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Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics, reaction intermediates, and toxicity assessment Full text
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.
Show more [+] Less [-]Dechlorane Plus in surface soil of North China: levels, isomer profiles, and spatial distribution Full text
2014
Ma, Jin | Qiu, Xinghua | Liu, Di | Zhao, Yifan | Yang, Qiaoyun | Fang, Di
Eighty-seven soil samples collected from North China were analyzed for Dechlorane Plus (DP). The concentrations of DP ranged from not detectable (ND) to 12.21 ng/g with a mean of 0.55 ng/g. The mean concentrations of total DP and syn-DP in four regions of North China were in the following order: Jingjin (Beijing and Tianjin) > Shandong > Shanxi > Hebei, while the mean concentrations of anti-DP in the four regions were in a different order: Shandong > Jingjin > Shanxi > Hebei. The mean fₛyₙvalues for Jingjin (0.27), Hebei (0.24), and Shanxi (0.24) were close to 0.25, while the mean fₛyₙvalue for Shandong (0.31) was closer to 0.35. In addition, the fₛyₙvalue for Shandong was significantly higher (P < 0.01) than those of the other regions (Jingjin, Heibei, and Shanxi), indicating specific sources of DP. Syn-DP displayed a strong linear relationship with anti-DP (R² = 0.74), indicating that no obvious stereoselective process occurred in the soil of North China. Ordinary kriging was undertaken to map the spatial patterns of DP. High concentrations of DP in soils were present in south of Shanxi, central Hebei, south of Tianjin, and the south and northeast of Shandong, which were suggested to be connected with human activities such as e-waste dismantling.
Show more [+] Less [-]Sequential electrochemical treatment of dairy wastewater using aluminum and DSA-type anodes Full text
2014
Borbón, Brenda | Oropeza-Guzman, Mercedes Teresita | Brillas, Enric | Sirés, Ignasi
Dairy wastewater is characterized by a high content of hardly biodegradable dissolved, colloidal, and suspended organic matter. This work firstly investigates the performance of two individual electrochemical treatments, namely electrocoagulation (EC) and electro-oxidation (EO), in order to finally assess the mineralization ability of a sequential EC/EO process. EC with an Al anode was employed as a primary pretreatment for the conditioning of 800 mL of wastewater. A complete reduction of turbidity, as well as 90 and 81 % of chemical oxygen demand (COD) and total organic carbon (TOC) removal, respectively, were achieved after 120 min of EC at 9.09 mA cm⁻². For EO, two kinds of dimensionally stable anodes (DSA) electrodes (Ti/IrO₂-Ta₂O₅and Ti/IrO₂-SnO₂–Sb₂O₅) were prepared by the Pechini method, obtaining homogeneous coatings with uniform composition and high roughness. The·OH formed at the DSA surface from H₂O oxidation were not detected by electron spin resonance. However, their indirect determination by means of H₂O₂measurements revealed that Ti/IrO₂-SnO₂–Sb₂O₅is able to produce partially physisorbed radicals. Since the characterization of the wastewater revealed the presence of indole derivatives, preliminary bulk electrolyses were done in ultrapure water containing 1 mM indole in sulfate and/or chloride media. The performance of EO with the Ti/IrO₂-Ta₂O₅anode was evaluated from the TOC removal and the UV/Vis absorbance decay. The mineralization was very poor in 0.05 M Na₂SO₄, whereas it increased considerably at a greater Cl⁻content, meaning that the oxidation mediated by electrogenerated species such as Cl₂, HClO, and/or ClO⁻competes and even predominates over the·OH-mediated oxidation. The EO treatment of EC-pretreated dairy wastewater allowed obtaining a global 98 % TOC removal, decreasing from 1,062 to <30 mg L⁻¹.
Show more [+] Less [-]Larvicidal, ovicidal, and oviposition-deterrent activities of four plant extracts against three mosquito species Full text
2014
Prathibha, K. P. | Raghavendra, B. S. | Vijayan, V. A.
In mosquito control programs, insecticides of botanical origin have the potential to eliminate eggs, larvae, and adults. So, the larvicidal, ovicidal, and oviposition-deterrent activities of petroleum ether and ethyl acetate extracts of the leaves of Eugenia jambolana, Solidago canadensis, Euodia ridleyi, and Spilanthes mauritiana were assayed against the three vector mosquito species, namely Anopheles stephensi, Aedes aegypti, and Culex quinquefasciatus. The larval bioassay was conducted following the World Health Organization method. The maximum larval mortality was found with ethyl acetate extract of S. mauritiana against the larvae of A. stephensi, A. aegypti, and C. quinquefasciatus with LC₅₀values of 11.51, 28.1, 14.10 ppm, respectively. The mean percent hatchability of the ovicidal activity was observed at 48-h post-treatment. The percent hatchability was found to be inversely proportional to the concentration of the extract and directly proportional to the number of eggs. The flower head extract of S. mauritiana gave 100 % mortality followed by E. ridleyi, S. canadensis, and E. jambolana against the eggs of the three mosquito vectors. For oviposition-deterrent effect, out of the five concentrations tested (20, 40, 60, 80, and 100 ppm), the concentration of 100 ppm showed a significant egg laying-deterrent capacity. The oviposition activity index value of E. jambolana, E. ridleyi, S. canadensis, and S. mauritiana against A. aegypti, A. stephensi, C. quinquefasciatus at 100 ppm were −0.71, −0.71, −0.90, −0.93, −0.85, −0.91, −1, −1, −0.71, −0.85, −1, and −1, respectively. These results suggest that the leaf/flower extracts of certain local plants have the potential to be developed as possible eco-friendly means for the control of mosquitoes.
Show more [+] Less [-]Environmental assessment on electrokinetic remediation of multimetal-contaminated site: a case study Full text
2014
Kim, Do-Hyung | Yoo, Jong-Chan | Hwang, Bo-Ram | Yang, Jung-Seok | Baek, Kitae
In this study, an environmental assessment on an electrokinetic (EK) system for the remediation of a multimetal-contaminated real site was conducted using a green and sustainable remediation (GSR) tool. The entire EK process was classified into major four phases consisting of remedial investigations (RIs), remedial action construction (RAC), remedial action operation (RAO), and long-term monitoring (LTM) for environmental assessment. The environmental footprints, including greenhouse gas (GHG) emissions, total energy used, air emissions of criteria pollutants, such as NOₓ, SOₓ, and PM₁₀, and water consumption, were calculated, and the relative contribution in each phase was analyzed in the environmental assessment. In the RAC phase, the relative contribution of the GHG emissions, total energy used, and PM₁₀emissions were 77.3, 67.6, and 70.4 %, respectively, which were higher than those of the other phases because the material consumption and equipment used for system construction were high. In the RAO phase, the relative contributions of water consumption and NOₓand SOₓemissions were 94.7, 85.2, and 91.0 %, respectively, which were higher than those of the other phases, because the water and electricity consumption required for system operation was high. In the RIs and LTM phases, the environmental footprints were negligible because the material and energy consumption was less. In conclusion, the consumable materials and electrical energy consumption might be very important for GSR in the EK remediation process, because the production of consumable materials and electrical energy consumption highly affects the GHG emissions, total energy used, and air emissions such as NOₓand SOₓ.
Show more [+] Less [-]Source, distribution, and health risk assessment of polycyclic aromatic hydrocarbons in urban street dust from Tianjin, China Full text
2014
Yu, Binbin | Xie, Xiujie | Ma, Lena Q. | Kan, Haidong | Zhou, Qixing
To better assess and understand potential health risk of urban residents exposed to urban street dust, the total concentration, sources, and distribution of 16 polycyclic aromatic hydrocarbons (PAHs) in 87 urban street dust samples from Tianjin as a Chinese megacity that has undergone rapid urbanization were investigated. In the meantime, potential sources of PAHs were identified using the principal component analysis (PCA), and the risk of residents’ exposure to PAHs via urban street dust was calculated using the Incremental Lifetime Cancer Risk (ILCR) model. The results showed that the total PAHs (∑PAHs) in urban street dust from Tianjin ranged from 538 μg kg⁻¹to 34.3 mg kg⁻¹, averaging 7.99 mg kg⁻¹. According to PCA, the two to three- and four to six-ring PAHs contributed 10.3 and 89.7 % of ∑PAHs, respectively. The ratio of the sum of major combustion specific compounds (ΣCOMB) / ∑PAHs varied from 0.57 to 0.79, averaging 0.64. The ratio of Ant/(Ant + Phe) varied from 0.05 to 0.41, averaging 0.10; Fla/(Fla + Pyr) from 0.40 to 0.68, averaging 0.60; BaA/(BaA + Chry) from 0.29 to 0.51, averaging 0.38; and IcdP/(IcdP + BghiP) from 0.07 to 0.37, averaging 0.22. The biomass combustion, coal combustion, and traffic emission were the main sources of PAHs in urban street dust with the similar proportion. According to the ILCR model, the total cancer risk for children and adults was up to 2.55 × 10⁻⁵and 9.33 × 10⁻⁵, respectively.
Show more [+] Less [-]Metal distribution and spectroscopic analysis after soil washing with chelating agents and humic substances Full text
2014
Tsang, Daniel C. W. | Hartley, Neil R.
Biodegradable chelating agents ([S,S]-ethylenediamine-N,N-disuccinic acid (EDDS) and glutamic-N,N-diacetic acid (GLDA)) and natural humic substances (lignite-derived, standard, and commercially available humic acids) are potentially useful for enhancing soil remediation of timber treatment sites. This study integrated macroscopic and spectroscopic analyses to assess their influence on the distribution and chemical speciation of the remaining metals as well as their interaction with the soil surface after 48-h washing of a field-contaminated soil. The results demonstrated that EDDS and GLDA were an appealing alternative to non-biodegradable ethylenediamine-tetraacetic acid, but the three humic substances were less effective. As shown by sequential extractions, Cu was primarily extracted from the carbonate fraction while Cr and As extraction resulted from (co-)dissolution of the oxide fraction. As a result, the relative proportion of strongly bound organic matter and residual fractions increased by 7–16 %. However, it was noteworthy that the exchangeable fraction also increased by 5–11 %, signifying that a portion of the remaining metals was destabilized by chelating agents and transformed to be more labile in the treated soil. The X-ray photoelectron spectroscopy spectra confirmed the substantial removal of readily accessible Cu from the soil surface, but Cr maintained its original chemical forms of trivalent chromium oxides and iron–chromium coprecipitates, whereas As remained as arsenic trioxide/pentoxide and copper arsenate precipitates. On the other hand, the absence of characteristic peaks of adsorbed carboxylate groups in the Fourier-transform infrared (FTIR) spectra inferred that the extent of adsorption of chelating agents and humic substances on the bulk soil was insufficient to be characterized by FTIR analysis. These results suggested that attention should be paid to the exchangeable fraction of Cu and oxides/coprecipitates of As prior to possible on-site reuse of the treated soil.
Show more [+] Less [-]Lipid-soluble conjugates of hydroxylated polybrominated diphenyl ethers in blue mussels from the Baltic Sea Full text
2014
Lindqvist, Dennis | Jensen, Søren | Asplund, L. (Lillemor)
Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) of proposed natural origin have been detected throughout the food web of the Baltic Sea. Some OH-PBDEs have been shown to disrupt oxidative phosphorylation and the thyroid hormone system in exposed organisms. This paper describes an investigation into the fate of OH-PBDEs in the Baltic Sea’s predominant specie, the blue mussel. The main focus was on the conjugation of OH-PBDEs with lipophilic moieties (e.g., fatty acids) and the potential role this transformation mechanism may have in heavily exposed mussels in nature. Analytical methods were developed to accurately determine the concentrations of these conjugates in blue mussels collected on different occasions during the summer in a coastal area of the Baltic proper. The measured concentrations of conjugated OH-PBDEs were compared to those of the unconjugated parent compounds, and it was found that in some cases, the levels of the conjugated derivatives can be equal or even higher than the levels of the unconjugated OH-PBDEs. This is, to our knowledge, the first study on lipid-soluble OH-PBDE conjugates, and the first study to investigate the occurrence of such conjugates of halogenated phenolic compounds in environmentally exposed mussels. The mussels were also found to contain hydrolysable water-soluble derivatives of OH-PBDEs (such as e.g., glucuronic acid and/or sulfate conjugates etc.). These were tentatively determined to be of lower concentration (by up to an order of magnitude) than that of the OH-PBDEs which were conjugated with lipophilic moieties.
Show more [+] Less [-]Rapid and efficient removal of Ni2+ from aqueous solution by the one-pot synthesized EDTA-modified magnetic nanoparticles Full text
2014
Chen, Junyong | Hao, Yongmei | Chen, Man
A facile one-pot process has been proposed to prepare the novel ethylenediaminetetraacetic acid (EDTA)-modified magnetite nanoparticles (EDTA-MNPs). The bared Fe₃O₄magnetite nanoparticles and EDTA-MNPs were characterized using FTIR spectroscopy, TEM, VSM, and X-ray diffraction. The application of the modified magnetite nanoparticles for metal ion uptake was studied using Ni²⁺as a model. The adsorption was fast and the equilibrium was established within 5 min, and the adsorption kinetics of Ni²⁺onto EDTA-MNPs followed the pseudo second-order chemisorption mechanism. Maximum adsorption capacity for Ni²⁺reached as high as 41.3 mg/g at pH 6. The successive adsorption–desorption studies indicated that the EDTA-MNPs kept the adsorption and desorption efficiencies constant over ten cycles. Importantly, EDTA-MNPs were able to remove nearly 100 % of Ni²⁺from real water.
Show more [+] Less [-]Spatial and temporal distribution of the leaching of surface applied tracers from an irrigated monolith of a loamy vineyard soil Full text
2014
Bloem, E. | Hermon, K. M. | Rooij, G. H. de | Stagnitti, F.
Fresh water scarcity is an increasing problem worldwide. Strategies to alleviate water scarcity include the use of low-quality water for irrigation. The risk of groundwater contamination by pollutants in this water is affected by soil heterogeneity and preferential flow. These risk factors can be assessed by measuring the spatio-temporal redistribution of uniformly applied water and solutes. We placed a soil monolith (height 29 cm) from an Australian vineyard on a 100-cell multi-compartment sampler (MCS). At this vineyard, treated wastewater is used in response to the severe shortage of water in the summer. We studied the leaching risk associated with heterogeneous or preferential flow by irrigating the soil column with 24 applications to simulate one year. We applied simulated rainfall as well as wastewater (which contained chloride) during summer while relying on rainfall only in winter. We compared the chloride leaching with the leaching of bromide, which was applied during one of the applications as a pulse. During the entire simulated year, leaching of solutes from the monolith was measured. The results indicate that the assumption of uniform flow would underestimate the risk for the fresh groundwater reserves: 25 % of the solutes are transported though 6 % of the soil’s cross-section. The spatial distribution of drainage and solute leaching varied little during the experiment. Consequently, the mass flux density pattern of the bromide pulse was comparable to that of the repeatedly applied chloride. However, the MCS data suggested lateral ‘escape’ from chloride to non-mobile areas, which means in the long run, considerable quantities of these solutes can build up in areas that do not receive irrigation water.
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