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1.
The effective diffusivity of uranium(VI) in Inada granite has been determined by through-diffusion. Experiments were performed at room temperature (20–25°C) in a 0.1 mol 1−1 KCl solution where uranium is present predominantly as the poorly sorbing UO22+. An effective diffusivity (De) of (3.6 ± 1.6) × 10−14 m2 s−1 was obtained, close to that for uranine (nonsorbing organic tracer), but one order of magnitude lower than those obtained for Sr2+ and NpO2+, and two orders of magnitude lower than that obtained for I. According to well established theory, a proportional relationship exists between De and the diffusivity in the bulk of the solution (Dv). The effective diffusivity obtained in granite was not proportional to Dv. This agrees with results obtained for effective diffusivity in a Swedish granite. The ratio De/Dv was found to be not constant but increased with De or Dv. This result suggests a limit to the application of the theory.  相似文献   

2.
The migration behavior of the actinyl ions U(VI)O22+, Np(V)O2+ and Pu(V,VI)O2(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO2+ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0–9.4) and concentration (0.4 μM–40 μM) conditions. pH is adjusted by variation of CO2 partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85 ± 0.01 Å for the adsorbed and 1.82 ± 0.01 Å for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45 ± 0.02 Å. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46 ± 0.01 Å. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05 ± 0.03 Å and 3 to 6 oxygen backscatterers (O-eq2) at 3.31 ± 0.02 Å. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased KD values after desorption compared to adsorption.  相似文献   

3.
A historical input of trace metals into tidal marshes fringing the river Scheldt may be a cause for concern. Nevertheless, the specific physicochemical form, rather than the total concentration, determines the ecotoxicological risk of metals in the soil. In this study the effect of tidal regime on the distribution of trace metals in different compartments of the soil was investigated. As, Cd, Cu and Zn concentrations in sediment, pore water and in roots were determined along a depth profile. Total sediment metal concentrations were similar at different sites, reflecting pollution history. Pore water metal concentrations were generally higher under less flooded conditions (mean is (2.32 ± 0.08) × 10−3 mg Cd L−1 and (1.53 ± 0.03) × 10−3 mg Cd L−1). Metal concentrations associated with roots (mean is 202.47 ± 2.83 mg Cd kg−1 and 69.39 ± 0.99 mg Cd kg−1) were up to 10 times higher than sediment (mean is 20.48 ± 0.19 mg Cd kg−1 and 20.42 ± 0.21 mg Cd kg−1) metal concentrations and higher under dryer conditions. Despite high metal concentrations associated with roots, the major part of the metals in the marsh soil is still associated with the sediment as the overall biomass of roots is small compared to the sediment.  相似文献   

4.
Jing An  Qixing Zhou  Yuebing Sun  Zhiqiang Xu   《Chemosphere》2009,76(10):1428-1434
Biochemical responses of wheat (Triticum aestivum L.) seedlings stressed by two typical personal care products (PCPs) – triclosan (TCS) and galaxolide (HHCB) were experimentally investigated to assess their ecological risks. The results showed that wheat shoot and root elongation was significantly inhibited by 50–250 mg L−1 TCS and HHCB. Wheat roots were sensitive to TCS, while shoots were sensitive to HHCB. The median effect concentration (EC50) of TCS and HHCB based on the inhibition of their sensitive sites were 147.8 and 143.4 mg L−1, respectively. Moreover, the damage of wheat seedlings treated by low concentration of TCS and HHCB during a long period cannot be neglected. After a 21-d exposure, 0.2–3.0 mg L−1 TCS and HHCB treatment caused the damage to the accumulation of chlorophyll (CHL), the synthesis of soluble protein (SP), and the activity of peroxidase (POD) and superoxide dismutases (SOD) in different degree. However, different changing trends of these physiological indexes treated by different PCPs were observed after 7-d to 14-d exposures, especially the activity of POD and SOD. The activity of POD and SOD in wheat leaves and roots decreased with an increase in the concentration of TCS and the exposure time. However, the enzyme activities in wheat leaves treated by 0.2–3.0 mg L−1 HHCB increased after a 14-d exposure, and with the prolongation of exposure time, the enzyme activities significantly decreased. The variations in these physiological indexes of wheat could be considered as good biomarkers of serious stress by TCS and HHCB in the environment.  相似文献   

5.
In this study, uranium(VI) was successfully removed from aqueous solutions using heat-treated carbon microspheres based on a batch adsorption technique. Influence of the parameters, such as solution pH, contact time, initial uranium(VI) concentration, and temperature on the removal efficiency have been investigated in detail. The results reveal that the maximum adsorption capacity of the heat-treated carbon microspheres toward uranium(VI) is 92.08 mg g?1, displaying a high efficiency for the removal of uranium(VI) from aqueous solution. The experimental data are analyzed using sorption kinetic models. It is revealed that the process obey the pseudo-second-order kinetic model, the determining step might be chemical sorption. The thermodynamic parameters, such as ΔH°, ΔS°, and ΔG° show that the process is endothermic and spontaneous. This work provides an efficient, fast, and convenient approach for the removal of uranium(VI) from aqueous solutions.  相似文献   

6.
The aim of this study is to present the organic and inorganic spectral aerosol module-radiative (ORISAM-RAD) module, allowing the 3D distribution of aerosol radiative properties (aerosol optical depth, single scattering albedo and asymmetry parameter) from the ORISAM module. In this work, we test ORISAM-RAD for one selected day (24th June) during the ESCOMPTE (expérience sur site pour contraindre les modèles de pollution atmosphérique et de transport d’emissions) experiment for an urban/industrial aerosol type. The particle radiative properties obtained from in situ and AERONET observations are used to validate our simulations. In a first time, simulations obtained from ORISAM-RAD indicate high aerosol optical depth (AOD)0.50–0.70±0.02 (at 440 nm) in the aerosol pollution plume, slightly lower (10–20%) than AERONET retrievals. In a second time, simulations of the single scattering albedo (ωo) have been found to well reproduce the high spatial heterogeneities observed over this domain. Concerning the asymmetry parameter (g), ORISAM-RAD simulations reveal quite uniform values over the whole ESCOMPTE domain, comprised between 0.61±0.01 and 0.65±0.01 (at 440 nm), in excellent agreement with ground based in situ measurements and AERONET retrievals. Finally, the outputs of ORISAM-RAD have been used in a radiative transfer model in order to simulate the diurnal direct radiative forcing at different locations (urban, industrial and rural). We show that anthropogenic aerosols strongly decrease surface solar radiation, with diurnal mean surface forcings comprised between −29.0±2.9 and −38.6±3.9 W m−2, depending on the sites. This decrease is due to the reflection of solar radiations back to space (−7.3±0.8<ΔFTOA<−12.3±1.2 W m−2) and to its absorption into the aerosol layer (21.1±2.1<ΔFATM<26.3±2.6 W m−2). These values are found to be consistent with those measured at local scale.  相似文献   

7.
A thin-film continuous flow-through reactor was used to investigate reactions between aqueous Cr(VI) and two iron oxides, geothite and magnetite. Delayed effluent breakthrough of Cr(VI) indicated significant uptake by both oxides. Accumulation and remobilization of Cr(VI) depends on pH and the redox properties of the surface. For geothite the surface was quickly saturated and no further adsorption observed. Chromate anion (CrO42−) exhibited Langmuir-type adsorption. For magnetite, a significant slow steady-state rate of Cr(VI) uptake was observed. We propose two different mechanisms of chromium uptake: surface complexation of Cr(VI) species on geothite, and reductive precipitation of Cr(VI) at Fe(II) sites on magnetite.  相似文献   

8.
The atmospheric reaction of the methylthiyl radical (CH3S) with O3 was investigated as a function of temperature (259–381 K), in the pressure range of 25–300 Torr, using the technique of laser photolysis/laser-induced fluorescence. The resulting Arrhenius expression, with an uncertainty of ±2σ, was k1(T=259–381 K)=(1.02±0.30)×10−12 exp[(432±77) K/T] cm3 molecule−1 s−1. The obtained rate constant k1 was independent of pressure over the limited range employed. Our results are compared with the previous studies carried out, at single temperature and as a function of temperature, by different techniques.  相似文献   

9.
This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH2 linkage in J, with a rate constant derived from the quantum chemical results of 1 × 1015 exp(−68 kcal/mol/RT) s−1 for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 1012 exp(−53 kcal/mol/RT) s−1 over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.  相似文献   

10.
The interaction of N2O5 with dispersed samples of Arizona Test Dust (ATD), Calcite (CaCO3) and quartz (SiO2) was investigated at varying relative humidity using an aerosol flow reactor. Reactive uptake coefficients, γ, obtained at close to zero relative humidity were (4.8 ± 0.7) × 10−3 for CaCO3, (8.6 ± 0.6) × 10−3 for Quartz and (9.8 ± 1.0) × 10−3 for ATD. In the case of calcite, evidence was obtained for an enhanced rate of uptake at relative humidities above ≈ 50%. The results are compared to literature values obtained using bulk substrates and to previous aerosol uptake data on Saharan dust.  相似文献   

11.
Hexavalent chromium [Cr(VI)] and arsenite [As(III)] are the most toxic forms of chromium and arsenic respectively, and reduction of Cr(VI) to Cr(III) and oxidation of As(III) to As(V) has great environmental implications as they affect toxicity and mobility of these toxic species. Bacillus firmus strain TE7, resistant to chromium and arsenic was isolated from tannery effluent. The strain exhibited ability to reduce Cr(VI) and oxidize As(III). It reduced 100 mg L?1 Cr(VI) within 60 h in nutrient broth and oxidized 150 mg L?1 As(III) within 10 h in minimal medium. It also completely reduced 15 mg L?1 Cr(VI) and oxidized 50 mg L?1 of As(III) simultaneously in minimal medium. To the best of our knowledge, this is the first bacterial strain showing simultaneous reduction of Cr(VI) and oxidation of As(III) and is a potential candidate for bioremediation of environments contaminated with these toxic metal species.  相似文献   

12.
The utilization of sustainable and biodegradable lignocellulosic fiber to detoxify the noxious Cr(VI) from wastewater is considered a versatile approach to clean up a contaminated aquatic environment. The aim of the present research is to assess the proficiency and mechanism of biosorption on Ficus carica bast fiber via isotherm models (Langmuir, Freundlich, Temkin, Harkin’s–Jura, and Dubinin–Radushkevich), kinetic models, and thermodynamic parameters. The biomass extracted from fig plant was characterized by scanning electron microscopy and Fourier-transform infrared spectroscopy. To optimize the maximum removal efficiency, different parameters like effect of initial concentration, effect of temperature, pH, and contact time were studied by batch method. The equilibrium data were best represented by the Langmuir isotherm model, and the maximum adsorption capacity of Cr(VI) onto biosorbent was found to be 19.68 mg/g. The pseudo-second-order kinetic model adequately described the kinetic data. The calculated values of thermodynamic parameters such as enthalpy change (?H 0), entropy change (?S 0), and free energy change (?G 0) were 21.55 kJ/mol, 76.24 J/mol?K, and ?1.55 kJ/mol, respectively, at 30 °C which accounted for spontaneous and endothermic processes. The study of adsorbent capacity for Cr(VI) removal in the presence of Na+, Mg2+, Ca2+, SO 4 2? , HCO 3 ? and Cl? illustrated that the removal of Cr(VI) increased in the presence of HCO3? ions; the presence of Na+, SO 4 2? or Cl? showed no significant influence on Cr(VI) adsorption, while Ca2+ and Mg2+ ions led to an insignificant decrease in Cr(VI) adsorption. Further, the desorption studies illustrated that 31.10 % of metal ions can be removed from an aqueous system, out of which 26.63 % of metal ions can be recovered by desorption in first cycle and the adsorbent can be reused. The results of the scale-up study show that the ecofriendly detoxification of Cr(VI) from aqueous systems was technologically feasible.  相似文献   

13.
Diffusion coefficients (T=23±2 °C) and accessible porosities for HTO, 36Cl and 125I were measured on Opalinus Clay (OPA) samples from the Mont Terri Underground Rock Laboratory (URL) using the through-diffusion technique. The direction of transport (diffusion) was perpendicular to bedding. Special cells that allowed the application of confining pressure were designed and constructed. The pressures ranged from 1 to 5 MPa, the latter value simulating the overburden at the Mont Terri URL (about 200 m). The test solution used in the experiments was a synthetic version of the Opalinus Clay pore water, which has Na+ and Cl as the main components (I=0.42 M).The measured values of the effective diffusion coefficients (De) and rock capacity factors (α) are: De=1.2–1.5×10−11 m2 s−1 and α=0.09–0.11 for HTO, De=4.0–5.5×10−12 m2 s−1 and α=0.05 for 36Cl and De=3.2–4.6×10−12 m2 s−1 and α=0.07–0.10 for 125I. For non-sorbing tracers (HTO, 36Cl) the rock capacity factor α is equal to the diffusion-accessible porosity . The experimental results showed that pressure only had a small effect on the value of the diffusion coefficients. Increasing the pressure from 1 to 5 MPa resulted in a decrease of the diffusion coefficient of 17% for HTO, 28% for 36Cl and 30% for 125I. Moreover, the diffusion coefficients for 36Cl and 125I are smaller than for HTO, which is consistent with an effect arising from anion exclusion.The diffusion coefficients of HTO and 125I measured in this study are in good agreement with recent measurements at three other laboratories performed within the framework of a laboratory comparison exercise. The values of the diffusion-accessible porosities show a larger degree of scatter.  相似文献   

14.

In this present study, adsorptive membranes for Cr(VI) ion removal were prepared by blending polyethersulfone (PES) with hydrous ferric oxide (HFO) nanoparticles (NPs). The effects of HFO NPs to PES weight ratio (0–1.5) on the physicochemical properties of the resultant HFO/PES adsorptive membranes were investigated with respect to the surface chemistry and roughness as well as structural morphologies using different analytical instruments. The adsorptive performance of the HFO NPs/PES membranes was studied via batch adsorption experiments under various conditions by varying solution pH, initial concentration of Cr(VI), and contact time. The results showed that the membrane made of HFO/PES at a weight ratio of 1.0 exhibited the highest adsorption capacity which is 13.5 mg/g. Isotherm and kinetic studies revealed that the mechanism is best fitted to the Langmuir model and pseudo-second-order model. For filtration of Cr(VI), the best promising membranes showed improved water flux (629.3 L/m2 h) with Cr(VI) ion removal of 75%. More importantly, the newly developed membrane maintained the Cr(VI) concentration below the maximum contamination level (MCL) for up to 9 h.

  相似文献   

15.
Mangosteen peel, rich in polyphenolic compounds, was used to prepare the adsorbent exhibiting highly selective adsorption for Cr(VI) over other metal ions such as Pb2+, Fe3+, Zn2+, Cd2+, and Cr3+ at the pH values of 1~4. The chemical modification method proposed by using calcium hydroxide is quite cost-effective and ecofriendly without using any toxic reagents or causing any secondary pollution. The adsorption isotherm results revealed that the adsorption of Cr(VI) on the gel fit well the Langmuir adsorption model, and the maximum adsorption capacity for Cr(VI) at pH levels 1, 2, 3, and 4 was evaluated to be 2.46, 2.44, 1.99, and 2.14 mol/kg, respectively. The adsorption mechanism for Cr(VI) on the saponified gel was verified to follow an esterifiaction reaction coupled with the reduction of Cr(VI) to Cr(III) in which H+ plays a role of promoter. Thus, modified mangosteen peel gel has the prominent selectivity and low cost for Cr(VI) removal.  相似文献   

16.
Smog chamber/FTIR techniques were used to study the relative reactivity of OH radicals with methanol, ethanol, phenol, C2H4, C2H2, and p-xylene in 750 Torr of air diluent at 296±2 K. Experiments were performed with, and without, 500–8000 μg m−3 (4000–50 000 μm2 cm−3 surface area per volume) of NaCl, (NH4)2SO4 or NH4NO3 aerosol. In contrast to the recent findings of Oh and Andino (Atmospheric Environment 34 (2000) 2901, 36 (2002) 149; International Journal of Chemical Kinetics 33 (2001) 422) there was no discernable effect of aerosol on the rate of loss of the organic compounds via reaction with OH radicals. Gas kinetic theory arguments cast doubt upon the findings of Oh and Andino. The available data suggest that the answer to the title question is “No”. As part of this work the rate constants for reactions of OH radicals with methanol, ethanol, and phenol in 750 Torr of air at 296 K were determined to be: kOH+CH3OH=(8.12±0.54)×10−13, kOH+C2H5OH=(3.47±0.32)×10−12 and kOH+phenol=(3.27±0.31)×10−11 cm3 molecule−1 s−1.  相似文献   

17.
The influence of biodegradable chelating ligands on arsenic and iron uptake by hydroponically grown rice seedlings (Oryza sativa L.) was investigated. Even though the growth solution contained sufficient Fe, the growth of rice seedlings gradually decreased up to 76% with the increase of pH of the solution from 7 to 11. Iron forms insoluble ferric hydroxide complexes at neutral or alkaline pH in oxic condition. Chelating ligands produce soluble ‘Fe–ligand complex’ which assist Fe uptake in plants. The biodegradable chelating ligand hydroxyiminodisuccinic acid (HIDS) was more efficient then those of ethylenediaminetetraacetic acid (EDTA), ethylenediaminedisuccinic acid (EDDS), and iminodisuccinic acid (IDS) in the increase of Fe uptake and growth of rice seedling. A total of 79 ± 20, 87 ± 6, 116 ± 15, and 63 ± 18 mg dry biomass of rice seedlings were produced with the addition of 0.5 mM of EDDS, EDTA, HIDS, and IDS in the nutrient solution, respectively. The Fe concentrations in rice tissues were 117 ± 15, 82 ± 8, 167 ± 25, and 118 ± 22 μmol g−1 dry weights when 0.25 mM of EDDS, EDTA, HIDS, and IDS were added to the nutrient solution, respectively. Most of the Fe accumulated in rice tissues was stored in roots after the addition of chelating ligands in the solution. The results indicate that the HIDS would be a potential alternative to environmentally persistent EDTA for the increase of Fe uptake and plant growth. The HIDS also increased As uptake in rice root though its translocation from root to shoot was not augmented. This study reports HIDS for the first time as a promising chelating ligand for the enhancement of Fe bioavailability and As phytoextraction.  相似文献   

18.
19.
Chlorophenols and chloroguaiacols were quantified in juvenile chinook salmon captured near bleached kraft mills in the upper Fraser River in December 1987. Fish captured in April 1988 showed up to 55-fold induction of hepatic mixed function oxidase activity (EROD), and were contaminated with up to 370 ng·kg−1 of 2,3,7,8-TCDF and 68 ng·kg−1 of 2,3,7,8-TCDD. The implications for the survival of these salmon are uncertain.  相似文献   

20.
A nationwide study of indoor air concentrations of 26 VOCs was conducted in Canada in 1991. The study design was based upon random selection of private residences from 1986 Census data and incorporated a temporal stratification feature that allowed sampling of residences in each of four regions of the country at different times of the year with equal probability. Average 24 h concentrations of 26 VOCs in 754 residences were obtained by a passive monitoring method. Initially, climatic parameters were found to have the second highest relative weight among 14 factors identified by factor analysis. Further analysis by linear regression showed that individual VOC concentrations and average outdoor temperature or relative humidity were poorly correlated (r > 0.13). Detailed analysis of the data from four regions of Canada also gave poor correlations between household VOC concentrations and temperature or relative humidity. Concentrations of all 26 VOCs averaged 7.8 μg m−3 in winter, 10.3 μg m−3 in spring, 4.4 μg m−3 in summer and 10.8μ m−3 in fall. The highest concentrations of individual compounds averaged 84μm−3 for toluene in the spring and 42 μg m−3 in the fall, and 44 μg m−3 for decane in the spring and 48 μg m−3 in the fall. Segregation of the results into outdoor temperature ranges of 0°C, 0–15 and > 15°C gave mean indoor VOC concentrations of 10.3, 9.8 and 50μgm−3, respectively. Further examination of the results revealed that the likely presence of sources within homes had a far greater influence on indoor concentrations than ventilation which is partly influenced by climate.  相似文献   

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