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Acute and chronic toxicity of benzotriazoles to aquatic organisms Full text
2012
Seeland, Anne | Oetken, Matthias | Kiss, Aliz | Fries, Elke | Oehlmann, Jörg
PURPOSE: Resulting from their intensive use as corrosion inhibitors in aircraft deicing and anti-icing fluids (ADAF) and for silver protection in dishwasher detergents benzotriazoles (BTs) are widespread in European surface waters. The current study aimed on an ecotoxicological characterization of 1H-benzotriazole (1H-BT) and 5-methyl-1H-benzotriazole (5MBT). METHODS: Acute and chronic OECD guideline tests were conducted with primary producers (Desmodesmus subspicatus, Lemna minor) and two daphnia species (Daphnia magna, Daphnia galeata) to characterize the hazard of these chemicals. Additionally, the estrogenic activity of both BTs was analyzed in vitro using a recombinant yeast estrogen screen (YES). RESULTS: Both BTs revealed significant effects in acute and chronic experiments, but exhibited no estrogenic activity in the YES. The algal growth test displayed an inhibited cell number increase with effect concentration (EC) values of EC10 1.18 and 2.86 mg l-1 for 1H-BT and 5MBT, respectively. In the Lemna test, EC10 values were 3.94 mg l-1 (1H-BT) and 2.11 mg l-1 (5MBT). D. magna was also affected with EC50 (48 h) values of 107 mg l-1 for 1H-BT and 51.6 mg l-1 for 5MBT. D. galeata was more sensitive with an EC50 (48 h) of 14.7 mg 1H-BT l-1 and 8.13 mg 5MBT l-1. In the 21-day reproduction tests with D. magna, the EC10 for 5MBT was 5.93 mg l-1 while 1H-BT showed no adverse effects. D. galeata turned out to be more sensitive in the chronic study with EC10 values of 0.97 mg l-1 for 1H-BT and 0.40 mg l-1 for 5 MBT. CONCLUSION: Because BTs are regularly found in the aquatic environment at lower μg l-1 concentrations reflecting their persistence and poor elimination during wastewater treatment processes, a preliminary risk assessment was conducted. There is little indication that BTs pose a risk for aquatic ecosystems at current exposure levels during most of the year. However, it cannot be excluded that in winter with a higher usage of ADAFs environmental concentrations may well exceed the level that is considered safe for aquatic organisms.
Show more [+] Less [-]Performance of Eleocharis macrostachya and its importance for arsenic retention in constructed wetlands Full text
2012
Olmos-Márquez, Mario Alberto | Alarcón Herrera, María Teresa | Martín-Domínguez, Ignacio Ramiro
INTRODUCTION: Arsenic (As) can be removed from water via rhizofiltration using phytostabilizing plants. The aim of this study was to investigate the performance of Eleocharis macrostachya in constructed wetland prototypes, as well as the plant's arsenic mass retention and the distribution of As along the wetland flow gradient and the soil in the wetland mesocosmos. MATERIALS AND METHODS: Experiments were carried out in laboratory-scale wetland prototypes, two planted with E. macrostachya and one without plants. Samples of water were taken at the inlet and outlet of the wetlands during the 33-week test period. At the end of the experiment, plants and soil (silty-sand) from each prototype were divided in three equal segments (entrance, middle and exit) and analyzed for their arsenic content. Results revealed that the planted wetlands have a higher As-mass retention capacity (87–90% of the total As inflow) than prototypes without plants (27%). RESULTS: As mass balance in the planted wetlands revealed that 78% of the total inflowing As was retained in the soil bed. Nearly 2% was absorbed in the plant roots, 11% was flushed as outflow, and the fate of the remaining 9% is unknown. In the prototype without plants, the soil retained 16% of As mass, 72% of the arsenic was accounted for in the outflow, and 12% was considered unknown. Although E. macrostachya retained only 2% of the total arsenic mass in their roots, its presence was a determining factor for arsenic retention in the wetland soil medium. CONCLUSION: Hence, planted wetlands might be a suitable option for treating As-contaminated water.
Show more [+] Less [-]Evaluation of adsorption characteristics of an anionic azo dye Brilliant Yellow onto hen feathers in aqueous solutions Full text
2012
Mittal, Alok | Thakur, Vijay | Gajbe, Vibha
PURPOSE AND AIM: Removal of an anionic azo dye Brilliant Yellow has been carried out from its aqueous solutions by using hen feathers as potential adsorbent. MATERIALS AND METHODS: Hen feathers procured from local poultry were cut, washed, and activated. Detailed chemical and physical analysis of hen feathers and its characterization through scanning electron microscopy, X-ray diffraction, and infrared measurements have been made. Procured dye has been adsorbed over under batch measurements and adsorption process is monitored using UV spectrophotometer. RESULTS: Optimum parameters for the adsorption of Brilliant Yellow over hen feathers have been determined by studying the effect of pH, temperature, concentration of dye, and amount of adsorbent. On the basis of Langmuir adsorption, isotherms feasibility of the ongoing adsorption has been ascertained and thermodynamic parameters have been calculated. Attempts have also been made to verify Freundlich, Tempkin, and Dubinin–Radushkevich adsorption isotherm models. It is found that during adsorption, uniform distribution of binding energy takes place due to interaction of the dye molecules and the ongoing adsorption process is chemisorptions. The kinetic measurements indicate dominance of pseudo-second-order process during the adsorption. The mathematical treatment on the kinetic data reveals the rate-determining step to be governed through particle diffusion at 8 × 10−5 M and involvement of film diffusion mechanism at higher concentration at temperatures at all the temperatures. CONCLUSIONS: The developed process is highly efficient and it can be firmly concluded that hen feather exhibits excellent adsorption capacity towards hazardous azo dye Brilliant Yellow.
Show more [+] Less [-]Impacts of urbanization on surface sediment quality: evidence from polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) contaminations in the Grand Canal of China Full text
2012
Hong, Youwei | Yu, Shen | Yu, Guangbin | Liu, Yi | Li, Guilin | Wang, Min
INTRODUCTION: Organic pollutants, especially synthetic organic compounds, can indicate paces of anthropogenic activities. Effects of urbanization on polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) distributions in surface sediment were conducted in urban sections of the Grand Canal, China, consisting of a four-level urbanization gradient. MATERIALS AND METHODS: The four-level urbanization gradients include three countryside towns, two small-size cities, three medium-size cities, and a large-size city. Diagnostic ratio analysis and factor analysis–multiple linear regression model were used for source apportionment of PAHs. Sediment quality guidelines (SQGs) of USA and Canada were employed to assess ecological risks of PAHs and PCBs in surface sediments of the Canal. RESULTS AND DISCUSSION: Ranges of PAH and PCB concentrations in surface sediments were 0.66–22 mg/kg and 0.5–93 μg/kg, respectively. Coal-related sources were primary PAH sources and followed by vehicular emission. Total concentration, composition, and source apportionment of PAHs exhibited urbanization gradient effects. Total PCB concentrations increased with the urbanization gradient, while total PAHs concentration in surface sediments presented an inverted U Kuznets curve with the urbanization gradient. Elevated concentrations of both PAHs and PCBs ranged at effect range low levels or interim SQG, assessed by USA and Canadian SQGs. CONCLUSIONS: PAHs and PCBs in surface sediments of the Grand Canal showed urbanization gradient effects and low ecological risks.
Show more [+] Less [-]Photocatalytic behavior of nanosized TiO2 immobilized on layered double hydroxides by delamination/restacking process Full text
2012
Paušová, Šárka | Krýsa, Josef | Jirkovský, Jaromír | Mailhot, Gilles | Prevot, Vanessa
INTRODUCTION: Efficient immobilization of TiO2 nanoparticles on the surface of Mg2Al-LDH nanosheets was performed by delamination/restacking process. EXPERIMENTAL PART: The structural and textural properties of as-prepared nanocomposite were deeply analyzed using different solid-state characterization techniques such as: X-ray powder diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopies, chemical analysis, X-ray photoelecton spectroscopy, N2 adsorption–desorption, and electronic microscopy. RESULTS AND DISCUSSION: The photocatalytic properties of immobilized TiO2 nanoparticles on Mg2Al were investigated using the photodegradation of two model pollutants: Orange II and 4-chlorophenol, and compared with pure colloidal TiO2 solution. CONCLUSION: It appears that Orange II photodegradation was systematically faster and more efficient than 4-chlorophenol photodegradation regardless of the medium pH. Moreover under slightly basic conditions, even if the TiO2 photocatalytic efficiency decreases, photodegradation performed in presence of easily recovered TiO2/Mg2Al1.5 nanocomposite gives rise to comparable or better results than pure TiO2.
Show more [+] Less [-]Highly efficient degradation of ofloxacin by UV/Oxone/Co2+ oxidation process Full text
2012
Sun, Jianhui | Song, Mengke | Feng, Jinglan | Pi, Yunqing
INTRODUCTION: In this study, UV/Oxone/Co2+ oxidation process was applied to degradation of ofloxacin (OFL) in the presence of Co2+ as the catalytic and Oxone as the oxidant. The operation parameters including pH, temperature, dosages of reagents, and reaction time were studied in detail. RESULTS: The results showed that the optimum conditions for the UV/Oxone/Co2+ processes were determined as follows: temperature = 25°C, pH = 5.0, [Oxone] = 0.6 mmol/L, [Oxone]/[Co2+] = 1,000, and reaction time = 60 min. Under these conditions, 100% of the OFL degraded. The kinetics was also studied, and degradation of OFL by the UV/Oxone/Co2+ process could be described by first-order kinetics. CONCLUSIONS: Mineralization of the process was investigated by measuring the total organic carbon (TOC), and the TOC decreased by 87.0% after 60 min. This process could be used as a pretreatment method for wastewater containing ofloxacin.
Show more [+] Less [-]Improving the prediction of ammonium nitrogen removal through struvite precipitation Full text
2012
Zhou, Shaoqi | Wu, Yanyu
PURPOSE: Both an optimization statistical model and a chemical thermodynamic equilibrium computer model were proposed to develop, improve, and optimize struvite precipitation process. METHODS AND RESULT: The NH4-N in synthetically prepared wastewater was removed using struvite precipitation technology. A quadratic statistical modeling, response surface methodology (RSM), was applied to investigate the improvement availability for high-level removal of ammonium-nitrogen by struvite precipitation. Then, a chemical equilibrium model, Visual MINTEQ, was used to calculate the equilibrium speciation and saturation index in aqueous solution and solid phases. In addition, the availability of Mg2+, NH 4 + , and PO 4 3− ions as a function of pH was modeled. The predicted and experimental data indicated that the two models might describe the experiments well. The results showed that pH was an important parameter in ammonium-nitrogen removals at low initial NH4-N concentration. P/N molar ratio was a limiting factor on struvite precipitation at high initial NH4-N concentration. CONCLUSION: Within the ranges of the investigated factors, Visual MINTEQ program can be proposed to predetermine the concentration of ammonium precipitated by struvite, and RSM can be used to predict total NH4-N removal by both struvite precipitation and ammonia volatilization from our investigated system operated at high pH and opened to the atmosphere.
Show more [+] Less [-]Comparison of micrometeorological and two-film estimates of air–water gas exchange for alpha-hexachlorocyclohexane in the Canadian archipelago Full text
2012
Wong, Fiona | Jantunen, Liisa M. | Papakyriakou, Tim | Staebler, Ralf | Stern, Gary A. | Bidleman, Terry F.
The air–sea gas exchange of alpha-hexachlorocyclohexane (α-HCH) in the Canadian Arctic was estimated using a micrometeorological approach and the commonly used Whitman two-film model. Concurrent shipboard measurements of α-HCH in air at two heights (1 and 15 m) and in surface seawater were conducted during the Circumpolar Flaw Lead study in 2008. Sampling was carried out during eight events in the early summer time when open water was encountered. The micrometeorological technique employed the vertical gradient in air concentration and the wind speed to estimate the flux; results were corrected for atmospheric stability using the Monin–Obukhov stability parameter. The Whitman two-film model used the concentrations of α-HCH in surface seawater, in bulk air at 1 and 15 m above the surface, and the Henry’s law constant adjusted for temperature and salinity to derive the flux. Both approaches showed that the overall net flux of α-HCH was from water to air. Mean fluxes calculated using the micrometeorological technique ranged from −3.5 to 18 ng m−2 day−1 (mean 7.4), compared to 3.5 to 14 ng m−2 day−1 (mean 7.5) using the Whitman two-film model. Flux estimates for individual events agreed in direction and within a factor of two in magnitude for six of eight events. For two events, fluxes estimated by micrometeorology were zero or negative, while fluxes estimated with the two-film model were positive, and the reasons for these discrepancies are unclear. Improvements are needed to shorten air sampling times to ensure that stationarity of meteorological conditions is not compromised over the measurement periods. The micrometeorological technique could be particularly useful to estimate fluxes of organic chemicals over water in situations where no water samples are available.
Show more [+] Less [-]Detection of antibacterial-like activity on a silica surface: fluoroquinolones and their environmental metabolites Full text
2012
Lewis, Gareth | Juhasz, Albert | Smith, Euan
BACKGROUND, SCOPE, AND AIMS: Antibacterial fluoroquinolones (FQs) are third-generation antibiotics that are commonly used as therapeutic treatments of respiratory and urinary tract infections. They are used far less in intensively farmed animal production systems, though their use may be permitted in the veterinary treatments of flocks or in medicated feeds. When used, only a fraction of ingested parent FQ actually reaches the in vivo target site of infection, while the remainder is excreted as the parent FQ and its metabolized products. In many species’ metabolism, enrofloxacin (EF) is converted into ciprofloxacin (CF) while both FQs are classified as parent FQs in human treatments. It is therefore likely that both FQs and their metabolic products will contribute to a common pool of metabolites in biological wastes. Wastes from intensive farming practices are either directly applied to agricultural land without treatment or may be temporarily stored prior to disposal. However, human waste is treated in sewage treatment plants (STPs) where it is converted into biosolids. In the storage or treatment process of STPs, FQs and their in vivo metabolites are further converted into other environmental metabolites (FQEMs) by ex vivo physicochemical processes that act and interact to produce complex mixtures of FQEMs, some of which have antibacterial-like activities. Biosolids are then often applied to agricultural land as a fertilizer amendment where FQs and FQEMs can be further converted into additional FQEMs by soil processes. It is therefore likely that FQ-contaminated biowaste-treated soils will contain complex mixtures of FQEMs, some of which may have antibacterial-like activities that may be expressed on bacteria endemic to the receiving agricultural soil environment. Concern has arisen in the scientific and in the general community that repeated use of FQ-contaminated biowaste as fertilizer amendments of nutrient-impoverished agricultural land may create a selective environment in which FQ-resistant bacteria might grow. The likelihood of this happening will depend, to some extent, on whether bioactive FQEMs are first synthesized from the parent FQs by the action and interaction of in vivo and ex vivo processes producing bioactive FQEMs in biowastes and biosolids. The postulated creation of a selective environment will also depend, in part, on whether such bioactive FQEMs are biologically available to bacteria, which may, in turn, be influenced by soil type, amendment regime, and the persistence of the bioactive FQEMs. Additionally, soil bacteria and soil processes may be affected in different ways or extents by bioactive FQEMs that could possibly act additively or synergistically at ecological targets in these non-target bacteria. This is an important consideration, since, while parent FQs have well-defined ecological targets (DNA gyrase and topoisomerase IV) and modes of bactericidal action, the FQEMs and their possible modes of action on the many different species of soil bacteria is less well studied. It is therefore understandable that there is a lack of conclusive evidence directly attributing biosolid usage to any increase in FQ-resistant bacteria detected in biowaste-amended agricultural soil. However, a lack of evidence may simply imply that a causal relationship between biosolid usage programs and any detection of low levels of FQ-resistant bacteria in soils has yet to be established, rather than an assumption of no relationship whatsoever. Based on results presented in this paper, the precautionary principle should be applied in the usage of FQ-contaminated biosolids as fertilizer amendments of agricultural land. The aim of this research was to test whether any bioactive FQEMs of EF could be synthesized by aerobic fermentation processes using Mycobacterium gilvum (American Tissue Culture Collection) and a mixed culture of microorganisms derived from an agricultural soil. High-performance thin-layer chromatography (HPTLC) and bioautography were tested as screening techniques in the detection and analysis of bioactive FQEMs. MATERIALS AND METHODS: FQEMs derived from M. gilvum and mixed (soil) culture aerobic ferments were fractionated using preparative HPTLC. A standard strain of Escherichia coli was then used as the reporter organism in a bioautography assay in the detection of bioactive-FQEMs on a mid-section of the HPTLC plate. Plate sections were reassembled, and a photograph was taken under low-intensity ultraviolet (UV) light to reveal regions that contained analytes that had UV chromophores and antibacterial-like activities. RESULTS AND DISCUSSION: Many fractionated FQEMs displayed antibacterial-like activity while bound to silica gel HPTLC plates. These results also provide evidence that sufficient quantities of biologically active FQEMs were biologically available from a silica gel surface to prevent the adherent growth of E. coli. Six to seven FQEMs derived from EF using aerobic fermentation processes had antibacterial-like activities, while two FQEMs were also detectable using UV light. Furthermore, similar banding patterns of antibacterial-like activity were observed in both the monoculture (M. gilvum) and mixed culture bioautography assays, indicating that similar processes operated in both aerobic fermentations, either producing similar biologically active FQEMs or biologically active FQEMs that had similar physicochemical properties in both ferments. The simplest explanation for these findings is that the tested agricultural soil also contained mycobacteria that metabolized EF in a similar way to the purchased standard monoculture M. gilvum. Additionally, the marked contrast between the bioautography results and the UV results indicated that the presence of UV chromophores is not a prerequisite for the detection of antibacterial-like activity. CONCLUSIONS: A reliance on spectrophotometric techniques in the detection of bioactive FQEMs in the environment may underestimate component antibacterial-like activity and, possibly, total antibacterial-like activity expressed by EF and its FQEMs. The described bioautography method provides a screening technique with which antibacterial-like activities derived from EF and possibly other FQs can be detected directly on silica gel HPTLC plates. RECOMMENDATIONS: It is recommended that both bioassay and instrumental analytical techniques be used in any measurement of hazard and risk relating to antibacterial-like activities in the environment that are derived from fluoroquinolone antibiotics and their environmental metabolites.
Show more [+] Less [-]Characterization of PM10 atmospheric aerosol at urban and urban background sites in Fuzhou city, China Full text
2012
Xu, Lingling | Chen, Xiaoqiu | Chen, Jinsheng | Zhang, Fuwang | He, Chi | Du, Ke | Wang, Yang
BACKGROUND: PM10 aerosol samples were simultaneously collected at two urban and one urban background sites in Fuzhou city during two sampling campaigns in summer and winter. PM10 mass concentrations and chemical compositions were determined. METHODS: Water-soluble inorganic ions (Cl−, NO 3 − , SO 4 2− , NH 4 + , K+, Na+, Ca2+, and Mg2+), carbonaceous species (elemental carbon and organic carbon), and elements (Al, Si, Mg, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, and Pb) were detected using ion chromatography, thermal/optical reflectance, and proton-induced X-ray emission methods, respectively. RESULTS: PM10 mass concentrations, as well as most of the chemical components, were significantly increased from urban background to urban sites, which were due to enhanced anthropogenic activities in urban areas. Elements, carbonaceous species, and most of the ions were more uniformly distributed at different types of sites in winter, whereas secondary ion SO 4 2− , NO 3 − , and NH 4 + showed more evident urban-background contrast in this season. The chemical mass closure indicated that mineral dust, organic matters, and sulfate were the most abundant components in PM10. The sum of individually measured components accounted for 86.9–97.7% of the total measured PM10 concentration, and the discrepancy was larger in urban area than in urban background area. CONCLUSION: According to the principal component analysis–multivariate linear regression model, mineral dust, secondary inorganic ions, sea salt, and motor vehicle were mainly responsible for the PM10 particles in Fuzhou atmosphere, and contributed 19.9%, 53.3%, 21.3%, and 5.5% of PM10, respectively.
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