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Photooxidation of arsenite by natural goethite in suspended solution
2013
Wang, Yajie | Xu, Jing | Zhao, Yan | Zhang, Lin | Xiao, Mei | Wu, Feng
Iron and arsenic have been found to coexist in a water environment and the fate of arsenite in the aquatic system is influenced by iron. Goethite is a form of iron hydroxide, which is commonly found in sediments. In previous studies, we have used iron complexes to degrade organic pollutants. Results have shown that some organic pollutants could be totally degraded by iron complexes and our work indicated that iron might cause conversion of arsenic when irradiated. This work attempts to investigate the conversion of arsenite [As(III)] using natural goethite, as the iron source, to quantify the effect of various factors on photooxidation. We also consider the possible mechanism for photooxidation of As(III) using a suspension of natural goethite. The As(III) concentration variation under illumination was compared with the one in the dark to quantify the contribution of light to As(III) oxidation to As(V) in goethite suspended solution. The experiments under N₂ and air atmosphere confirmed the participation of dissolved oxygen. The photooxidation efficiency of As(III) under different conditions was compared to determine the effect of different environmental factors such as pH value, goethite concentration, and humic acid concentration on the photooxidation reaction. In the solution containing 100 μg L⁻¹ arsenite and 0.1 g L⁻¹ suspended goethite at pH 3.0, nearly 80 % of As(III) was photooxidized after irradiation by a 250-W metal halogen lamp (λ ≥ 313 nm) after 6 h. The effects of initial pH and goethite concentration and humic acid concentration were all examined. The results show that the greatest efficiency of photooxidation of As(III) was at pH 3.0. The extent of photooxidation decreased with increasing goethite concentration and fell sharply in the presence of humic acid under the conditions in this work. Although about 80 % of As(III) was photooxidized after irradiation by a 250-W halogen lamp at pH 3.0 in the presence of goethite suspension, photooxidation was also affected by factors such as pH, concentration of goethite, and presence of humic acid. The scavenger experiments showed that the HO• radical and photogenerated hole are the predominant oxidants in this system responsible for 87.1 % oxidation of As(III), while HO ₂ • /O ₂ •⁻ is responsible for 12.9 % oxidation of As(III).
Show more [+] Less [-]Variation patterns in individual fish responses to chemical stress among estuaries, seasons and genders: the case of the European flounder (Platichthys flesus) in the Bay of Biscay
2013
Laroche, Jean | Gauthier, Olivier | Quiniou, Louis | Devaux, Alain | Bony, Sylvie | Evrard, Estérine | Cachot, Jérôme | Chérel, Yan | Larcher, Thibaut | Riso, Ricardo | Pichereau, Vianney | Devier, Marie Hélène | Budzinski, Hélène
The objective was to describe and model variation patterns in individual fish responses to contaminants among estuaries, season and gender. Two hundred twenty-seven adult European flounders were collected in two seasons (winter and summer) in four estuaries along the Bay of Biscay (South West France), focusing on a pristine system (the Ster), vs. three estuaries displaying contrasted levels of contaminants (the Vilaine, Loire and Gironde). Twenty-three variables were measured by fish, considering the load of contaminants (liver metals, liver and muscle persistent organic pollutants, muscle polycyclic aromatic hydrocarbons); the gene expression (Cyt C oxydase, ATPase, BHMT, Cyt P450 1A1, ferritin); the blood genotoxicity (Comet test); and liver histology (foci of cellular alteration–tumour, steatosis, inflammation, abnormal glycogen storage). Canonical redundancy analysis (RDA) was used to model these variables using gender, season and estuary of origin as explanatory variables. The results underlined the homogeneity of fish responses within the pristine site (Ster) and more important seasonal variability within the three contaminated systems. The complete model RDA was significant and explained 35 % of total variance. Estuary and season respectively explained 30 and 5 % of the total independent variation components, whilst gender was not a significant factor. The first axis of the RDA explains nearly 27 % of the total variance and mostly represents a gradient of contamination. The links between the load of contaminants, the expression of several genes and the biomarkers were analysed considering different levels of chemical stress and a possible multi-stress, particularly in the Vilaine estuary.
Show more [+] Less [-]Influence of iron and copper oxides on polychlorinated diphenyl ether formation in heterogeneous reactions
2013
Liu, Wenxia | Shen, Lianfeng | Zhang, Fawen | Liu, Wenbin | Zheng, Minghui | Yang, Xitian
Polychlorinated diphenyl ether (PCDE) has attracted great attention recently as an important type of environmental pollutant. The influence of iron and copper oxides on formation of PCDEs was investigated using laboratory-scale flow reactors under air and under nitrogen at 350 °C, a temperature corresponding to the post-combustion zone of a municipal solid waste incinerator. The results show that the 2,2',3,4,4',5,5',6-otachlorodiphenyl ether (OCDE) formed from the condensation of pentachlorophenol (PCP) and 1,2,4,5-tetrachlorobenzene (Cl4Bz) is the predominant congener formed on the SiO2/Fe2O3 surface with and without oxygen. This indicated that HCl elimination between PCP and 1,2,4,5-Cl4Bz molecules formed 2,2',3,4,4',5,5',6-OCDE in the presence of Fe2O3. On the other hand, decachlorodiphenyl ether, nonachlorodiphenyl ether, and OCDE were the dominant products on the SiO2/CuO surface without oxygen, although the 2,2',3,4,4',5,5',6-OCDE was the dominant product on the SiO2/CuO surface with oxygen. Therefore, the presence of Fe2O3 and CuO influences the formation and homologue distribution of PCDEs, which shifted towards the lower chlorinated species. Fe2O3 can promote both the condensation and dechlorination reaction without oxygen. On the contrary, with oxygen, Fe2O3 suppresses the condensation of chlorobenzene and chlorophenol to form PCDEs and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). CuO can increase the formation of lower chlorinated PCDEs and PCDDs without oxygen. In conclusion, the different fly ash components have a major influence on PCDE emissions.
Show more [+] Less [-]GPR-Analyzer: a simple tool for quantitative analysis of hierarchical multispecies microarrays
2013
Dittami, Simon M. | Edvardsen, Bente
Monitoring of marine microalgae is important to predict and manage harmful algae blooms. It currently relies mainly on light-microscopic identification and enumeration of algal cells, yet several molecular tools are currently being developed to complement traditional methods. MIcroarray Detection of Toxic ALgae (MIDTAL) is an FP7-funded EU project aiming to establish a hierarchical multispecies microarray as one of these tools. Prototype arrays are currently being tested with field samples, yet the analysis of the large quantities of data generated by these arrays presents a challenge as suitable analysis tools or protocols are scarce. This paper proposes a two-part protocol for the analysis of the MIDTAL and other hierarchical multispecies arrays: Signal-to-noise ratios can be used to determine the presence or absence of signals and to identify potential false-positives considering parallel and hierarchical probes. In addition, normalized total signal intensities are recommended for comparisons between microarrays and in order to relate signals for specific probes to cell concentrations using external calibration curves. Hybridization- and probe-specific detection limits can be calculated to help evaluate negative results. The suggested analyses were implemented in “GPR-Analyzer”, a platform-independent and graphical user interface-based application, enabling non-specialist users to quickly and quantitatively analyze hierarchical multispecies microarrays. It is available online at http://folk.uio.no/edvardse/gpranalyzer .
Show more [+] Less [-]Physicochemical and toxicological characteristics of urban aerosols during a recent Indonesian biomass burning episode
2013
Pavagadhi, Shruti | Betha, Raghu | Venkatesan, Shriram | Balasubramanian, Rajasekhar | Hande, Manoor Prakash
Air particulate matter (PM) samples were collected in Singapore from 21 to 29 October 2010. During this time period, a severe regional smoke haze episode lasted for a few days (21–23 October). Physicochemical and toxicological characteristics of both haze and non-haze aerosols were evaluated. The average mass concentration of PM₂.₅ (PM with aerodynamic diameter of ≤2.5 μm) increased by a factor of 4 during the smoke haze period (107.2 μg/m³) as compared to that during the non-smoke haze period (27.0 μg/m³). The PM₂.₅ samples were analyzed for 16 priority polycyclic aromatic hydrocarbons (PAHs) listed by the United States Environmental Protection Agency and 10 transition metals. Out of the seven PAHs known as potential or suspected carcinogens, five were found in significantly higher levels in smoke haze aerosols as compared to those in the background air. Metal concentrations were also found to be higher in haze aerosols. Additionally, the toxicological profile of the PM₂.₅ samples was evaluated using a human epithelial lung cell line (A549). Cell viability and death counts were measured after a direct exposure of PM₂.₅ samples to A459 cells for a period of 48 h. The percentage of metabolically active cells decreased significantly following a direct exposure to PM samples collected during the haze period. To provide further insights into the toxicological characteristics of the aerosol particles, glutathione levels, as an indirect measure of oxidative stress and caspase-3/7 levels as a measure of apoptotic death, were also evaluated.
Show more [+] Less [-]Remediation of polycyclic aromatic hydrocarbon and metal-contaminated soil by successive methyl-β-cyclodextrin-enhanced soil washing–microbial augmentation: a laboratory evaluation
2013
Sun, Mingming | Luo, Yongming | Teng, Ying | Jia, Zhongjun | Li, Zhengao | Deng, Shiping
Polycyclic aromatic hydrocarbon (PAH) and metal-polluted sites caused by abandoned coking plants are receiving wide attention. To address the associated environmental concerns, innovative remediation technologies are urgently needed. This study was initiated to investigate the feasibility of a cleanup strategy that employed an initial phase, using methyl-β-cyclodextrin (MCD) solution to enhance ex situ soil washing for extracting PAHs and metals simultaneously, followed by the addition of PAH-degrading bacteria (Paracoccus sp. strain HPD-2) and supplemental nutrients to treat the residual soil-bound PAHs. Elevated temperature (50 °C) in combination with ultrasonication (35 kHz, 30 min) at 100 g MCD L⁻¹ was effective in extracting PAHs and metals to assist soil washing; 93 % of total PAHs, 72 % of Cd, 78 % of Ni, 93 % of Zn, 84 % of Cr, and 68 % of Pb were removed from soil after three successive washing cycles. Treating the residual soil-bound PAHs for 20 weeks led to maximum biodegradation rates of 34, 45, 36, and 32 % of the remaining total PAHs, 3-ring PAHs, 4-ring PAHs, and 5(+6)-ring PAHs after washing procedure, respectively. Based on BIOLOG Ecoplate assay, the combined treatment at least partially restored microbiological functions in the contaminated soil. The ex situ cleanup strategy through MCD-enhanced soil washing followed by microbial augmentation can be effective in remediating PAH and metal-contaminated soil.
Show more [+] Less [-]Removal of heavy metal ions from wastewater by a novel HEA/AMPS copolymer hydrogel: preparation, characterization, and mechanism
2013
Li, Zhengkui | Wang, Yueming | Wu, Ningmei | Chen, Qichun | Wu, Kai
This study aims to synthesize 2-hydroxyethyl acrylate (HEA) and 2-acrylamido-2-methylpropane sulfonic (AMPS) acid-based hydrogels by gamma radiation and to investigate their swelling behavior and heavy metal ion adsorption capabilities. The copolymer hydrogels prepared were characterized via scanning electron microscopy, Fourier transformed infrared spectra, thermal gravimetric analysis, and X-ray photoelectron spectroscopy. The research showed that the copolymer hydrogel was beneficial for permeation due to its porous structure. In addition, the experimental group A-2-d [70 % water volume ratio and (n (AMPS)/n (HEA)) = 1:1] was an optimal adsorbent. The optimal pH was 6.0 and the optimal temperature was 15 °C. Pb²⁺, Cd²⁺, Cu²⁺, and Fe³+ achieved adsorption equilibriums within 24 h, whereas Cr³⁺ reached equilibrium in 5 h. Pb²+, Cd²⁺, Cr³⁺, and Fe³⁺ maximum load capacity was 1,000 mg L⁻¹, whereas the Cu²⁺ maximum capacity was 500 mg L⁻¹. The priority order in the multicomponent adsorption was Cr³⁺>Fe³⁺>Cu²⁺>Cd²⁺>Pb²⁺. The adsorption process of the HEA/AMPS copolymer hydrogel for the heavy metal ions was mainly due to chemisorption, and was only partly due to physisorption, according to the pseudo-second-order equation and Langmuir adsorption isotherm analyses. The HEA/AMPS copolymer hydrogel was confirmed to be an effective adsorbent for heavy metal ion adsorption.
Show more [+] Less [-]Mesoporous hexagonal and cubic aluminosilica adsorbents for toxic nitroanilines from water
2013
El-Safty, Sherif A. | Ismael, M. | Shahat, A. | Shenashen, M. A.
In the present study, ordered mesocage hexagonal P6mm and cubic Pm3n aluminosilica nanoadsorbents with monolith-like morphology and micro-, meso-, and macro-pores were fabricated using a simple, reproducible, direct synthesis. Our results suggest that the aluminosilica nanoadsorbents attained the ordering and uniform hexagonal and cubic pores even at the high Si/Al ratio of 4. The acidity of nanoadsorbents significantly based on the amount of aluminum species in the walls of the silica pore framework. Aluminosilica nanoadsorbents were used as a removal of environmentally toxic aromatic amines, namely p-nitroaniline (p-NA), from wastewater. The loading amount of Bronsted acid sites, mesostructural geometries, and multi-directional pores (3D) of the aluminosilica adsorbents played a key factor in the enhancement of the coverage adsorbent surfaces and intraparticle diffusion of adsorbate molecules onto the network surfaces and into the pore architectures of monoliths. Significantly, we developed theoretical models to explain the 3D microscopic geometry and the pore orientation of aluminosilica monoliths. A key component of the nanoadsorbents is the ability to create revisable p-NA adsorption systems with multiple reuse cycles. However, simple treatment using an acidic aqueous solution was found to remove effectively the p-NA and to form “p-NA-free” pore surfaces without any mesostructural damage.
Show more [+] Less [-]Bioaccumulation and the soil factors affecting the uptake of arsenic in earthworm, Eisenia fetida
2013
Yi, Pyŏng-t'ae | Lee, Sang-Woo | Kim, Ki-Rak | Kim, Kyoung-Woong
To better understand arsenic (As) bioaccumulation, a soil invertebrate species was exposed to 17 field soils contaminated with arsenic due to mining activity. Earthworms (Eisenia fetida) were kept in the soils for 70 days under laboratory conditions, as body burden increased and failed to reach equilibrium in all soils. After 70 days of exposure, XANES spectra determined that As was biotransformed to a highly reduced form. Uptake kinetics for As was calculated using one compartment model. Stepwise multiple regression suggested that sorbed As in soils are bioaccessible, and uptake is governed by soil properties (iron oxide, sulfate, and dissolved organic carbon) that control As mobility in soils. As in soil solution are highly related to uptake rate except four soils which had relatively high chloride or phosphate. The results imply that uptake of As is through As interaction with soil characteristics as well as direct from the soil solution. Internal validation showed that empirically derived regression equations can be used for predicting As uptake as a function of soil properties within the range of soil properties in the data set.
Show more [+] Less [-]Removal of algal blooms from freshwater by the coagulation–magnetic separation method
2013
Liu, Dan | Wang, Peng | Wei, Guanran | Dong, Wenbo | Hui, Franck
This research investigated the feasibility of changing waste into useful materials for water treatment and proposed a coagulation–magnetic separation technique. This technique was rapid and highly effective for clearing up harmful algal blooms in freshwater and mitigating lake eutrophication. A magnetic coagulant was synthesized by compounding acid-modified fly ash with magnetite (Fe₃O₄). Its removal effects on algal cells and dissolved organics in water were studied. After mixing, coagulation, and magnetic separation, the flocs obtained from the magnet surface were examined by SEM. Treated samples were withdrawn for the content determination of chlorophyll-a, turbidity, chemical oxygen demand (COD), total nitrogen, and total phosphorus. More than 99 % of algal cells were removed within 5 min after the addition of magnetic coagulant at optimal loadings (200 mg L⁻¹). The removal efficiencies of COD, total nitrogen, and phosphorus were 93, 91, and 94 %, respectively. The mechanism of algal removal explored preliminarily showed that the magnetic coagulant played multiple roles in mesoporous adsorption, netting and bridging, as well as high magnetic responsiveness to a magnetic field. The magnetic–coagulation separation method can rapidly and effectively remove algae from water bodies and greatly mitigate eutrophication of freshwater using a new magnetic coagulant. The method has good performance, is low cost, can turn waste into something valuable, and provides reference and directions for future pilot and production scale-ups.
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