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Photocatalytic degradation of acetaminophen in modified TiO2 under visible irradiation
2014
Dalida, Maria Lourdes P. | Amer, Kristine Marfe S. | Su, Chia-Chi | Lü, Mingjun
This study investigated the photocatalytic degradation of acetaminophen (ACT) in synthetic titanium dioxide (TiO₂) solution under a visible light (λ >440 nm). The TiO₂photocatalyst used in this study was synthesized via sol–gel method and doped with potassium aluminum sulfate (KAl(SO₄)₂) and sodium aluminate (NaAlO₂). The influence of some parameters on the degradation of acetaminophen was examined, such as initial pH, photocatalyst dosage, and initial ACT concentration. The optimal operational conditions were also determined. Results showed that synthetic TiO₂catalysts presented mainly as anatase phase and no rutile phase was observed. The results of photocatalytic degradation showed that LED alone degraded negligible amount of ACT but with the presence of TiO₂/KAl(SO₄)₂, 95 % removal of 0.10-mM acetaminophen in 540-min irradiation time was achieved. The synthetic TiO₂/KAl(SO₄)₂presented better photocatalytic degradation of acetaminophen than commercially available Degussa P-25. The weak crystallinity of synthesized TiO₂/NaAlO₂photocatalyst showed low photocatalytic degradation than TiO₂/KAl(SO₄)₂. The optimal operational conditions were obtained in pH 6.9 with a dose of 1.0 g/L TiO₂/KAl(SO₄)₂at 30 °C. Kinetic study illustrated that photocatalytic degradation of acetaminophen fits well in the pseudo-first order model. Competitive reactions from intermediates affected the degradation rate of ACT, and were more obvious as the initial ACT concentration increased.
Show more [+] Less [-]Bayesian importance parameter modeling of misaligned predictors: soil metal measures related to residential history and intellectual disability in children
2014
Onicescu, Georgiana | Lawson, Andrew B. | McDermott, Suzanne | Aelion, C Marjorie | Cai, Bo
In this paper, we propose a novel spatial importance parameter hierarchical logistic regression modeling approach that includes measurement error from misalignment. We apply this model to study the relationship between the estimated concentration of soil metals at the residence of mothers and the development of intellectual disability (ID) in their children. The data consist of monthly computerized claims data about the prenatal experience of pregnant women living in nine areas within South Carolina and insured by Medicaid during January 1, 1996 and December 31, 2001 and the outcome of ID in their children during early childhood. We excluded mother-child pairs if the mother moved to an unknown location during pregnancy. We identified an association of the ID outcome with arsenic (As) and mercury (Hg) concentration in soil during pregnancy, controlling for infant sex, maternal race, mother’s age, and gestational weeks at delivery. There is some indication that Hg has a slightly higher importance in the third and fourth months of pregnancy, while As has a more uniform effect over all the months with a suggestion of a slight increase in risk in later months.
Show more [+] Less [-]Sequential electrochemical treatment of dairy wastewater using aluminum and DSA-type anodes
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 [-]Effectiveness of rodenticides for managing invasive roof rats and native deer mice in orchards
2014
Baldwin, Roger A. | Quinn, Niamh | Davis, David H. | Engeman, Richard M.
Roof rats (Rattus rattus) and deer mice (Peromyscus maniculatus) are occasional pests of nut and tree fruit orchards throughout California and in many other parts of the USA and beyond. In general, the most practical and cost-effective control method for rodents in many agricultural environments is the use of rodenticides (toxic baits), but little or no information exists on the efficacy of current rodenticides in controlling roof rats and deer mice in orchards. Therefore, our goals were to develop an index of rodent activity to monitor efficacy of rodenticides and to subsequently test the efficacy of three California Department of Food and Agriculture rodenticide baits (0.005 % chlorophacinone treated oats, 0.005 % diphacinone treated oats, and 0.005 % diphacinone wax block) to determine their utility for controlling roof rats and deer mice in agricultural orchards. We determined that a general index using the number of roof rat photos taken at a minimum of a 5-min interval was strongly correlated to the minimum number known estimate of roof rats; this approach was used to monitor roof rat and deer mouse populations pre- and post-treatment. Of the baits tested, the 0.005 % diphacinone treated oats was most effective for both species; 0.005 % chlorophacinone grain was completely ineffective against roof rats. Our use of elevated bait stations proved effective at providing bait to target species and should substantially limit access to rodenticides by many non-target species.
Show more [+] Less [-]Contrasting cellular stress responses of Baikalian and Palearctic amphipods upon exposure to humic substances: environmental implications
2014
Protopopova, Marina V. | Pavlichenko, Vasiliy V. | Menzel, Ralph | Putschew, Anke | Luckenbach, Till | Steinberg, Christian E. W.
The species-rich, endemic amphipod fauna of Lake Baikal does not overlap with the common Palearctic fauna; however, the underlying mechanisms for this are poorly understood. Considering that Palearctic lakes have a higher relative input of natural organic compounds with a dominance of humic substances (HSs) than Lake Baikal, we addressed the question whether HSs are candidate factors that affect the different species compositions in these water bodies. We hypothesized that interspecies differences in stress defense might reveal that Baikalian amphipods are inferior to Palearctic amphipods in dealing with HS-mediated stress. In this study, two key mechanisms of general stress response were examined: heat-shock protein 70 (HSP70) and multixenobiotic resistance-associated transporters (ABCB1). The results of quantitative polymerase chain reaction (qPCR) showed that the basal levels (in 3-day acclimated animals) of hsp70 and abcb1 transcripts were lower in Baikalian species (Eulimnogammarus cyaneus, Eulimnogammarus verrucosus, Eulimnogammarus vittatus—the most typical littoral species) than in the Palearctic amphipod (Gammarus lacustris—the only Palearctic species distributed in the Baikalian region). In the amphipods, the stress response was induced using HSs at 10 mg L⁻¹dissolved organic carbon, which was higher than in sampling sites of the studied species, but well within the range (3–10 mg L⁻¹) in the surrounding water bodies populated by G. lacustris. The results of qPCR and western blotting (n = 5) showed that HS exposure led to increased hsp70/abcb1 transcripts and HSP70 protein levels in G. lacustris, whereas these transcript levels remained constant or decreased in the Baikalian species. The decreased level of stress transcripts is probably not able to confer an effective tolerance to Baikalian species against further environmental stressors in conditions with elevated HS levels. Thus, our results suggest a greater robustness of Palearctic amphipods and a higher sensitivity of Baikalian amphipods to HS challenge, which might prevent most endemic species from migrating to habitats outside Lake Baikal.
Show more [+] Less [-]Unexpected toxic interactions in the freshwater amphipod Gammarus pulex (L.) exposed to binary copper and nickel mixtures
2014
Charles, Jérémie | Crini, Grégorio | Degiorgi, François | Sancey, Bertrand | Morin-Crini, Nadia | Badot, Pierre-Marie
To document the toxicity of copper and nickel in binary mixtures, freshwater amphipods Gammarus pulex were exposed to the metals given independently or as mixtures. Toxicity to Cu alone was relatively high: 96-h LC₁₀and LC₅₀were found at 91 and 196 μg L⁻¹, respectively. Toxicity to Ni alone was very low, with 96-h LC₁₀and LC₅₀of 44,900 and 79,200 μg L⁻¹, respectively. Mixture toxicities were calculated from single toxicity data using conventional models. Modeled toxicity was then compared with the measured toxicity of the binary mixture. Two kinds of mixtures were tested. Type I mixtures were designed as combinations of Cu and Ni given at the same effect concentrations, when taken independently, to identify possible interactions between copper and nickel. In type II mixtures, Cu concentrations varied from 0 to 600 μg L⁻¹while the nickel concentration was kept constant at 500 μg L⁻¹to mimic conditions of industrial wastewater discharges. Ni and Cu showed synergic effects in type I mixtures while type II mixtures revealed antagonistic effects. Low doses of Ni reduced Cu toxicity towards G. pulex. These results show that even for simple binary mixtures of contaminants with known chemistry and toxicity, unexpected interactions between the contaminants may occur. This reduces the reliability of conventional additivity models.
Show more [+] Less [-]Characterization of the interactions between tetracycline antibiotics and microbial extracellular polymeric substances with spectroscopic approaches
2014
Song, Chao | Sun, Xue-Fei | Xing, Su-Fang | Xia, Peng-Fei | Shi, Yi-Jing | Wang, Shu-Guang
The antibiotics have attracted global attentions for their impact on aquatic ecosystem. The knowledge about the fate of antibiotics encountering extracellular polymeric substances (EPS) is, however, limited. In this study, we investigated the interacting mechanisms of tetracycline (TC) to EPS extracted from aerobic activated sludge. The contributions of the main components of EPS, extracellular proteins, and polysaccharides were evaluated using bovine serum albumin and alginate sodium, respectively. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and nuclear magnetic resonance indicated that hydroxyl, carboxyl, and amino groups were the domain chemical groups involved in the interaction between TC and EPS, and the binding of TC onto EPS changed the structure of these chemical groups, thus causing shifts in their UV–visible absorption spectra. In addition, we found that extracellular proteins, rather than polysaccharides, were the major active contents involved in the interaction. Three-dimensional excitation–emission matrix fluorescence spectroscopy showed that the fluorophores in EPS were clearly quenched by TC and the static quenching process was observed, implying the complex formation of TC and EPS. Furthermore, thermodynamic analysis indicated that the binding of TC with EPS is spontaneous and dominated by electrostatic forces.
Show more [+] Less [-]Seasonal and spatial variation of organic tracers for biomass burning in PM₁ aerosols from highly insolated urban areas
2014
van Drooge, B. L. | Fontal, M. | Bravo, N. | Fernández, P. | Fernández, M. A. | Muñoz-Arnanz, J. | Jimenez, B. | Grimalt, J. O.
PM₁ aerosol characterization on organic tracers for biomass burning (levoglucosan and its isomers and dehydroabietic acid) was conducted within the AERTRANS project. PM₁ filters (N = 90) were sampled from 2010 to 2012 in busy streets in the urban centre of Madrid and Barcelona (Spain) at ground-level and at roof sites. In both urban areas, biomass burning was not expected to be an important local emission source, but regional emissions from wildfires, residential heating or biomass removal may influence the air quality in the cities. Although both areas are under influence of high solar radiation, Madrid is situated in the centre of the Iberian Peninsula, while Barcelona is located at the Mediterranean Coast and under influence of marine atmospheres. Two extraction methods were applied, i.e. Soxhlet and ASE, which showed equivalent results after GC-MS analyses. The ambient air concentrations of the organic tracers for biomass burning increased by an order of magnitude at both sites during winter compared to summer. An exception was observed during a PM event in summer 2012, when the atmosphere in Barcelona was directly affected by regional wildfire smoke and levels were four times higher as those observed in winter. Overall, there was little variation between the street and roof sites in both cities, suggesting that regional biomass burning sources influence the urban areas after atmospheric transport. Despite the different atmospheric characteristics in terms of air relative humidity, Madrid and Barcelona exhibit very similar composition and concentrations of biomass burning organic tracers. Nevertheless, levoglucosan and its isomers seem to be more suitable for source apportionment purposes than dehydroabietic acid. In both urban areas, biomass burning contributions to PM were generally low (2 %) in summer, except on the day when wildfire smoke arrive to the urban area. In the colder periods the contribution increase to around 30 %, indicating that regional biomass burning has a substantial influence on the urban air quality.
Show more [+] Less [-]Three major nucleolar proteins migrate from nucleolus to nucleoplasm and cytoplasm in root tip cells of Vicia faba L. exposed to aluminum
2014
Qin, Rong | Zhang, Huaning | Li, Shaoshan | Jiang, Wusheng | Liu, Donghua
Results from our previous investigation indicated that Al could affect the nucleolus and induce extrusion of silver-staining nucleolar particles containing argyrophilic proteins from the nucleolus into the cytoplasm in root tip cells of Vicia faba L. So far, the nucleolar proteins involved have not been identified. It is well known that nucleophosmin (B23), nucleolin (C23), and fibrillarin are three major and multifunctional nucleolar proteins. Therefore, effects of Al on B23, C23, and fibrillarin in root tip cells of V. faba exposed to 100 μM Al for 48 h were observed and analyzed using indirect immunofluorescence microscopy and Western blotting. The results from this work demonstrated that after 100 μM of Al treatment for 48 h, B23 and C23 migrated from the nucleolus to the cytoplasm and fibrillarin from the nucleolus to the nucleoplasm. In some cells, fibrillarin was present only in the cytoplasm. Western blotting data revealed higher expression of the three major nucleolar proteins in Al-treated roots compared with the control and that the B23 content increased markedly. These findings confirmed our previous observations.
Show more [+] Less [-]Behavior of sartans (antihypertensive drugs) in wastewater treatment plants, their occurrence and risk for the aquatic environment
2014
Bayer, Anne | Asner, Robert | Schüssler, Walter | Kopf, Willi | Weiss, Klaus | Sengl, Manfred | Letzel, Marion
Pharmaceuticals and other anthropogenic trace contaminants reach wastewaters and are often not satisfactorily eliminated in sewage treatment plants. These contaminants and/or their degradation products may reach surface waters, thus influencing aquatic life. In this study, the behavior of five different antihypertonic pharmaceuticals from the sartan group (candesartan, eprosartan, irbesartan, olmesartan and valsartan) is investigated in lab-scale sewage plants. The elimination of the substances with related structures varied broadly from 17 % for olmesartan up to 96 % for valsartan. Monitoring data for these drugs in wastewater effluents of six different sewage treatment plants (STPs) in Bavaria, and at eight rivers, showed median concentrations for, e.g. valsartan of 1.1 and 0.13 μg L⁻¹, respectively. Predicted environmental concentrations (PEC) were calculated and are mostly consistent with the measured environmental concentrations (MEC). The selected sartans and the mixture of the five sartans showed no ecotoxic effects on aquatic organisms in relevant concentrations. Nevertheless, the occurrence of pharmaceuticals in the environment should be reduced to minimize the risk of their distribution in surface waters, ground waters and bank filtrates used for drinking water.
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