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Occurrence and distribution of oligomeric organophosphorus flame retardants in different treatment stages of a sewage treatment plant
2018
Liang, Gang | Shi, Fengqiong | Liu, Jingfu
Oligomeric organophosphate esters (OOPEs) like 2,2-bis(chloromethyl)-propane-1,3-diyltetrakis (2-chloroethyl) bisphosphate (V6), resorcinol bis(diphenylphosphate) (RDP) and bisphenol A bis(diphenylphosphate) (BDP), are widely used as alternatives of Deca-BDE in plastic and electronic consumer products. However, studies on the environmental occurrence and fate of OOPEs are very scarce. This work studied the occurrence, distribution and fate of V6, BDP and RDP during the different treatment stages of a sewage treatment plant (STP) in Beijing, China. To accomplish this, a method to analyze trace V6, BDP and RDP in suspended solids samples and aqueous samples of sewage and sludge was developed by using liquid chromatography tandem mass spectrometry (LC-MS/MS). Using this method, BDP and RDP were detected for the first time in suspended solids of sewage and sludge with a concentration of 2.06–5.82 ng/g dry weight and 0.44–3.45 ng/g dry weight, respectively, whereas their concentration level in the aqueous phase of these samples were below the detection limits of the method. However, V6 was detected in all treatment stages of the STP, with concentrations in the range of 10.2–27.1 ng/L in aqueous phase and 0.40–1.73 ng/g dw in solid phase. Mass balance results indicated that 75.6% of the original V6 mass flow was discharged along with effluent, while 83.3% and 72.2% of the initial RDP and BDP mass flow were lost due to biodegradation, respectively. Nevertheless, compared to the 14 widely used monomeric organophosphate esters (MOPEs), the concentration levels of OOPEs in this studied STP were relatively low.
Mostrar más [+] Menos [-]Adsorption, Kinetics and Equilibrium Studies on Removal of Catechol and Resorcinol from Aqueous Solution Using Low-Cost Activated Carbon Prepared from Sunflower (Helianthus annuus) Seed Hull Residues
2018
Vunain, Ephraim | Houndedjihou, Dégninou | Monjerezi, Maurice | Muleja, Adolp Anga | Kodom, BarthélémyTomkouani
This study reports on the feasibility of remediation of catechol- and resorcinol-contaminated water using low-cost sunflower seed hull activated carbon (SSHAC). Sunflower seed hull (SSH), an abundant agricultural waste in Malawi, was used as precursor to prepare highly porous activated carbon by physicochemical activation, with zinc chloride (ZnCl₂) as an activating agent. The activated carbon was characterized by FTIR, SEM-EDS, XRD and BET analyses. In this work, pertinent parameters that affect the adsorption efficiency—pH, initial adsorbate concentration, contact time, adsorbent dosage, and solution temperature—were investigated in batch mode. At the same experimental conditions, more catechol was adsorbed than resorcinol may be due to the compound’s affinity towards water and the position of the hydroxyl group on the benzene ring. A maximum equilibrium adsorption of 271 and 250 mg/g was obtained at pH 9.0 and pH 8.0 for catechol and resorcinol, respectively. The adsorption behaviour of both adsorbates (catechol and resorcinol) on SSHAC can be well described by Langmuir isotherm model and pseudo-second-order kinetic model. The value ∆G, ∆S and ∆H indicated spontaneous and endothermic adsorption process. The adsorption process was readily reversible allowing reusability of the adsorbate. This study’s outcome is value addition to this category of wastes for environmental protection.
Mostrar más [+] Menos [-]Changes in levels of legacy and emerging organophosphorus flame retardants and plasticizers in indoor dust from a former e-waste recycling area in South China: 2013–2017
2022
Tang, Bin | Christia, Christina | Luo, Xiao-Jun | Covaci, Adrian | Poma, Giulia | Mai, Bi-Xian
To assess the impacts of e-waste regulations on environmental pollution, the levels, compositions, and human exposure assessment of organophosphorus flame retardants (PFRs), emerging PFRs (ePFRs), phthalate esters (PAEs), and alternative plasticizers (APs) were investigated in indoor dust samples collected from homes in a former e-waste dismantling area in 2013 and in 2017, 4 years after the implementation of legislation and regulations governing e-waste dismantling activities in this area. The median concentrations of ΣPFRs, ΣePFRs, ΣPAEs, and ΣAPs in dust decreased from 5680, 1650, 167,200, and 140,600 ng/g in 2013 to 1210, 476, 95,000, and 45,300 ng/g in 2017, respectively, suggesting that the national and local regulations prohibiting primitive e-waste dismantling activities is effective in mitigating the pollution status for these chemicals. In the analyzed dust samples, tris(1-chloro-2-propyl) phosphate (TCIPP), triphenyl phosphate (TPHP), resorcinol bis(diphenylphosphate) (RDP), and bisphenol A-bis(diphenyl phosphate) (BDP) were the major PFRs/ePFRs, contributing to 77% and 76% of the total PFRs/ePFRs in 2013 and 2017, respectively. Di(2-ethylhexyl) phthalate (DEHP), di-iso-nonyl phthalate (DINP), di-iso-decyl phthalate (DIDP), and di-n-butyl phthalate (DNBP) were the major PAEs/APs, with contributions of 89% and 95% for the total PAEs/APs in 2013 and 2017, respectively. The results of the human exposure assessment demonstrated that exposure to these levels of the target chemicals via dust ingestion and dermal contact was unlikely to cause health concerns for local residents.
Mostrar más [+] Menos [-]Correction to: Adsorption, Kinetics and Equilibrium Studies on Removal of Catechol and Resorcinol from Aqueous Solution Using Low-Cost Activated Carbon Prepared from Sunflower (Helianthus annuus) Seed Hull Residues
2019
Vunain, Ephraim | Houndedjihou, Dégninou | Monjerezi, Maurice | Muleja, Adolph Anga | Kodom, BarthélémyTomkouani
In the original publication, the given name of the fourth author was mispelled as Adolp instead of Adolph. The correct name of the fourth author is Adolph Anga Muleja.
Mostrar más [+] Menos [-]Effect of Nitrite on the Formation of Trichloronitromethane (TCNM) During Chlorination of Polyhydroxy-Phenols and Sugars
2017
Gan, Guojuan | Qiu, Lin | Wu, Huan | Hong, Huachang | Mazumder, Asit | Pan, Xiangliang | Liang, Yan
Occurrence of halonitromethanes (HNMs) in drinking water has been a concern recently due to the potentially high human health risks of HNMs. Mechanisms of formation of HNMs during disinfection has remained controversial. The objective of this study was to investigate the effects of nitrite on the formation of trichloronitromethane (TCNM), a dominant HNM species occurring in chlorinated water. Polyhydroxy-phenols (hydroquinone, catechol, resorcinol, and phloroglucinol) and sugars (glucose, maltose, and lactose) were compared as surrogates/model compounds of common organic precursors of humic and non-humic substances in natural organic matter, respectively. The results showed that TCNM was not detectable after chlorinated sugars with the addition of nitrite. Upon chlorinating the polyhydroxy-phenols, TCNM formation varied greatly among different compounds, i.e., resorcinol > phloroglucinol > catechol >> hydroquinone. The results demonstrated that TCNM formation in the presence of nitrite was a function of aromaticity as well as the position and number of hydroxyl groups on the benzene rings of a compound, and the TCNM formation potential of humic substances was greater than that of non-humic substances. For catechol, resorcinol, and phloroglucinol, TCNM formation varied greatly with pH but generally remained stable with the increase of reaction time and temperature.
Mostrar más [+] Menos [-]Analysis of adsorption processes of dissolved organic matter (DOM) on ferrihydrite using surrogate organic compounds
2017
Yang, Yu | Lohwacharin, Jenyuk | Takizawa, S (Satoshi)
Ferrihydrite (Fh) has been recently used in water treatment for removing dissolved organic matter (DOM), but its governing interactions with low-molecular weight DOM are largely unknown. This study aimed to elucidate the influence of chemical structure of DOM on the interactions between functional groups of DOM and Fh using various surrogates representing DOM in natural waters. We tested four surrogate compounds: L-glutamic acid, resorcinol, L-serine, and tannic acid, which represent the main chemical groups of carboxylic and hydroxyl groups; and the Suwannee River NOM (SRNOM) that represents the composition of DOM in natural aquatic systems. Batch adsorption experiments revealed that the DOM adsorption onto Fh was significantly influenced by the steric arrangements of –COOH and –OH functional groups. Both L-serine with α-carboxyl group and resorcinol with hydroxyl groups in meta-position were marginally removed by Fh, indicating that the adsorption of DOM on Fh was determined by their chemical structures and the relative positions of carboxylate and hydroxyl groups. The adsorption of L-glutamic acid was controlled by the pH-dependent ligand exchange of γ-carboxyl groups, which was similar to the SRNOM adsorption. In contrast, adsorption of tannic acid was not affected by pH, which can be explained by a two-step adsorption, namely, ligand exchange followed by multi-layer adsorption to the partitioning phase. The results of kinetic experiments demonstrated that adsorption of DOM by Fh was significant and rapid. The kinetic adsorption data can be expressed by the pseudo-second-order equation, indicating that the adsorption step might be the rate-limiting step.
Mostrar más [+] Menos [-]Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics, reaction intermediates, and toxicity assessment
2014
El-Ghenymy, Abdellatif | Rodríguez, Rosa Ma. (Rosa María) | Brillas, Enric | Oturan, Nihal | Oturan, Mehmet A.
The degradation of 230 mL of a 0.6-mM sulfanilamide solution in 0.05 M Na₂SO₄of pH 3.0 has been studied by electro-Fenton process. The electrolytic cell contained either a Pt or boron-doped diamond (BDD) anode and a carbon-felt cathode. Under these conditions, organics are oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between initially added (and then electrochemically regenerated) Fe²⁺and cathodically generated H₂O₂. From the decay of sulfanilamide concentration determined by reversed-phase liquid chromatography, an optimum Fe²⁺concentration of 0.20 mM in both cells was found. The drug disappeared more rapidly using BDD than Pt, and, in both cases, it was more quickly removed with raising applied current. Almost total mineralization was achieved using the BDD/carbon-felt cell, whereas the alternative use of Pt anode led to a slightly lower mineralization degree. In both cells, the degradation rate was accelerated at higher current but with the concomitant fall of mineralization current efficiency due to the greater increase in rate of the parasitic reactions of hydroxyl radicals. Reversed-phase liquid chromatography allowed the identification of catechol, resorcinol, hydroquinone, p-benzoquinone, and 1,2,4-trihydroxybenzene as aromatic intermediates, whereas ion exclusion chromatography revealed the formation of malic, maleic, fumaric, acetic, oxalic, formic, and oxamic acids. NH₄⁺, NO₃⁻, and SO₄²⁻ions were released during the electro-Fenton process. A plausible reaction sequence for sulfanilamide mineralization involving all detected intermediates has been proposed. The toxicity of the solution was assessed from the Vibrio fischeri bacteria luminescence inhibition. Although it acquired its maximum value at short electrolysis time, the solution was completely detoxified at the end of the electro-Fenton treatment, regardless of the anode used.
Mostrar más [+] Menos [-]New insight into monitoring degradation products during the TiO2-photocatalysis process by multivariate molecular spectroscopy
2017
Stets, Sandra | do Amaral, Bianca | Bach, Larissa | Nagata, Noemi | Peralta-Zamora, Patricio G.
This study focuses on the feasibility of a spectroscopic multivariate method for monitoring the concentration of phenol and its main degradation products during heterogeneous photocatalysis. Phenolic compounds were chosen as model to evaluate the degradation process due to their toxicity and persistence in the environment and also their well-known degradation pathway. The predictive capability of the multivariate method developed by partial least squares regression (PLSR) over the spectral range of 200–350 nm was satisfactory, allowing mean predicted errors below 5.0 % in the simultaneous determination of the target compounds using six latent variables and smoothing spectra. Suitable results were reported for the simultaneous determination of hydroquinone, resorcinol, pyrocatechol, and p-benzoquinone in accordance to the chromatographic method. Characteristics such as simplicity, low cost, and fast data acquisition are remarkable in this procedure, which makes it appropriate for this type of analytical control.
Mostrar más [+] Menos [-]Effect of substituted hydroxyl groups in the changes of solution turbidity in the oxidation of aromatic contaminants
2017
Villota, N | JM, Lomas | LM, Camarero
This paper deals with the changes of turbidity that are generated in aqueous solutions of phenol when they are oxidized by using different Fenton technologies. Results revealed that if the Fenton reaction was promoted with UV light, the turbidity that was generated in the water doubled. Alternatively, the use of ultrasonic waves produced an increase in turbidity which initially proceeded slowly, reaching intensities eight times higher than in the conventional Fenton treatment. As well, the turbidity showed a high dependence on pH. It is therefore essential to control acidity throughout the reaction. The maximum turbidity was generated when operating at pH = 2.0, and it slowly decreased with increasing to a value of pH = 3.0, at which the turbidity was the lowest. This result was a consequence of the presence of ferric ions in solution. At pH values greater than 3.5, the turbidity increased almost linearly until at pH = 5.0 reached its maximum intensity. In this range, ferrous ions may generate an additional contribution of radicals that promote the degradation of the phenol species that produce turbidity. Turbidity was enhanced at ratios R = 4.0 mol H₂O₂/mol C₆H₆O. This value corresponds to the stoichiometric ratio that leads to the production of turbidity-precursor species. Therefore, muconic acid would be a species that generate high turbidity in solution according to its isomerism. Also, the results revealed that the turbidity is not a parameter to which species contribute additively since interactions may occur among species that would enhance their individual contributions to it. Analyzing the oxidation of phenol degradation intermediates, the results showed that meta-substituted compounds (resorcinol) generate high turbidity in the wastewater. The presence of polar molecules, such as muconic acid, would provide the structural features that are necessary for resorcinol to act as a clip between two carboxylic groups, thus establishing directional hydrogen bonds that would generate an adduct in the 2:2 ratio. In addition, some similarity is observed between the turbidity and the presence of dihydroxybenzoquinone. This molecule has a structure that could establish hydrogen bond links with the carboxylic groups in 1:2 ratio. Such supramolecular structures would possess high molecular weight and robustness that would hinder the passage of light through the water, generating high turbidity.
Mostrar más [+] Menos [-]Larvicidal and pupicidal activities of eco-friendly phenolic lipid products from Anacardium occidentale nutshell against arbovirus vectors
2019
de Carvalho, George Harrison Ferreira | de Andrade, Milene Aparecida | de Araújo, Carla Nunes | Santos, Maria Lucília | de Castro, Natália Alves | Charneau, Sébastien | Monnerat, Rose | de Santana, Jaime Martins | Bastos, Izabela Marques Dourado
Aedes aegypti and Culex quinquefasciatus are vectors of diseases that constitute public health problems. The discovery of products capable of inhibiting their development which are less harmful to the environment would have a huge impact on vector control. Here, natural cashew nut shell liquid (CNSL), technical CNSL, anacardic acid, cardanol, and cardol were isolated from Anacardium occidentale and evaluated for larvicidal and pupicidal activity against Ae. aegypti and Cx. quinquefasciatus under laboratory and field conditions. The activities of phenol, resorcinol, salicylic acid, and pentadecane, commercial chemicals similar in structure to nut shell derivatives, were also evaluated. All of the fractions extracted from A. occidentale oil exerted larvicidal effects against both mosquito species (LC₅₀ 5.4–22.6 mg/L), and two of the aforementioned were effective against pupae (LC₅₀ 90.8–109.7 mg/L). Of all the fractions tested, cardol demonstrated the strongest larvicidal and pupicidal effects and presented the most prolonged residual activity against the larvae and pupae of Ae. aegypti and Cx. quinquefasciatus under field conditions. This study suggests that A. occidentale nut shell derivatives are sustainable and promising candidates for the development of novel insecticides to overcome the problem of harmful chemical insecticides.
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