Main Transformation Products Research Articles

Diclofenac and two of its photooxidation products in the marine environment: Their toxicology and occurrence in Red Sea coastal waters

Direct effects of sunlight irradiation on the photochemical degradation of diclofenac (DCF) has been investigated in coastal Saudi Arabia (Jeddah) under controlled field conditions. Indirect effects from processes like sensitization and photocatalysis were excluded for this study. Photodecomposition of DCF under natural sunlight is essentially identical during summer and winter but slowed down considerably under cloudy conditions. 9H-Carbazole-1-acetic acid (D1) and 8-chloro-9H-carbazole-1-acetic acid (D2) were the main transformation products. When exposed to sunlight under the same conditions, the former acid reacted more slowly than DCF, the latter more rapidly. DCF exhibits antibacterial activity against multidrug-resistant bacteria, the carbazoles do not, and both DCF and the carbazoles are nontoxic to brine shrimp (Artemia salina). Only 9H-carbazole-1-acidic acid expresses antitumor activity against the Lymphoma cell line and Lewis lung carcinoma (LD50 = 0.044 and 0.066 mM, respectively). A new quantitative analytical method was adopted and validated for simultaneous ultra-trace quantification of DCF, D1, and D2 in contaminated surface waters from the Saudi coast of the eastern Red Sea. The analytical method involved solid-phase extraction (on HLB – hydrophilic – lipophilic balanced phases) followed by liquid-chromatographic separation and tandem mass-spectrometric detection and quantification. DCF was found in the concentration up to 26.9 ng/L. Both D1 and D2 were detected at relatively low concentration ranges (up to 3.3 ng/L and 1.9, respectively).

Degradation of climbazole by UV/chlorine process: Kinetics, transformation pathway and toxicity evaluation

Climbazole is an antifungal agent widely used in household personal care products, and it was found persistent in chlorination disinfection process. Here we investigated the kinetics and mechanism of climbazole degradation by UV/chlorine process. The results showed that the UV/chlorine process dramatically enhanced degradation of climbazole when compared to the UV photolysis and chlorination alone. The neutral condition (pH 7) produced the highest reaction rate for the climbazole by UV/chlorine among the various pH conditions. Dissolved organic matter and inorganic ions in natural water showed moderate inhibition effects on the degradation of climbazole in the UV/chlorine process. Hydroxyl radical (OH and chlorine radical (Cl) were found to be the main reactive species in the degradation of climbazole, with the second-order rate constant of 1.24 × 1010 M−1 s−1 and 6.3 × 1010 M−1 s−1, respectively. In addition, the OH and Cl in the UV/chlorine at 100 μM accounted for 82.2% and 7.7% contributions to the removal of climbazole, respectively. Eleven of main transformation products of climbazole were identified in the UV/chlorine process. These oxidation products did not cause extra toxicity than climbazole itself. The findings from this study show that the combination of chlorination with UV photolysis could provide an effective approach for removal of climbazole during conventional disinfection process.

Degradation of Paracetamol by an UV/Chlorine Advanced Oxidation Process: Influencing Factors, Factorial Design, and Intermediates Identification.

The combination of a low-pressure mercury lamp and chlorine (UV/chlorine) was applied as an emerging advanced oxidation process (AOP), to examine paracetamol (PRC) degradation under different operational conditions. The results indicated that the UV/chlorine process exhibited a much faster PRC removal than the UV/H2O2 process or chlorination alone because of the great contribution of highly reactive species (•OH, •Cl, and ClO•). The PRC degradation rate constant (kobs) was accurately determined by pseudo-first-order kinetics. The kobs values were strongly affected by the operational conditions, such as chlorine dosage, solution pH, UV intensity, and coexisting natural organic matter. Response surface methodology was used for the optimization of four independent variables (NaOCl, UV, pH, and DOM). A mathematical model was established to predict and optimize the operational conditions for PRC removal in the UV/chlorine process. The main transformation products (twenty compound structures) were detected by liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS).

Comparative assessment of endocrine disrupting compounds removal in heterotrophic and enriched nitrifying biomass

Despite the number of studies that have investigated the fate of endocrine disrupting compounds (EDCs), to date results are still contradictory and more research is required to evaluate the contribution of the microbial communities present in different engineered treatment systems. Thus, autotrophic and heterotrophic types of biomass were here compared in terms of efficiency in the removal of estrone (E1), 17β-estradiol (E2), estriol (E3), 17α-ethynilestradiol (EE2) and bisphenol A (BPA). Experiments were performed with enriched nitrifying activated sludge (NAS) and enriched ammonia oxidizing bacteria (AOB) sludge cultivated at lab-scale, as well as with conventional activated sludge (CAS) from a full-scale wastewater treatment plant. Both enriched NAS and AOB demonstrated a negligible degrading capacity. In both cases, the studied EDCs exhibited low removals (<14%) and showed no correlation with the increasing nitrification rates contradicting some of the hypothesis present in literature. Contrariwise, the biodegradation capabilities of the heterotrophic fraction of CAS were highlighted. E2 and E3 were removed by up to 100% and 78%, respectively. E1 was found to be the main transformation product of E2 (almost quantitative oxidation) and it was also highly eliminated. Finally, EE2 and BPA were more persistent biologically with removals ranging from 10% to 39%. For these two compounds similar removals were obtained during experiments with heat-inactivated biomass suggesting that sorption could be a relevant route of elimination.

Identification of new metabolites of vardenafil with the use of HLM and photochemical methods by LC-ESI-HRMS combined with multivariate chemometric analysis

The in vitro metabolism of vardenafil, a selective phosphodiesteraze type 5 (PDE-5) inhibitor was investigated with the use of biological HLM method in comparison to TiO2 and WO3 assisted photocatalytic approach. The main objective of this study was to identify the transformation routes and elucidate metabolite structures. The samples were analyzed by LC-ESI-HRMS system to obtain metabolism pathways and confirm the structures of new metabolites. Deethylated vardenafil was identified as a main transformation product and additionally, nine new, not yet described, metabolites were found in HLM samples. The photocatalytic process with the use of TiO2 and WO3 allowed to observe five and seven transformation products respectively. The multivariate chemometric comparison of the obtained results shows WO3 assisted photocatalysis as a more suitable approach of phase I metabolism simulation method.

Schwertmannite transformation via direct or indirect electron transfer by a sulfate reducing enrichment culture

Understanding the mechanism of the microbial transformation of Fe(III)-oxyhydroxysulfate minerals is of considerable interest, because this transformation plays an important role in controlling the behaviour of toxic metals from acid mine drainage (AMD). In this study, we examined a sulfate reducing enrichment culture from AMD-contaminated sediments and predicted the possible pathway of electron transfer when incubated with schwertmannite, a common Fe(III)-oxyhydroxysulfate occurring in the AMD environment. Experiments were designed to distinguish the mechanisms by which bacteria facilitate direct (i.e., bacteria allowed to adhere to the mineral) or indirect (i.e., bacteria separated from the mineral by dialysis bag) electron transfer to reduce the mineral. The effects of adding anthraquinone-2,6-disulfonate (AQDS) as an exogenous electron shuttle were also investigated. Vivianite was detected as the main product of schwertmannite transformation. Reduction of sulfate and iron were more pronounced in direct treatments, while more non-reductive dissolution were observed in indirect treatments. The addition of AQDS lead to the production of more dissolved Fe2+ over 20 d than in the absence of AQDS. Microbial community composition differed in direct and indirect treatments, while the addition of AQDS did not significantly affect the community structure in each treatment. After incubation for 20 d, the growth of Desulfovibrio exceeded that of the originally dominant Citrobacter in direct treatments, while an unknown genus most closely related to Citrobacter within Enterobacteriaceae was predominant in indirect treatments. This monodominant community in indirect treatments was assumed not to transfer electron directly to schwertmannite but to rely on shuttling mechanism. PICRUSt results implied that bacteria in indirect treatment have potential to produce shuttling compounds or complexing agents. The absence of dsr genes and the putative fermentative process suggested that the Enterobacteriaceae might indirectly facilitate the dissolution and transformation of schwertmannite.

Effect of a weak magnetic field on triclosan removal using zero-valent iron under aerobic and anaerobic conditions

The aim of this study was to quantify the removal of halogenated pollutants (using triclosan as a model pollutant) from aqueous solution by zero-valent iron coupled with a weak magnetic field. We determined the removal efficiency of triclosan from a sodium sulfate solution at different pH values under both aerobic and anaerobic conditions. The removal of triclosan followed pseudo-first-order kinetics in both the presence and absence of a weak magnetic field. The calculated rate constants indicated higher removal efficiencies of triclosan under the aerobic condition compared to the anaerobic condition. In addition, increase of triclosan removal from acidic solutions was achieved with the assistance of weak magnetic field. X-ray diffraction and X-ray photoelectron spectroscopy analysis indicated that FeO(OH) and Fe3O4 were the main aerobic transformation products, suggesting that the zero-valent iron surfaces were completely oxidized. The aerobic and anaerobic transformation products of triclosan were analyzed by liquid chromatography tandem mass spectrometry. The results indicated that the application of a weak magnetic field could be an efficient and cheap treatment process to improve the removal of halogenated pollutants by zero-valent iron, which may be developed for future use.

Comprehensive Effect of P-Nitrophenol Degradation in the Iron Oxide/Oxalate Suspension

The degradation and transformation of p-nitrophenol (PNP) was evaluated with as-prepared iron oxides (γ-FeOOH, Fe3O4, and α-Fe2O3) as catalyst. Results showed that α-Fe2O3 exhibited higher catalytic activity than the other two samples for reduction transformation and oxidative degradation of PNP. α-Fe2O3 showed higher surface-bound Fe(II) contents in the presence of oxalic acid and stronger affinity to PNP, leading to an increase in PNP reductive transformation. And α-Fe2O3 could effectively adsorb visible light and hinder the recombination of charge carriers, resulting in higher oxidative degradation activity. p-Aminophenol (PAP), as the main reduction transformation product of PNP, could be removed further by oxidative degradation in the reaction system itself. A possible mechanism was suggested for the comprehensive effect of PNP degradation during the reaction process.

APPROACHES TO TOXICOLOGICAL AND HYGIENE ASSESSMENT OF UNSTABLE METAL-ORGANIC COMPOUNDS ON THE EXAMPLE OF MAGNESOCENE (CP2MG) (BIS (CYCLOPENTADIENYL) MAGNESIUM)

Approaches to the evaluation of toxicity and hazard of unstable substance bis(cyclopentadienyl) magnesium MAGNESOCENE (Cp2Mg)) are presented . The toxicity of the substance is determined by its main transformation products -magnesium oxide, magnesium hydroxide and cyclopentadiene. Due to the instability of the substance (it exists only in an inert environment) it is not possible to conduct studies on its sensitizing effect ,its reprotoxic, teratogenic, mutagenic and carcinogenic action on the organism. Control of the unstable compound bis (cyclopentadienyl) magnesium in the air of the working area and human habitat should be based on its transformation products: magnesium oxide and cyclopentadiene.

Correlation between pH and molar iron/ligand ratio during ciprofloxacin degradation by photo-Fenton process: Identification of the main transformation products

Ciprofloxacin has been determined with high frequency in studies involving environmental waters matrixes. However, no study evaluating the correlation between the initial pH and molar iron/organic ligand ratio has been published. This paper describes the degradation of the antibiotic ciprofloxacin by the photo-Fenton process using different sources of iron (Fe2+, Fe3+ and Fe3+-citrate and Fe3+-oxalate, named FeCit and FeOx, respectively) and molar iron/organic ligand ratios at initial pH values of 2.5 and 6.5. The best results at initial pH 2.5 were achieved using FeCit and FeOx at molar iron/organic ligand ratios of 1:1 and 1:3 respectively, when the ciprofloxacin concentration reached values below the quantitation limit of the HPLC after 20 min of treatment. However, at initial pH 6.5, improvements in the results (15% for FeCit, and 46% for FeOx) were achieved by increasing the molar iron/organic ligand ratios to 1:4 (FeCit) and 1:9 (FeOx), respectively. Three transformation products, (C17H19FN3O4, m/z 348; C17H21FN3O5, m/z 366; and C13H12FN2O3, m/z 263) of ciprofloxacin degradation were identified, one of them not yet being reported in the literature (C17H21FN3O5, m/z 366). Their formation and degradation was monitored and the initial steps of their formation and degradation were proposed. The results show that the piperazine ring is more susceptible to hydroxyl radical attack than the quinolone ring, which persists in the intermediates identified. Therefore, this process can be a good alternative for the treatment of this type of pollutant at near-neutral conditions.

Spatial (bio)accumulation of pharmaceuticals, illicit drugs, plasticisers, perfluorinated compounds and metabolites in river sediment, aquatic plants and benthic organisms.

Organic contaminants such as pharmaceuticals, personal care products (PPCPs) and other emerging contaminants (ECs) are known to persist in the aquatic environment and many are indicated as endocrine, epigenetic, or other toxicants. Typically, the study of PPCPs/ECs in the aquatic environment is limited to their occurrence dissolved in river water. In this study, accumulation and spatial distribution of thirteen PPCPs/ECs were assessed in aquatic sediment (n=23), periphyton (biofilm, n=8), plants Callitriche sp. (n=8) and Potamogeton sp. (n=7) as well as amphipod crustaceans (Gammarus pulex, n=10) and aquatic snails (Bithynia tentaculata, n=9). All samples (n=65) were collected from the Hogsmill, Blackwater and Bourne Rivers in southern England. Targeted PPCPs/ECs included pharmaceuticals, plasticisers, perfluorinated compounds, illicit drugs and metabolites. Extraction from solid matrices occurred using ultrasonic-assisted extraction followed by an in-house validated method for solid-phase extraction and subsequent liquid-chromatography tandem mass-spectrometry. Field-derived bioconcentration-factors and biota-sediment accumulation-factors were determined for all studied biota. Residues of studied contaminants were found in all sediment and biota. Concentrations of contaminants were generally higher in biota than sediment. Evidence suggests that the studied aquatic plants may effectively degrade bisphenol-A into its main transformation product hydroxyacetophenone, potentially mediated by cytochrome p450 and internalisation of contaminants into the cellular vacuole. A positive association between both hydrophobicity and PFC chain length and contaminant accumulation was observed in this work. Only PFCs, plasticisers and HAP were classified as either 'bioaccumulative' or 'very bioaccumulative' using BCF criteria established by guidelines of four governments. Contaminants appeared to be differentially bioaccumulative in biota, indicating there may be a need for a species-specific BCF/BSAF classification system. These data form a detailed accounting of PPCP/EC fate and distribution in the aquatic environment highlighting accumulation at lower trophic levels, a potential source for higher organisms.

Effect of p-nitrophenol degradation in aqueous dispersions of different crystallized goethites

Abstract Different crystallized goethites (α-FeOOH) were obtained via air oxidation. The reductive transformation and oxidative degradation of p-nitrophenol (PNP) was evaluated with as-prepared α-FeOOH as catalyst. Results showed that the α-FeOOH sample exhibited high reactivity for reduction transformation and oxidative degradation of PNP with decreasing degree of catalyst crystallization. In α-FeOOH/Fe(II) systems, low-crystalline α-FeOOH showed high surface-bound Fe(II) contents on the catalyst surface, which led to elevated PNP rates of reduction transformation. p-Aminophenol (PAP), as the main reduction transformation product of PNP, could be removed and mineralized further by photo-Fenton reaction in the low-crystalline α-FeOOH/H2O2 system under visible light irradiation. A possible mechanism was suggested for the comprehensive effect of PNP degradation during the reaction process.

Evaluation of a Commercially Available Enzyme‐Linked Immunosorbent Assay and a Liquid Chromatography–Tandem Mass Spectrometric Method for the Analysis of Glyphosate in Wheat, Oats, Barley, Malt, and Lentils

An accurate and precise ultra‐high performance liquid chromatography with tandem mass spectrometry (UHPLC‐MS/MS) method was validated for the analysis of glyphosate and its main transformation product (aminomethylphosphonic acid) in barley, malt, wheat, oats, and lentils. The validation data demonstrated good performance of the method. This UHPLC‐MS/MS method was also used to evaluate the performance of a commercially available enzyme‐linked immunosorbent assay (ELISA) test kit. For all of the grain matrices examined, the ELISA showed poor accuracy and precision at its stated lower working limit of 0.075 mg/kg; however, performance was acceptable at 0.30 mg/kg, as well as higher concentrations relevant to established maximum residue limits. At these relevant concentrations, the ELISA also produced results higher than the UHPLC‐MS/MS method. Although results from the two methods were linearly correlated, differences in the result values from the two methods differed among the grains studied and ranged from +1% for oats to +40% for glyphosate concentrations in barley. ELISA is a useful tool that is complemented by the comprehensive and sensitive UHPLC‐MS/MS method.

Priority pesticide dichlorvos removal from water by ozonation process: Reactivity, transformation products and associated toxicity

Abstract The treatability of waters contaminated with priority pesticide dichlorvos (DDVP) by means of ozonation has been assessed for the first time. In order to do so, reaction kinetics, transformation mechanisms and associated toxicity have been inspected in detail. Second-order rate constants of DDVP reactions with O 3 and OH were determined to be 590 and 2.2·10 9 M −1 s −1 , respectively. These values partly explained the degradation profiles obtained during experiments with and without the presence of an OH scavenger, in which the significant contribution of the indirect degradative route in the removal of DDVP was revealed. LC-MS analyses for ozonated samples allowed the elucidation of desmethyl dichlorvos (d-DDVP), dichloroacetic acid (DCA) and dimethyl phosphate (DMP) as main transformation products (TPs). DMP was found to be present in both O 3 and OH -mediated oxidation pathways. Three possible degradation routes were proposed for OH degradation, whereas the direct oxidation by O 3 was only well-explained by the addition of this oxidant to the double bond of DDVP dichlorovinyl moiety. Microtox® bioassays revealed the inability of molecular ozone to reduce the toxicity of the medium and pointed out the importance of OH contribution in the degradation process. In general, ozonation could be a suitable treatment alternative for DDVP, formed TPs and associated toxicity abatement.

Photodegradation kinetics, transformation, and toxicity prediction of ketoprofen, carprofen, and diclofenac acid in aqueous solutions.

Photodegradation of 3 commonly used nonsteroidal anti-inflammatory drugs, ketoprofen, carprofen, and diclofenac acid, was conducted under ultraviolet (UV) irradiation. The kinetic results showed that the 3 pharmaceuticals obeyed the first-order reaction with decreasing rate constants of 1.54 × 10-4 , 5.91 × 10-5 , and 7.78 × 10-6 s-1 for carprofen, ketoprofen, and diclofenac acid, respectively. Moreover, the main transformation products were identified by ion-pair liquid-liquid extraction combined with injection port derivatization-gas chromatography-mass spectrometry and high-performance liquid chromatography-quadrupole-time of flight mass spectrometric analysis. There were 8, 3, and 6 transformation products identified for ketoprofen, carprofen, and diclofenac acid, respectively. Decarboxylation, dechlorination, oxidation, demethylation, esterification, and cyclization were proposed to be associated with the transformation of the 3 pharmaceuticals. Toxicity prediction of the transformation products was conducted on the EPI Suite software based on ECOSAR model, and the results indicate that some of the transformation products were more toxic than the parent compounds. The present study provides the foundation to understand the transformation behavior of the studied pharmaceuticals under UV irradiation. Environ Toxicol Chem 2017;36:3232-3239. © 2017 SETAC.

Fate of pharmaceuticals and their transformation products in integrated membrane systems for wastewater reclamation

The removal of pharmaceuticals (PhACs) present in urban wastewater by membrane bioreactors (MBRs) followed by reverse osmosis (RO) or nanofiltration (NF) membranes has been frequently addressed in the literature. However, data regarding the removal of their main human metabolites and transformation products (TPs) is still scarce. In this study, the presence of 13 PhACs and 20 of their metabolites and TPs was monitored during 2 consecutive years in the different treatment steps of urban raw wastewater (sewer, primary treatment, MBR and RO/NF). Rejection of the selected contaminants when using low pressure NF membranes (NF-90) or RO membranes (ESPA 2) after the MBR step was also investigated. The analgesic acetaminophen, which was found at the highest concentrations in the sewer and influent samples (18–74µgL−1) over the two experimental periods, was fully eliminated during MBR treatment. Those PhACs that were only partially removed after the MBR, were almost completely removed (>99%) by the RO membrane working under different process conditions. At a similar average permeate fluxes (18Lm−2h−1), the NF membrane showed high removal efficiencies (>90%) for all of the PhACs and their metabolites, though lower than those achieved by the RO membrane. When the flux of the NF90 membrane was increased to 30Lm−2h−1 (while still operating at a feed pressure lower than the RO membrane at 18Lm−2h−1) the performance of the membrane increased, achieving 98% rejection of PhACs.

Biotransformation of ritalinic acid by laccase in the presence of mediator TEMPO

Methylphenidate is widely used as a medication for the treatment of attention deficit hyperactivity disorder (ADHD) in children. Less than 1% of methylphenidate is excreted unchanged in urine, while 80% of an oral dose is excreted as ritalinic acid (which is reportedly poorly degradable). This study aims to investigate the biotransformation of ritalinic acid by free and immobilized enzymes. The influence of various laccase mediators on biotransformation efficiency has been tested. Formation of the main transformation products has been monitored and their potential structures suggested. The effective transformation of ritalinic acid was observed only in the presence of 2,2,6,6-tetramethylpiperidine 1-oxyl mediator (TEMPO). The most effective enzyme was the laccase of T. versicolor 159. The main transformation product was an N-methyl derivative of ritalinic acid. Ritalinic acid was also reduced to aldehyde and alcohol, and a broad spectrum of intermediate complexes with oxoammonium ion of TEMPO were detected. This is the first time the biotransformation of ritalinic acid has been investigated in detail.

Ozone pretreatment of process waste water generated in course of fluoroquinolone production

During production of active pharmaceutical ingredients, process waste water is generated at several stages of manufacturing. Whenever possible, the resulting waste water will be processed by conventional waste water treatment plants. Currently, incineration of the process waste water is the method to eliminate compounds with high biological activity. Thus, ozone treatment followed by biological waste water treatment was tested as an alternative method. Two prominent representatives of the large group of fluoroquinolone antibiotics (ciprofloxacin and moxifloxacin) were investigated, focussing on waste water of the bulk production. Elimination of the target compounds and generation of their main transformation products were determined by liquid chromatography – high resolution mass spectrometry (LC-HRMS). The obtained results demonstrated, that the concentration of moxifloxacin and its metabolites can be effectively reduced (>99.7%) prior entering the receiving water. On the contrary, the concentration of ciprofloxacin and its metabolites remained too high for safe discharge, necessitating application of prolonged ozonation for its further degradation. The required ozonation time can be estimated based on the determined kinetics. To assure a low biological activity the ecotoxicity of the ozonated waste water was investigated using three trophic levels. By means of multiple-stage mass spectrometry (MSn) experiments several new transformation products of the fluoroquinolones were identified. Thus, previously published proposed structures could be corrected or confirmed.

Effect of operational and water quality parameters on conventional ozonation and the advanced oxidation process O3/H2O2: Kinetics of micropollutant abatement, transformation product and bromate formation in a surface water

The efficiency of ozone-based processes under various conditions was studied for the treatment of a surface water (Lake Zürich water, Switzerland) spiked with 19 micropollutants (pharmaceuticals, pesticides, industrial chemical, X-ray contrast medium, sweetener) each at 1 μg L−1. Two pilot-scale ozonation reactors (4–5 m3 h−1), a 4-chamber reactor and a tubular reactor, were investigated by either conventional ozonation and/or the advanced oxidation process (AOP) O3/H2O2. The effects of selected operational parameters, such as ozone dose (0.5–3 mg L−1) and H2O2 dose (O3:H2O2 = 1:3–3:1 (mass ratio)), and selected water quality parameters, such as pH (6.5–8.5) and initial bromide concentration (15–200 μg L−1), on micropollutant abatement and bromate formation were investigated. Under the studied conditions, compounds with high second-order rate constants kO3>104 M−1 s−1 for their reaction with ozone were well abated (>90%) even for the lowest ozone dose of 0.5 mg L−1. Conversely, the abatement efficiency of sucralose, which only reacts with hydroxyl radicals (OH), varied between 19 and 90%. Generally, the abatement efficiency increased with higher ozone doses and higher pH and lower bromide concentrations. H2O2 addition accelerated the ozone conversion to OH, which enables a faster abatement of ozone-resistant micropollutants. Interestingly, the abatement of micropollutants decreased with higher bromide concentrations during conventional ozonation due to competitive ozone-consuming reactions, except for lamotrigine, due to the suspected reaction of HOBr/OBr− with the primary amine moieties. In addition to the abatement of micropollutants, the evolution of the two main transformation products (TPs) of hydrochlorothiazide (HCTZ) and tramadol (TRA), chlorothiazide (CTZ) and tramadol N-oxide (TRA-NOX), respectively, was assessed by chemical analysis and kinetic modeling. Both selected TPs were quickly formed initially to reach a maximum concentration followed by a decrease of their concentrations for longer contact times. For the studied conditions, the TP's concentrations at the outlet of the reactors ranged from 0 to 61% of the initial parent compound concentration, CTZ being a more persistent TP against further oxidation than TRA-NOX. Finally, it was demonstrated in both reactors that the formation of bromate (BrO3−), a potentially carcinogenic oxidation by-product, could be controlled by H2O2 addition with a general improvement on micropollutant abatement. Post-treatment by granular activated carbon (GAC) filtration enabled the reduction of micropollutants and TPs concentrations but no changes in bromate were observed. The combined algae assay showed that water quality was significantly improved after oxidation and GAC post-treatment, driven by the abatement of the spiked pesticides (diuron and atrazine).

Dissipation kinetics of organophosphorus pesticides in milled toasted maize and wheat flour (gofio) during storage.

The dissipation/degradation of the pesticides dimethoate, terbufos, disulfoton, and pirimiphos-methyl were evaluated in milled toasted maize and wheat flour (gofio) during three months of storage. Their dissipation kinetics and residual levels were determined, as well as their possible decomposition into some of their main transformation products (disulfoton sulfoxide, terbufos sulfone and disulfoton sulfone). For this purpose, pesticide-free milled toasted maize and wheat samples were spiked with the pesticides, and they were then stored in the darkness at ambient temperature in a closed container to simulate current storage conditions of such packed food. A multiresidue analysis based on the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method was performed for the simultaneous determination of these pesticides and their metabolites. After three months of storage, the dissipation of residues ranged between 34% (pirimiphos-methyl) and 86% (disulfoton) for maize gofio and between 69% (terbufos) and 92% (disulfoton and pirimiphos-methyl) for wheat gofio. The results demonstrated that the degradation was slower in gofio than in wheat gofio and that none of the selected metabolites were detected in any of the samples. Dissipation curves of all studied pesticides fitted to a first-order decay curve in both types of cereals.