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Residues and dissipation kinetics of famoxadone and its metabolites in environmental water and soil samples under different conditions
2019
López-Ruiz, Rosalía | Romero González, Roberto | Garrido Frenich, Antonia
The dissipation of famoxadone as well as the behaviour of its metabolites in environmental samples such as water and soil is a major concern. In this study, the dissipation of the target compound in both matrices was carried out applying an analytical method based on ultra-high performance liquid chromatography coupled to Orbitrap mass spectrometry (UHPLC-Orbitrap-MS). The dissipation of famoxadone was monitored over a period of 100 days after the plant protection product, Equation Pro®, was administered to the target matrices. This study was performed at two doses, normal and double in the case of soils and fivefold instead of double dose in water. The concentration of famoxadone steadily decreased during the monitoring period in both matrices. Half-life (DT₅₀) values were lower than 30 days in most cases except for loam soils, for which it was 35 days. Therefore, persistence of this pesticide in both matrices was low. Famoxadone metabolites such as IN-KF015 ((5RS)-5-methyl-5-(4-phenoxyphenyl)-1,3- oxazolidine-2,4-dione) and IN-JS940 ((2RS)-2-hydroxy-2-(4- phenoxyphenyl)propanoic acid) were detected in both matrices and their concentration increased while the concentration of the parent compound decreased. Metabolite IN-JS940 was the compound detected at highest concentration for both matrices. In water the maximum concentration was 20% of the initial famoxadone content and in soils it was 50% of initial famoxadone content. In addition, another metabolite, IN-MN467 ((5RS)-5-methyl-3-[(2-nitrophenyl)amino]- 5-(4-phenoxyphenyl)-1,3-oxazolidine-2,4-dione), was detected in soils, following the same behaviour as the other metabolites. These results provided ample information about the behaviour of metabolites and the necessity of knowing their toxicity in both matrices in order to detect possible risks for living beings.
显示更多 [+] 显示较少 [-]Use of toxicant sensitivity distributions (TSD) for development of exposure guidelines for risk to human health from benzene
2019
Edokpolo, Benjamin | Yu, Qiming Jimmy | Connell, Des
This technique for setting guideline values differs from that currently used by regulatory agencies throughout the world. Data for benzene were evaluated from epidemiological studies on human populations (29 studies). Exposure durations were evaluated in terms of Long Term Exposure (LTE) and Lifetime Exposure. All data was reported as Lowest Observed Adverse Effect Levels (LOAEL) and converted into exposure doses using Average Daily Dose (ADD) and Lifetime Average Daily Dose (LADD). These values were plotted as a Toxicant Sensitivity Distribution (TSD) which was the cumulative probability of LOAEL-ADD and LOAEL-LADD. From the TSD plots, linear regression equations gave correlation coefficients (R2) ranging from 0.69 to 0.97 indicating normal distributions. Guideline Values (GVs) for LTE (8hr/day) and Lifetime (24hr/70yrs) exposure to benzene were calculated using data from human epidemiological studies as 5% level of cumulative probability (CP) of LOAEL–ADD and LOAEL–LADD from the cumulative probability distributions (CPD). The derived guideline values from the human epidemiological studies were 92 μg/kg/day for LTE and 3.4 μg/kg/day for lifetime exposure. GV for LTE is appropriate for occupational exposure and GV derived for lifetime exposure appropriate for the general population. The guideline value for occupational exposure limit was below all the guideline values developed by regulatory agencies. But the general population guideline is within the range of values formulated by European Union, ATSDR, EPAQS, USEPA and OEHHA for air quality for the general population. This is an alternative method which eliminates the application of safety factors and other sources of errors in deriving guideline values for benzene.
显示更多 [+] 显示较少 [-]Underwater noise level predictions of ammunition explosions in the shallow area of Lithuanian Baltic Sea
2019
Bagočius, Donatas | Narščius, Aleksas
Among the noisiest man-made activities in the seas, emitting very high acoustic energy are the underwater explosions of various objects and ship shock trials. Sound energy emitted by high explosives can be predicted or measured at sea. Sometimes, it can be convenient to apply empirical formulas and scaling laws to approximate the energy of underwater explosions. In addition, at some instances the determination of the spectral properties of the explosions is useful, i.e. when possible animal exposure to impulsive noise has to be evaluated. This paper presents an example of an application of freely available scaling laws and equations for prediction of noise levels of underwater explosions of historical ordnance in the shallow sea environments.Main findings of the study: An available scaling laws applied to model underwater explosion properties; spatial extent of explosion mapped; arising issues of modelling of underwater explosions in the shallow marine areas discussed.
显示更多 [+] 显示较少 [-]A simple method for preparing ultra-light graphene aerogel for rapid removal of U(VI) from aqueous solution
2019
Zhao, Donglin | Wang, Yangyang | Zhao, Siyu | Wakeel, Muhammad | Wang, Zheng | Shaikh, Rehan S. | Hayat, Tasawar | Chen, Changlun
In this study, graphene aerogel (GA) was successfully prepared through a simple hydrothermal method. The resulting GA exhibited a porous network structure with a large specific surface area (350.8 m²/g), ultra-light mass and easy separation from water. The pHIEP value of the GA was estimated to be 3.5. The adsorption process and the factors that affect adsorption capacity were studied. The adsorption could be conducted in a wide pH range from 2.0 to 7.0. The maximum adsorption capacity of GA towards U(VI) at pH 4.0 and T = 298 K was 238.67 mg/g calculated from the Langmuir model. The GA had greatly rapid adsorption property for the removal of U(VI) at pH 4.0. Kinetic data showed good correlation with pseudo-second-order equation. Fourier transform infrared spectroscopy and X-ray photoelectron spectrometry characterizations showed that GA adsorbed U(VI) through chemical interaction by oxygen-containing and nitrogen-containing groups functional groups. The results show that GA has excellent application potential as an adsorbent material for removing U(VI) from aqueous solution.
显示更多 [+] 显示较少 [-]Noncovalent interactions between fluoroquinolone antibiotics with dissolved organic matter: A 1H NMR binding site study and multi-spectroscopic methods
2019
Zhao, Xiating | Hu, Zhongzheng | Yang, Xing | Cai, Xuewei | Wang, Zhaowei | Xie, Xiaoyun
Fluoroquinolone antibiotics (FQs) are considered to be emerging environmental contaminants that have been detected extensively in aquatic environment. It is of quite importance to explore FQs interacting with dissolved organic matter (DOM). The interactions of FQs with DOM were examined by nuclear magnetic resonance (NMR) spectroscopy, fluorescence quenching, UV–vis, Fourier transform infrared (FT-IR) spectroscopic techniques. The bindings of FQs to DOM had one single binding site and their quenching mechanisms were static, which were evaluated by the Stern-Volmer and Site-binding equations. Addition of DOM could result in micro-environmental changes of fluorophores groups in FQs. The location adjacent oxygen right of Ofloxacin (OFL) and the aromatic ring (the adjacency replaced by two nitrogen-containing groups) of Ciprofloxacin (CIP), Enrofloxacin (ENR), Norfloxacin (NOR) might be highly affected by DOM molecule. The negative enthalpy change (ΔH⁰), negative entropy change (ΔS⁰) and the positive Gibbs' energy change (ΔG⁰) figured out that the binding processes were exothermic but not thermodynamic favorable, the formation of HA-FQs complexes would be powered chiefly by the ΔS⁰. H-bonding, electrostatic effect, van der Waals force were the acting force in the binding reactions and the π-π stacking effect was the major binding force under alkaline conditions. Moreover, the protonated, deprotonated, or partially protonated state of FQs were found to have different binding capacity to DOM, and the binding reactions for FQs-HA system were suppressed as the ionic strength increased. Meanwhile, alterations of FQs conformation in the presence of DOM were evaluated by FT-IR and UV–vis spectra.
显示更多 [+] 显示较少 [-]Effects of myo-inositol hexakisphosphate, ferrihydrite coating, ionic strength and pH on the transport of TiO2 nanoparticles in quartz sand
2019
Tang, Yadong | Wang, Xiaoming | Yan, Yupeng | Zeng, Huan | Wang, Gang | Tan, Wenfeng | Liu, Fan | Feng, Xionghan
Evaluating the fate and transport of nanoparticles (NPs) in the subsurface environment is critical for predicting the potential risks to both of the human health and environmental safety. It is believed that numerous environmental factors conspire to control the transport dynamics of nanoparticles, yet the effects of organic phosphates on nanoparticles transport remain largely unknown. In this work, we quantified the transport process of TiO2 nanoparticle (nTiO2) and their retention patterns in water-saturated sand columns under various myo-inositol hexakisphosphate (IHP) or phosphate (Pi) concentrations (0–180 μM P), ferrihydrite coating fractions (λ, 0–30%), ionic strengths (1–50 mM KCl), and pH values (4–8). The transport of nTiO2 was enhanced at increased P concentration due to the enhanced colloidal stability. As compared with Pi at the equivalent P level, IHP showed stronger effect on the electrokinetic properties of nTiO2 particles due to its relatively more negative charge and higher adsorption affinity, thereby facilitating the nTiO2 transport (and thus reduced retention) in porous media. At the IHP concentration of 5 μM, the retention of nTiO2 increased with increasing λ and ionic strength, while decreased with pH. In addition, the retention profiles of nTiO2 showed a typical hyperexponential pattern for most scenarios mainly due to the unfavorable attachment, and can be well described by a hybrid mathematical model that coupled convection dispersion equations with a two-site kinetic model and DLVO theory. These quantitative estimations revealed the importance of IHP on affecting the transport of nTiO2 typically in phosphorus-enriched environments. It provides new insights into advanced understanding of the co-transport of nanoparticles and phosphorus in natural systems, essential for both nanoparticle exposure and water eutrophication.
显示更多 [+] 显示较少 [-]Kinetic characteristics and predictive models of methylmercury production in paddy soils
2019
Du, Shuyang | Wang, Xingxiang | Zhang, Taolin | Ding, Changfeng
Understanding the mercury (Hg) methylation process is important for the management of paddy soils contaminated by Hg. In this work, samples of eighteen paddy soils with varying soil properties were spiked with inorganic Hg and subjected to a 90 d flooding period. Soil pH and redox potential (Eh) were measured in situ at intervals, and soils were sampled for the analysis of methylmercury (MeHg). The Hg methylation efficiency increased with flooding time and reached a relatively steady state at 30 d of incubation, ranging from 0.08% to 2.52%, and was significantly correlated with the in situ soil pH and Eh. The Elovich equation could adequately describe the kinetic production of MeHg. MeHg production was well predicted by the in situ soil pH and Eh of flooded soils, in addition to the organic matter content of air-dried soil samples and flooding time. The two predictive models explained 78% and 68% of the variability of the Hg methylation efficiency. The results suggested that the methylation of inorganic Hg in paddy soils after flooding can be predicted as a function of routinely measured soil properties and flooding time, a correlation that can be utilized to improve understanding of the extent of Hg methylation and the management of Hg-contaminated paddy soils.
显示更多 [+] 显示较少 [-]Rapid thermal-acid hydrolysis of spiramycin by silicotungstic acid under microwave irradiation
2019
Chen, Zheng | Dou, Xiaomin | Zhang, Yu | Yang, Min | Wei, Dongbin
Spiramycin is a widely used macrolide antibiotic and exists at high concentration in production wastewater. A thermal-acid hydrolytic pretreatment using silicotungstic acid (STA) under microwave (MW) irradiation was suggested to mitigate spiramycin from production wastewater. Positive correlations were observed between STA dosage, MW power, interaction time and the hydrolytic removal efficiencies, and an integrative equation was generalized quantitively. Rapid and complete removal 100 mg/L of spiramycin was achieved after 8 min of reaction with 1.0 g/L of STA under 200 W of MW irradiation, comparing to 30.1% by MW irradiation or 15.9% by STA alone. The synergetic effects of STA and MW irradiation were originated from the dissociated-proton catalysis by STA and the dipolar rotation heating effect of MW. STA performed much better than the mineral acid H2SO4 under MW, due to the much stronger Brönsted acidity and higher Hammett acidity. After 8 min, 98.0% of antibacterial potency was also reduced. The m/z 558.8614 fragment (P1) and m/z 448.1323 fragment (P2) were identified as the primary products, which were formed by breaking glucosidic bonds and losing mycarose and forosamine for P1 and further mycaminose moiety for P2. Finally, production wastewater with 433 mg/L of spiramycin was effectively treated using this thermal-acid hydrolytic method. Spiramycin and its antibacterial potency both dropped to 0 after 6 min. The potency drop was supposed from the losing of mycarose and/or forosamine. To decrease both the concentration of spiramycin and its antibacterial potency, combinedly using STA and MW was suggested in this work to break down the structural bonds of the functional groups rather than to destroy the whole antibiotic molecules. It is promising for pretreating spiramycin-contained production wastewater to mitigate both the antibiotic and its antibacterial potency.
显示更多 [+] 显示较少 [-]Polycyclic aromatic hydrocarbons in urban soils of China: Distribution, influencing factors, health risk and regression prediction
2019
Zhang, Yan | Peng, Chi | Guo, Zhaohui | Xiao, Xiyuan | Xiao, Ruiyang
Polycyclic aromatic hydrocarbons (PAHs) in urban soils are a risk to the health of residents. To predict those risks, the distribution and the factors influencing the concentration of PAHs were studied by collecting 1120 records of soil PAHs published during 2006–2017 from 26 cities. The mean concentrations of 16 PAHs (∑PAHs) in soil varied from 123 μg/kg to 5568 μg/kg, with a mean value of 1083 μg/kg, suggesting that a few cities were polluted. The distribution of ∑PAHs in the cities followed two gradients, namely from northern China through eastern China to southern China and from industrial cities through developed cities to cities that are main tourist attractions. The concentrations were significantly correlated to annual temperature, the efficiency of energy use, and to such measures of air quality as PM₁₀ and NO₂ concentrations. A regression equation developed to predict the concentration of ∑PAHs in soil and the corresponding health risks to residents of 35 major Chinese cities of China showed that the risks to adults and children were slight in most cities but those in a few industrial cities were of concern, and field investigations are recommended to assess the risk in greater detail. The method offers a useful tool for predicting such risks in other cities even when data on soils PAHs are not available.
显示更多 [+] 显示较少 [-]Prenatal aluminum exposure is associated with increased newborn mitochondrial DNA copy number
2019
Liu, Bingqing | Song, Lulu | Zhang, Lina | Wu, Mingyang | Wang, Lulin | Cao, Zhongqiang | Zhang, Bin | Xu, Shunqing | Wang, Youjie
Aluminum is a widely distributed metal that has been reported to have embryotoxicity and fetotoxicity in animal studies. However, there has been no study of the association between prenatal aluminum exposure and newborn mitochondrial DNA copy number (mtDNAcn). We aimed to investigate the effect of prenatal aluminum exposure on newborn mtDNAcn. A total of 762 mother-newborn pairs were recruited between November 2013 and March 2015 in Wuhan city, China. We measured maternal urinary aluminum concentrations at three trimesters of pregnancy. Relative mtDNAcn was measured in DNA extracted from umbilical cord blood samples. We used generalized estimating equations to assess the relationship between prenatal aluminum exposure and newborn mtDNAcn. The geometric means of creatinine corrected aluminum concentrations were 31.0 μg/g Cr (95% CI: 27.6, 34.7), 40.9 μg/g Cr (95% CI: 35.7, 46.8) and 58.4 μg/g Cr (95% CI: 51.2, 67.4) for the first, second and third trimesters, respectively. After adjustment for potential confounding factors, a doubling of maternal urinary aluminum concentrations during the second and third trimesters was related to 3.16% (95% CI: 0.88, 5.49) and 4.20% (95% CI: 1.64, 6.81) increases in newborn mtDNAcn, respectively, while the association between maternal urinary aluminum concentration during the first trimester and newborn mtDNAcn was not significant (percent difference: 0.70%, 95% CI: −2.25, 3.73). Prenatal aluminum exposure during the second and third trimesters was positively associated with newborn mtDNAcn. Further studies are essential to elucidate on the potential health consequences of newborn mtDNAcn.
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