C/FC process after 30 min treatment (<1 μgL -1  = limit of quantification (LOQ)) than in FC process in dark (2.3 μgL -1 ). Noteworthy, while in FC treated wastewater chloroform concentration increased after treatment, UV-C/FC process resulted in a significant decrease (residual concentrations below the LOQ), even after 24 h and 48 h post-treatment incubation. The formation of radicals due to UV-C/FC process can reduce THMs compared to chlorination process, because part of FC reacts with UV-C radiation to form radicals and it is no longer available to form THMs. These results are encouraging in terms of possible use of UV-C/FC process as advanced treatment of urban wastewater even for possible effluent reuse., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Agriculture is considered as the main source of water contamination by pesticides. However, food packaging or processing industries are also recognised as relevant point sources of contamination by these compounds, not yet investigated in depth. The objective of this work has been to improve current knowledge about the presence and concentration of pesticides in the effluent of a food processing industry, as well as to investigate their main transformation products (TPs). An analytical strategy combining target and suspect analysis has been applied to provide an evaluation of the effluents. The methodology involves solid-phase extraction (SPE) of wastewater samples followed by (i) liquid chromatography quadrupole-linear ion trap tandem mass spectrometry (LC-QqLIT-MS/MS) for quantitative target analysis and (ii) liquid chromatography coupled to quadrupole-time-of-flight high resolution mass spectrometry (LC-QTOF-HRMS) to identify non-target pesticides and possible TPs. The results revealed the presence of 17 of the target pesticides analysed and 3 additional ones as a result of the suspect screening performed by HRMS. The TPs were investigated for the pesticides found at the highest concentrations: imazalil (7038-19802 ng/L), pyrimethanil (744-9591 ng/L) and thiabendazole (341-926 ng/L). Up to 14 TPs could be tentatively identified, demonstrating the relevance of this type of studies. These data provide a better understanding of the occurrence of pesticides and their TPs in agro-food industrial effluents., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

It is well known that wastewater treatment plant (WWTP) effluents usually contain micropollutants such as pharmaceuticals (or their transformation products, TPs) or pesticides, which is a major issue when evaluating their possible reuse (e.g. for irrigation in agriculture). In search for an improved accuracy and simplicity, methods based on the direct injection of the sample (DI) represent a recent trend taking advantage of the increasing sensitivity of new mass spectrometry (MS) instruments. Thus, the present study shows the development and validation of a DI-based method by ultra-high-performance liquid chromatography quadrupole-linear ion trap analyser (UHPLC-QqLIT-MS/MS). The proposed method was applied to the monitoring of 115 organic microcontaminants (including pharmaceuticals, TPs and pesticides) at the ngL -1 /μgL -1 level in wastewater effluents from urban WWTPs. Sample pre-treatment was reduced to acetonitrile addition and filtration of the mixture previous to LC-MS analysis. Total analysis time was <15min. A subsequent validation protocol was carried out in treated WW (TWW), following indications of SANTE and Eurachem Guidelines. Linearity and matrix effect were evaluated in the range of 10-1000ngL -1 . 70% of the analytes showed a moderate matrix effect (≤25%). Trueness (expressed as recovery) and precision (calculated as relative standard deviation, RSD) were evaluated at four concentration levels (20, 50, 500 and 1000ngL -1 ) in TWW samples. The LODs ranged from 1 to 357ngL -1 and the LOQs from 10 to 500ngL -1 . 92% of the compounds showed limits of quantification ≤100ngL -1 . In most cases, mean recoveries were in the range 70-120%, and RSD values were ≤20%. The validated method was successfully applied to the analysis of 10 TWW samples, demonstrating the occurrence of 67 target compounds at concentration levels from 26705ngL -1 (4-aminoantipyrine) to 10ngL -1 (tebuconazole and bezafibrate)., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A method has been developed and validated for the simultaneous detection and quantification of phytochemicals in nutraceutical products obtained from green tea. For that purpose, ultra-high performance liquid chromatography coupled to single-stage Orbitrap high resolution mass spectrometry (UHPLC-Orbitrap-MS) has been used. A database containing 37 compounds has been used for the detection and identification of the target compounds. The developed methodology was based on solid-liquid extraction, using a mixture of methanol:H2O (80:20, v/v, pH 4), followed by dilution (10 times) with a mixture of ammonium acetate:methanol (50:50, v/v). Chromatographic conditions were optimised and full scan accurate mass data acquisition using electrospray ionisation in positive and negative ion mode was used. Moreover, all-ion fragmentation mode was used to get information of fragment ions, and they were used for identification purposes. The developed method was validated, obtaining repeatability (intra-day) and inter-day precision values (expressed as relative standard deviation, RSD) lower than 16% and 20%, respectively. Lower limits were also evaluated and limits of detection (LODs) ranged from 1 to 50 μg L(-1), while limits of quantification (LOQs) ranged from 2 to 150 μg L(-1). Recovery was performed at five levels and it ranged from 70% to 109%. Finally, this method was used to evaluate the phytochemical content in 10 samples (tablets or capsules), showing concentrations of (+)-catechin, (-)-epicatechin, gallic acid, (-)-gallocatechin and quercetin-3-O-rutinoside, ranging from 258 (C6) to 10,729 (C6) mg kg(-1)., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Phytochemicals content, including several families such as phenolic acids, isoflavones, flavones, flavonols, isothiocyanates, and glucosinolates, was determined in pre-cooked convenience vegetables by ultra high performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry (UHPLC-QqQ-MS/MS). It was observed that there is not a common behavior of the individual concentration of phytochemicals during the lifetime and cooking of the matrix, and compounds change their concentration without a specific trend. It was observed that neither lifetime nor cooking process have significant effects on the total content of phytochemicals except in broccoli, although some changes in the individual content of the target compounds were observed, suggesting that interconversion processes could be performed during the lifetime and/or cooking process of the product.

A method for the determination of 14 biopesticides and piperonyl butoxide (PBO), often applied in organic farming, in vegetables and fruits has been developed. Extraction was performed using the Quick, Easy, Cheap, Effective, Rugged, and Safe method, and the determination was carried out by ultra-performance LC/MS/MS in 9 min. Several different food commodities were evaluated as representative matrixes, namely, cucumber, tomato, pepper (high water content), and strawberry and orange (high acid and water content). Biopesticides were quantified using matrix-matched calibration, and the optimized method was validated at three concentration levels, i.e., 10, 50, and 100 microg/kg, for all the compounds, yielding recoveries in the range 70-112%, 71-112%, and 70-109%, respectively, with RSDs <28%. LOQs were <3 microg/kg for all biopesticides. The validated procedure was applied to the analysis of vegetables and fruits, including products from organic farming; PBO was detected in one sample at 8 microg/kg.

A method based on QuEChERS (quick, easy, cheap, effective, rugged, and safe) has been developed and validated for the determination and quantification of more than 140 pesticides in nutraceutical products obtained from green tea (Camellia sinensis). Extraction was performed with acidified acetonitrile (acetic acid 1%, v/v) and a clean-up step using primary secondary amine (50 mg), graphitized black carbon (100 mg) and magnesium sulfate (200 mg) was needed. Pesticide determination was achieved utilizing GC coupled to triple quadrupole MS/MS using the selective-reaction monitoring mode. The total run time was 23 min. Pesticides were quantified using matrix-matched calibration. Recoveries ranged from 70 to 120% and relative SD was lower than 25% at 10, 50, and 100 μg/kg. LOQs were lower than 10 μg/kg. 148 pesticides were validated. The validated method was applied to commercial nutraceutical products, detecting 4,4-dichlorobenzophenone (28 μg/kg), o,p'-dicofol (38 μg/kg) and p,p-dicofol (44 μg/kg) in a few samples., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A review of sample preparation and analytical techniques currently used to analyze pesticides in nutraceutical products is shown. Different sample treatments are commented, and the QuEChERS method is the most used (quick, easy, cheap, effective, rugged and safe). For the chromatographic determination, gas chromatography (GC) and liquid chromatography (LC) are evaluated. Different detection modes are discussed, and simple quadrupole mass spectrometry (Q-MS) and triple quadrupole tandem mass spectrometry (QqQ-MS/MS) are the most used. Finally, a review of the occurrence of pesticides (from the revised literature) in real samples is presented, evaluating several matrices, such as nutraceuticals, dietary supplements, medicinal plants, and fish oil. The occurrence of several pesticides was reported: γ-HCH (lindane), endosulfan, procymidone, azoxystrobin, p,p'-DDE, metalaxyl, quintozene, tolclofos-methyl, chlorpyrifos and hexachlorobenzene., (© 2013 Elsevier B.V. All rights reserved.)

A multiresidue and multiclass method for the simultaneous determination of more than 350 compounds including pesticides, biopesticides and veterinary drugs in different meat matrices (beef, pork and chicken) by ultra-high performance liquid chromatography coupled to Orbitrap MS has been developed. In the present study, the determination of fragments was accomplished as an essential tool for a reliable identification of compounds using high resolution MS. To obtain these fragments, different strategies have been carried out in order to ensure an appropriate fragment assignment and identification. The analytical method is suitable for qualitative analysis, and it was also evaluated for quantitative analysis. Generic extraction conditions were optimized, obtaining adequate recovery and precision values for most of the studied analytes (>290). The limits of detection ranged from 2 to 16 µg kg(-1). Limits of quantification were 10 µg kg(-1) with the exception of few compounds with a higher value (50 or 100 µg kg(-1)). Limits of identification were also established, and they ranged from 2 to 150 µg kg(-1). This method was applied to the analysis of 18 meat samples and some veterinary drugs as enrofloxacin and sulfadiazine were detected and further identified/quantified (with triple quadrupole) in two different samples at 33 µg kg(-1) and trace levels, respectively. No pesticides were detected in the analyzed samples., (Copyright © 2014 John Wiley & Sons, Ltd.)