IAREN Water Institute of the Northern Region

Matosinhos, Portugal

IAREN Water Institute of the Northern Region

Matosinhos, Portugal
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Silva T.F.C.V.,University of Porto | Silva M.E.F.,Escola Superior de Tecnologia de Viseu | Cunha-Queda A.C.,University of Lisbon | Fonseca A.,Efacec Engineering e Sistemas S.A. Unidade de Negocios Ambiente | And 7 more authors.
Water Research | Year: 2013

A multistage treatment system, at a scale close to the industrial, was designed for the treatment of a mature raw landfill leachate, including: a) an activated sludge biological oxidation (ASBO), under aerobic and anoxic conditions; b) a solar photo-Fenton process, enhancing the bio-treated leachate biodegradability, with and without sludge removal after acidification; and c) a final polishing step, with further ASBO. The raw leachate was characterized by a high concentration of humic substances (HS) (1211mg CHS/L), representing 39% of the dissolved organic carbon (DOC) content, and a high nitrogen content, mainly in the form of ammonium nitrogen (>3.8g NH4 +-N/L).In the first biological oxidation step, a 95% removal of total nitrogen and a 39% mineralization in terms of DOC were achieved, remaining only the recalcitrant fraction, mainly attributed to HS (57% of DOC). Under aerobic conditions, the highest nitrification rate obtained was 8.2mg NH4 +-N/h/g of volatile suspended solids (VSS), and under anoxic conditions, the maximum denitrification rate obtained was 5.8mg (NO2 --N+NO3 --N)/h/g VSS, with a C/N consumption ratio of 2.4mg CH3OH/mg (NO2 --N+NO3 --N). The precipitation of humic acids (37% of HS) after acidification of the bio-treated leachate corresponds to a 96% DOC abatement. The amount of UV energy and H2O2 consumption during the photo-Fenton reaction was 30% higher in the experiment without sludge removal and, consequently, the reaction velocity was 30% lower. The phototreatment process led to the depletion of HS >80%, of low-molecular-weight carboxylate anions>70% and other organic micropollutants, thus resulting in a total biodegradability increase of >70%. The second biological oxidation allowed to obtain a final treated leachate in compliance with legal discharge limits regarding water bodies (with the exception of sulfate ions), considering the experiment without sludge. Finally, the high efficiency of the overall treatment process was further reinforced by the total removal percentages attained for the identified organic trace contaminants (>90%). © 2013 Elsevier Ltd.


Sousa M.A.,University of Porto | Sousa M.A.,IAREN Water Institute of the Northern Region | Goncalves C.,University of Porto | Goncalves C.,IAREN Water Institute of the Northern Region | And 4 more authors.
Analytical and Bioanalytical Chemistry | Year: 2011

This work describes the development and validation of an offline solid-phase extraction with simultaneous cleanup capability, followed by liquid chromatography-(electrospray ionisation)-ion trap mass spectrometry, enabling the concurrent determination of 23 pharmaceuticals of diverse chemical nature, among the most consumed in Portugal, in wastewater samples. Several cleanup strategies, exploiting the physical and chemical properties of the analytes vs. interferences, alongside with the use of internal standards, were assayed in order to minimise the influence of matrix components in the ionisation efficiency of target analytes. After testing all combinations of adsorbents (normal-phase, ion exchange and mixed composition) and elution solvents, the best results were achieved with the mixed-anion exchange Oasis MAX cartridges. They provided recovery rates generally higher than 60%. The precision of the method ranged from 2% to 18% and 4% to 19% (except for diclofenac (22%) and simvastatin (26%)) for intra- and inter-day analysis, respectively. Method detection limits varied between 1 and 20 ng L -1, while method quantification limits were <85 ng L -1 (both excluding ibuprofen). This analytical method was applied to gather preliminary results on influents and effluents of two wastewater treatment plants (WWTPs) located in the urban region of Porto (Portugal). Typically, paracetamol, hydrochlorothiazide, furosemide, naproxen, ibuprofen, diclofenac and bezafibrate were detected in concentrations ranging from 1 to 20 μg L -1, while gemfibrozil, simvastatin, ketoprofen, azithromycin, bisoprolol, lorazepam and paroxetine were quantified in levels below 1 μg L -1. These WWTPs were given particular attention since they discharge their effluents into the Douro river, where water is extracted for the production of drinking water. Some sampling spots in this river were also analysed. © 2010 Springer-Verlag.


Zonja B.,CSIC - Institute of Environmental Assessment And Water Research | Goncalves C.,IAREN Water Institute of the Northern Region | Goncalves C.,University of Porto | Perez S.,CSIC - Institute of Environmental Assessment And Water Research | And 5 more authors.
Journal of Hazardous Materials | Year: 2014

The antiviral zanamivir has been recently reported to occur in surface waters where its presence may lead to the selection of resistant strains of virus in aquatic fauna. In order to evaluate the fate of zanamivir in surface waters, its susceptibility to phototransformation was evaluated using simulated and natural sunlight. Upon exposure of aqueous solutions (20μgL-1) to simulated sunlight, zanamivir in surface water degraded at t1/23.6h. Under natural sunlight in surface water about 30% of the initial concentration of the antiviral disappeared within 18 days. The experiments with surface water showed similar effect as humic acid addition with expected decreasing effect on degradation while nitrate addition showed increasing effect. In the experiments with artificial sunlight at high concentrations of zanamivir, four photoproducts were tentatively identified by hydrophilic interaction chromatography-LTQ-Orbitrap-MS, showing [M+H]+ ions at m/z 112 (TP111), m/z 275 (TP274), m/z 323 (TP322), and m/z 333 (TP332). However at 20μgL-1 only the formation of the recalcitrant TP111 was observed. The proposed structures were rationalized by photolysis mechanisms. Photoproduct TP111 was confirmed with a commercially available standard (isocytosine). In summary, the findings suggest that the photodegradation of zanamivir in surface waters proceeds with slow kinetics. © 2013 Elsevier B.V.


Rodriguez-Gonzalez N.,University of La Coruña | Beceiro-Gonzalez E.,University of La Coruña | Gonzalez-Castro M.J.,University of La Coruña | Alpendurada M.F.,IAREN Water Institute of the Northern Region
Journal of Chromatography A | Year: 2016

A fast, simple, selective and sensitive method has been developed for the determination of nine triazine herbicides (ametryn, atrazine, cyanazine, prometryn, propazine, simazine, simetryn, terbuthylazine and terbutryn) and eight degradation products (desethyl atrazine, desethyl-desisopropyl atrazine, desethyl 2-hydroxyatrazine, desethyl terbuthylazine, desisopropyl atrazine, desisopropyl 2-hydroxyatrazine, 2-hydroxyatrazine and 2-hidroxyterbuthylazine) in seawater samples. On-line solid-phase extraction coupled with ultra-pressure liquid chromatography-tandem mass spectrometry was employed for simultaneous analysis of all compounds in 11min. Validation parameters were studied through the estimation of the limits of detection and quantification, calibration curves and precision. Limits of quantification ranged from 0.023 to 0.657μgL-1. Good linearity was obtained for all compounds with R2 >0.99 in all cases. Furthermore, inter-day precision (0-2.1%) and intra-day precision (0-3.9%) were shown to be satisfactory. On-line solid-phase extraction recoveries in spiked unpolluted seawater sample were evaluated and acceptable values (80.3-99.8%) with adequate RSD (0.1-3.1%) were found.Finally, the proposed method was applied to the analysis of the target compounds in seawater samples collected from seawater nearby a zone of intensive horticulture of Matosinhos (Portugal). The concentrations of the herbicides were below the limit of detection in all cases. © 2016 Elsevier B.V.


MacHado S.,IAREN Water Institute of the Northern Region | Gonalves C.,IAREN Water Institute of the Northern Region | Gonalves C.,University of Porto | Cunha E.,University of Porto | And 3 more authors.
Talanta | Year: 2011

Fragrances are widespread aquatic contaminants due to their presence in many personal care products used daily in developed countries. Levels of galaxolide and tonalide are commonly found in surface waters, urban wastewaters and river sediments. On the other hand, earthy-musty compounds confer bad odour to drinking water at levels that challenge the analytical capabilities. The combined determination of earthy-musty compounds and fragrances in water would be a breakthrough to make the traditional organoleptic evaluation of the water quality stricter and safer for the analyst. Two approaches were attempted to improve the analytical capabilities: analyte pre-concentration with a newly developed PDMS-DVB solid-phase microextraction fibre on metal alloy core and sensitive detection by tandem mass spectrometry (MS/MS). The optimization of SPME parameters was carried out using a central composite design and desirability functions. The final optimum extraction conditions were: headspace extraction at 70 °C during 40 min adding 200 g L -1 of NaCl. The detection limits in tandem MS (0.02-20 ng L -1) were marginally lower compared to full scan except for geosmin and trichloroanisol which go down to 0.1 and 0.02 ng L -1, respectively. The analysis of different water matrices revealed that fragrances and earthy-musty compounds were absent from ground- and drinking waters. Surface waters of river Lea contained levels of galaxolide around 250 ng L -1 in the 4 terminal sampling stations, which are downstream of WWTPs and polluted tributaries. Geosmine was ubiquitously distributed in natural waters similarly in rivers Lea and Douro at concentrations <7 ng L -1. © 2011 Elsevier B.V. All rights reserved.


Vilar V.J.P.,University of Porto | Moreira F.C.,University of Porto | Ferreira A.C.C.,University of Porto | Sousa M.A.,IAREN Water Institute of the Northern Region | And 4 more authors.
Water Research | Year: 2012

This work proposes an efficient combined treatment for the decontamination of a pesticide-containing wastewater resulting from phytopharmaceutical plastic containers washing, presenting a moderate organic load (COD=1662-1960mgO 2L -1; DOC=513-696mgCL -1), with a high biodegradable organic carbon fraction (81%; BOD 5=1350-1600mgO 2L -1) and a remaining recalcitrant organic carbon mainly due to pesticides. Nineteen pesticides were quantified by LC-MS/MS at concentrations between 0.02 and 45mgL -1 (14-19% of DOC). The decontamination strategy involved a sequential three-step treatment: (a) biological oxidation process, leading to almost complete removal of the biodegradable organic carbon fraction; (b) solar photo-Fenton process using CPCs, enhancing the bio-treated wastewater biodegradability, mainly due to pesticides degradation into low-molecular-weight carboxylate anions; (c) and a final polishing step to remove the residual biodegradable organic carbon, using a biological oxidation process. Treatment performance was evaluated in terms of mineralization degree (DOC), pesticides content (LC-MS/MS), inorganic ions and low-molecular-weight carboxylate anions (IC) concentrations. The estimated phototreatment energy necessary to reach a biodegradable wastewater, considering pesticides and low-molecular-weight carboxylate anions concentrations, Zahn-Wellens test and BOD 5/COD ratio, was only 2.3kJ UVL -1 (45min of photo-Fenton at a constant solar UV power of 30Wm -2), consuming 16mM of H 2O 2, which pointed to 52% mineralization and an abatement higher than 86% for 18 pesticides. The biological oxidation/solar photo-Fenton/biological oxidation treatment system achieved pesticide removals below the respective detection limits and 79% mineralization, leading to a COD value lower than 150mgO 2L -1, which is in agreement with Portuguese discharge limits regarding water bodies. © 2012 Elsevier Ltd.


Sousa M.A.,University of Porto | Sousa M.A.,IAREN Water Institute of the Northern Region | Goncalves C.,IAREN Water Institute of the Northern Region | Vilar V.J.P.,University of Porto | And 2 more authors.
Chemical Engineering Journal | Year: 2012

Emerging pollutants, such as pharmaceuticals, are widely disseminated in the aquatic media. Though in low concentrations in the environment, they still pose concerns mainly over potential chronic toxicity effects. Consequently, this work reports on the successful attempt to develop a photocatalytic treatment method, using suspended TiO2 in a concentration of 200mgL-1 and solar UV radiation as the photon source, firstly designed for lorazepam (Lorenin® pills) degradation and further applied to the treatment of a real municipal WWTP effluent, containing several other emerging contaminants (ECs).Initial effluent physicochemical characterization revealed the presence of 22 pharmaceutical compounds in moderate concentrations (maximum of 680ngL-1, except for diclofenac ∼24μgL-1 and hydrochlorothiazide ∼3μgL-1) and a low dissolved organic carbon (DOC) content. Therefore, the main purpose of the work was not to increase the effluent's biodegradability, but to improve the removal rates of the several present ECs. Pharmaceuticals' degradation kinetics, using a solar pilot plant with CPCs, were thoroughly studied. A pseudo-first order kinetic model was able to successfully predict the experimental data. The overall treatment was considered efficient, with a complete removal of the majority of these micropollutants, except for ciprofloxacin (35%), ketoprofen (61%) and bisoprolol (77%). Nevertheless, a small increase in the reaction time could easily accomplish their total degradation. Zahn-Wellens biodegradability assay allowed withdrawing some conclusions about which pharmaceuticals could be degraded by means of biotreatment, thus avoiding the need to apply a photocatalytic treatment. Finally, Vibrio fischeri acute toxicity test showed that the effluent itself presented no significant toxicity and that the intermediate oxidation compounds, possibly formed during phototreatment, did not reflect any significant increase of toxicity. © 2012.


Sousa M.A.,University of Porto | Sousa M.A.,IAREN Water Institute of the Northern Region | Goncalves C.,IAREN Water Institute of the Northern Region | Pereira J.H.O.S.,University of Porto | And 3 more authors.
Solar Energy | Year: 2013

Lorazepam is a recalcitrant drug, frequently quantified in WWTPs' effluents and surface waters, even though it has never been studied under accelerated phototransformation processes. Therefore, the main goal of the present work was to comparatively evaluate lorazepam's photolytic and photocatalytic degradation kinetics using two experimental systems: a lab-scale photochemical reactor provided with an UV medium pressure mercury lamp (LsAUVP) and a solar pilot plant with compound parabolic collectors (SPP-CPCs). Lorazepam was tested in its most commercialized dosage form in Portugal - Lorenin® pills, 1. mg (Wyeth), thus simulating a more realistic scenario.Preliminary results showed that, using the LsAUVP apparatus, lorazepam's highest degradation yield was obtained through photolysis, while using the SPP-CPCs system, the best degradation performance was achieved by photocatalysis with a TiO2 concentration of 200mgL-1. Furthermore, the degradation kinetic constant obtained for the optimized method when using the SPP-CPCs system (k=1.49±0.03LkJ-1) was higher than that with the LsAUVP set-up (k=0.131±0.006LkJ-1), which in terms of necessary accumulated UV energy for complete lorazepam degradation, considering the respective method's detection limit (MDL), corresponds to ca. 3 and 25kJL-1, respectively. © 2012 Elsevier Ltd.


Pesticides, a group of compounds linked to human activity, may, when in toxic levels, have a profound effect on water quality, and hence result in adverse consequences to aquatic life and ultimately to human health. Analytical challenges arise when successfully trying to determine these levels in environmental complex matrices. Therefore, fast, simple, sensitive and selective analytical methodologies for multi-residue determination of pesticides (atrazine, azoxystrobin, bentazon, -cyhalothrin, penoxsulam and terbuthylazine) in sediment, macrophytes (algae and aquatic plants) and aquatic animals were developed and validated. The established methods were matrix-dependent and were based on Selective Pressurized Liquid Extraction (SPLE) followed by on-line Solid Phase Extraction and Ultra Performance Liquid Chromatography-tandem Mass Spectrometry (on-line SPE-UPLC-ESI-MS/MS). This cutting-edge research methodology uses a small amount of sample, is time saving and reduces the use of organic solvents in compliance with Green Chemistry principles. The analytical features were adequate for all compounds in all studied matrices. The established methodology was applied on real marine samples and no pesticide concentrations above their respective method quantification limits were measured in sediments or aquatic plants. However, terbuthylazine was found in the macroalgae Ulva spp. (108ngg(-1)dw) and all the prospected pesticides were measured above their respective method quantification limits in the bivalve Scrobicularia plana (atrazine: 48ngg(-1)dw, azoxystrobin: 64ngg(-1)dw, bentazon: 33ngg(-1)dw, -cyhalothrin: 2531ngg(-1)dw, penoxsulam: 50ngg(-1)dw, and terbuthylazine: 44ngg(-1)dw).


PubMed | University of La Coruña and IAREN Water Institute of the Northern Region
Type: | Journal: Journal of chromatography. A | Year: 2016

A fast, simple, selective and sensitive method has been developed for the determination of nine triazine herbicides (ametryn, atrazine, cyanazine, prometryn, propazine, simazine, simetryn, terbuthylazine and terbutryn) and eight degradation products (desethyl atrazine, desethyl-desisopropyl atrazine, desethyl 2-hydroxyatrazine, desethyl terbuthylazine, desisopropyl atrazine, desisopropyl 2-hydroxyatrazine, 2-hydroxyatrazine and 2-hidroxyterbuthylazine) in seawater samples. On-line solid-phase extraction coupled with ultra-pressure liquid chromatography-tandem mass spectrometry was employed for simultaneous analysis of all compounds in 11min. Validation parameters were studied through the estimation of the limits of detection and quantification, calibration curves and precision. Limits of quantification ranged from 0.023 to 0.657gL

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