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1.
The diffusive gradients in thin films technique (DGT) was used for uranium measurements in water. DGT devices with Dowex resin binding phase (Dow DGT) were tested in synthetic river water, which gave 84% response to total uranium concentration. The devices were also deployed in natural river water and compared to devices with other types of binding phases, Chelex 100 resin beads imbedded in polyacrylamide hydrogel (Chelex DGT) and DE 81 anion exchange membrane (DE DGT), deployed in the same location at the same time. The measurement by Dow DGT was the lowest among the different types of the DGT devices, 45% of total uranium, while measurement by DE DGT was the highest, 98% of total uranium. The results achieved by the three types of DGT devices were explained by three DGT working mechanisms, equilibrium between complexes of resin/uranyl carbonates and complexes of resin/competitive ligands in water, effective reduction of uranyl carbonate concentration by the binding phase and dissociation of UO2(CO3)22− and UO2(CO3)34− within the diffusive layer in a DGT device. It is hoped that by deploying the DGT devices with different binding phases in natural waters, additional information on uranium speciation could be obtained.  相似文献   

2.
介绍了近年来环境监测中两种新的原位被动采样技术.薄膜扩散平衡(DET)技术和薄膜扩散梯度(DGT)技术.综述了DET技术的原理、装置的组成和构造、特点及在环境监测中的应用.关于DGT技术着重论述了对被监测物质有效态的累积原理,总结了扩散相和结合相的发展,并展望了未来的发展方向.  相似文献   

3.
The performance of the Diffusive Gradients in Thin films (DGT) technique with Chelex®-100, Metsorb™ and Diphonix® as binding phases was evaluated in the vicinity of the former uranium mining sites of Chardon and L'Ecarpière (Loire-Atlantique department in western France). This is the first time that the DGT technique with three different binding agents was employed for the aqueous U determination in the context of uranium mining environments. The fractionation and speciation of uranium were investigated using a multi-methodological approach using filtration (0.45 μm, 0.2 μm), ultrafiltration (500 kDa, 100 kDa and 10 kDa) coupled to geochemical speciation modelling (PhreeQC) and the DGT technique. The ultrafiltration data showed that at each sampling point uranium was present mostly in the 10 kDa truly dissolved fraction and the geochemical modelling speciation calculations indicated that U speciation was markedly predominated by CaUO2(CO3)32−. In natural waters, no significant difference was observed in terms of U uptake between Chelex®-100 and Metsorb™, while similar or inferior U uptake was observed on Diphonix® resin. In turn, at mining influenced sampling spots, the U accumulation on DGT-Diphonix® was higher than on DGT-Chelex®-100 and DGT-Metsorb™, probably because their performance was disturbed by the extreme composition of the mining waters. The use of Diphonix® resin leads to a significant advance in the application and development of the DGT technique for determination of U in mining influenced environments. This investigation demonstrated that such multi-technique approach provides a better picture of U speciation and enables to assess more accurately the potentially bioavailable U pool.  相似文献   

4.
Commercially available Diphonix® resin (TrisKem International) was evaluated as a receiving phase for use with the diffusive gradients in thin-films (DGT) passive sampler for measuring uranium. This resin has a high partition coefficient for actinides and is used in the nuclear industry. Other resins used as receiving phases with DGT for measuring uranium have been prone to saturation and significant chemical interferences. The performance of the device was evaluated in the laboratory and in field trials. In laboratory experiments uptake of uranium (all 100% efficiency) by the resin was unaffected by varying pH (4–9), ionic strength (0.01–1.00 M, as NaNO3) and varying aqueous concentrations of Ca2+ (100–500 mg L−1) and HCO3 (100–500 mg L−1). Due to the high partition coefficient of Diphonex®, several elution techniques for uranium were evaluated. The optimal eluent mixture was 1 M NaOH/1 M H2O2, eluting 90% of the uranium from the resin. Uptake of uranium was linear (R2 = 0.99) over time (5 days) in laboratory experiments using artificial freshwater showing no saturation effects of the resin. In field deployments (River Lambourn, UK) the devices quantitatively accumulated uranium for up to 7 days. In both studies uptake of uranium matched that theoretically predicted for the DGT. Similar experiments in seawater did not follow the DGT theoretical uptake and the Diphonix® appeared to be capacity limited and also affected by matrix interferences. Isotopes of uranium (U235/U238) were measured in both environments with a precision and accuracy of 1.6–2.2% and 1.2–1.4%, respectively. This initial study shows the potential of using Diphonix®-DGT for monitoring of uranium in the aquatic environment.  相似文献   

5.
The diffusive gradients in thin films technique (DGT) was used to measure depth profiles of mercury in river and marine sediments in situ to a spatial resolution of 0.5 cm. Agarose gel was used as the diffusive gel in the DGT probes. Two different selective resins—Chelex 100 with iminodiacetic groups and Spheron-Thiol with thiol groups incorporated in the polyacrylamide resin gel—were tested. The different capture efficiencies of the two adsorbents enabled the fractions of mercury bound in different species in sediment pore water to be estimated. Mercury concentrations obtained by DGT with Spheron-Thiol resin were very similar to those obtained after centrifugation. This indicates that DGT with Sheron-Thiol resin reports on total dissolved mercury levels. The concentration of mercury measured by DGT with Chelex-100 resin was much lower (by a factor of 5–20) for the same sediment samples. Chelex-100 does not have such a high affinity to mercury as Spheron-Thiol, and so it only reports on the content of labile mercury species, such as inorganic ions and weak complexes. The content of labile mercury species in the river sediment was approximately 20% of the total dissolved mercury in pore water, whereas in marine sediment only 7% of the mercury was present as labile species.  相似文献   

6.
This work investigated the application of diffusive gradients in thin films technique (DGT) to uranium speciation measurements in natural water. Two binding phases were examined, a commercially available affinity membrane, Whatman DE 81 (DE 81), with amino binding functional groups and the conventionally used Chelex 100 beads imbedded polyacrylamide hydrogel (Chelex) with iminodiacetate functional groups. The DGT devices assembled with the binding phases of DE 81 (DE 81 DGT) and Chelex gel (Chelex DGT) were tested both in synthetic river water solutions and in local river water. DE 81 DGT and Chelex DGT measured 80% and 75% of the total uranium in synthetic river water solution, respectively, and measured 73% and 60% of the total uranium in St. Lawrence River, Canada, respectively. The binding properties of the DE 81 membrane and Chelex gel for uranium, and the diffusion of uranyl complexes in the polyacrylamide gel (PAM) were also studied.  相似文献   

7.
Three adsorbents (Chelex-100, manganese dioxide [MnO2] and Metsorb), used as binding layers with the diffusive gradient in thin film (DGT) technique, were evaluated for the measurement of inorganic uranium species in synthetic and natural waters. Uranium (U) was found to be quantitatively accumulated in solution (10–100 μg L−1) by all three adsorbents (uptake efficiencies of 80–99%) with elution efficiencies of 80% (Chelex-100), 84% (MnO2) and 83% (Metsorb). Consistent uptake occurred over pH (5–9), with only MnO2 affected by pH < 5, and ionic strength (0.001–1 mol L−1 NaNO3) ranges typical of natural waters, including seawater. DGT validation experiments (5 days) gave linear mass uptake over time (R2 ≥ 0.97) for all three adsorbents in low ionic strength solution (0.01 M NaNO3). Validation experiments in artificial sea water gave linear mass uptake for Metsorb (R2 ≥ 0.9954) up to 12 h and MnO2 (R2 ≥ 0.9259) up to 24 h. Chelex-100 demonstrated no linear mass uptake in artificial sea water after 8 h. Possible interferences were investigated with SO42− (0.02–200 mg L−1) having little affect on any of the three DGT binding layers. PO43− additions (5 μg L−1–5 mg L−1) interfered by forming anionic uranyl phosphate complexes that Chelex-100 was unable to accumulate, or by directly competing with the uranyl species for binding sites, as with MnO2 and the Metsorb. HCO3 (0.1–500 mg L−1) additions formed anionic species which interfered with the performance of the Chelex-100 and the MnO2, and the Ca2+ (0.1–500 mg L−1) had the affect of forming labile calcium uranyl species which aided uptake of U by all three resins. DGT field deployments in sea water (Southampton Water, UK) gave a linear mass uptake of U over time with Metsorb and MnO2 (4 days). Field deployments in fresh water (River Lambourn, UK) gave linear uptake for up to 7 and 4 days for Metsorb and MnO2 respectively. Field deployment of the Metsorb-DGT samplers with various diffusive layer thicknesses (0.015–0.175 cm) allowed accurate measurements of the diffusive boundary layer (DBL) and allowed DBL corrected concentrations to be determined. This DBL-corrected U concentration was half that determined when the effect of the DBL was not considered. The ability of the DGT devices to measure U isotopic ratios with no isotopic fractionation was shown by all three resins, thereby proving the usefulness of the technique for environmental monitoring purposes.  相似文献   

8.
The effect of sediment size, pH, temperature and conductivity on the transfer of uranium from sediment to water has been studied. The uranium concentration and the234U/238U,235U/238U activity ratios were measured in water, sediments and suspended matter sampled from Jucar River, using low level alpha-spectrometry. Distribution factors were obtained from these measurements. A more detailed sampling was done in the neighbourhood of the Cofrentes Nuclear Plant (Valencia, Spain). Total uranium activity,234U/238U activity ratio and distribution factors for234U and238U were found to vary with pH. Leaching and dilution, which depend on pH and salinity, are the probable mechanisms for these changes.  相似文献   

9.
Zheng J  Yamada M 《Talanta》2006,68(3):932-939
The determination of uranium is important for environmental radioactivity monitoring, which investigates the releases of uranium from nuclear facilities and of naturally occurring radioactive materials by the coal, oil, natural gas, mineral, ore refining and phosphate fertilizer industries, and it is also important for studies on the biogeochemical behavior of uranium in the environment. In this paper, we describe a quadrupole ICP-MS (ICP-QMS)-based analytical procedure for the accurate determination of U isotope ratios (235U/238U atom ratio and 234U/238U activity ratio) in sediment samples. A two-stage sample cleanup using anion-exchange and TEVA extraction chromatography was employed in order to obtain accurate and precise 234U/238U activity ratios. The factors that affect the accuracy and precision of U isotope ratio analysis, such as detector dead time, abundance sensitivity, dwell time and mass bias were carefully evaluated and corrected. With natural U, a precision lower than 0.5% R.S.D. for 235U/238U atom ratio and lower than 2.0% R.S.D. for 234U/238U activity ratio was obtained with less than 90 ng uranium. The developed analytical method was validated using an ocean sediment reference material and applied to an investigation into the uranium isotopic compositions in a sediment core in a brackish lake in the vicinity of U-related nuclear facilities in Japan.  相似文献   

10.
The present study was carried on distribution of uranium isotopes and Thorium in marine sediment from creek of Mumbai Harbour Bay (MHB) using radiochemical separation followed by alpha spectrometry. The activity concentration of uranium and thorium in sediment of MHB has ranged between 1–4 and 1.8–4.5 ppm respectively. The activity ratio of 234U/238U in sediment was found close to unity at most of the locations of creek suggesting a conservative behaviour. The observed Th/U ratio (0.9) in comparison to global Th/U ratio (?3.5) in the creek sediment indicates that it receives low radiogenic nature of terronenous input.  相似文献   

11.
A new resin- Diphonix® in Diffusive Gradients in Thin Films (DGT) technique for the determination of uranium was investigated and compared with previously used binding phases for uranium, Chelex®-100 and Metsorb™. The DGT gel preparation and the elution procedure were optimized for the new resin. The U uptake on Diphonix® resin gel was 97.4 ± 1.5% (batch method; [U] = 20 μg L−1; 0.01 M NaNO3; pH = 7.0 ± 0.2). The optimal eluent was found to be 1 M 1-hydroxyethane-1, 1-diphosphonic acid (HEDPA) with an elution efficiency of 80 ± 4.2%. Laboratory DGT study on U accumulation using a DGT samplers with Diphonix® resin showed a very good performance across a wide range of pH (3–9) and ionic strength (0.001–0.7 M NaNO3). Diffusion coefficients of uranium at different pH were determined using both, a diffusion cell and the DGT time-series, demonstrating the necessity of the implementation of the effective diffusion coefficients into U-DGT calculations. Diphonix® resin gel exhibits greater U capacity than Chelex®-100 and Metsorb™ binding phase gels (a Diphonix® gel disc is not saturated, even with loading of 10.5 μmol U). Possible interferences with Ca2+ (up to 1.33 × 10−2 M), PO43−PO43 (up to 1.72 × 10−4 M), SO42−SO42 (up to 4.44 × 10−3 M) and −HCO3HCO3 (up to 8.20 × 10−3 M) on U-DGT uptake ([U] = 20 μg L−1) were investigated. No effect or minor effect of Ca2+, PO43−PO43, SO42−SO42, and −HCO3HCO3 on the quantitative measurement of U by Diphonix®-DGT was observed. The results of this study demonstrated the DGT technique with Diphonix® resin is a reliable and robust method for the measurement of labile uranium species under laboratory conditions.  相似文献   

12.
Samples of coastal marine sediments of the East Coast of India were leached with a saturated solution of ammonium carbonate for the extraction of uranium from the sediment particle surface without attacking the mineral core of the particles. All the sediment samples were found to exhibit a234U/238U activity ratio in the range of 1.07 to 1.14. On removal of surface organic matter, the234U/238U activity ratio is close to 1.00, indicating that the anomaly between238U and234U exists only on the labile surface layer. However, no such variations are observed in235U/238U activity ratios. These ratios are close to 0.045 which is the same as that of natural uranium.  相似文献   

13.
Concentrations of Cd, Cu, Cr, Pb, Ni and Zn were monitored in the Svitava River (the Czech Republic) during April and September 2005. Total concentrations and total dissolved concentrations were obtained through regular water sampling, and the diffusive gradients in thin films technique (DGT) were used to gain information on the kinetically labile metal concentrations. Each measured concentration was compared with the corresponding average (bio)available concentration calculated from the mass of metal accumulated by the moss species Fontinalis antipyretica. The concentrations of Cd, Pb, Cr and Zn measured using DGT corresponded well with those obtained after the deployment of Fontinalis antipyretica moss bags in the Svitava River, but the concentrations of Cu and Ni did not. The calculated (bio)available Cu concentration correlated well with the total dissolved concentration of Cu, whereas no correlation was found to exist between the concentrations of Ni. Scheme of the Svitava River monitoring station, including the DGT sampling units and Fontinalis antipyretica moss bags Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.  相似文献   

14.
Summary The activity concentration of natural radionuclides and 137Cs in the bottom sediments cores from Kuwait Bay have been determined by γ-ray spectrometry. Particular attention was devoted to the exact determination of two uranium isotopes: 235U and 238U in order to find any presence of depleted uranium dispersed during the 1991 Gulf War. The calculated 238U/235U activity ratios for all the surface (15 cm) as well as the core profile (up to 70 cm in depth) samples were within the limit of one standard deviation close to the value of 21.5 for natural uranium. Simultaneous instrumental determination of the unsupported 210Pb and 226Ra in a few sediment core profiles was used for quantification of sediment accumulation rates. The calculated sedimentation rates (for the constant atmospheric 210Pb flux rate - CRS model) ranged from 0.2 to 0.6 cm . y-1 and were close to the data calculated by the Weibull distribution of 137Cs in undisturbed sediment cores.  相似文献   

15.
Nearshore surface sediments from various locations of the West Coast of India were leached by saturated ammonium carbonate solution for the extraction of uranium isotopes. The reagent chosen was found to have high efficiency for leaching uranium isotopes without attacking the mineral core of the sediment particle. The activity ratios of234U/238U are in the range of 1.11 to 1.14 and the activity ratios of235U/235U are in the range of 0.045 to 0.047. The respective activity ratios in leachates, and residues after removal of surface organic matter from the sediment particles by treatment with hydrogen peroxide and 0.05M HCl, revealed disequilibrium between238U and234U only in the surface organic matter. The activity ratios of234U/238U and235U/238U have also been determined in some seawater samples from the Arabian Sea.  相似文献   

16.
The technique of diffusive gradients in thin films (DGT) is a newly developed analytical technique capable of measuring in situ concentrations of trace metals in the environment. The technique employs a thin film diffusive hydrogel (with well-defined diffusion properties) in contact with a binding phase capable of binding metal ions of interest. In this work, we demonstrate, for the first time, the use of a commercially available solid ion exchange membrane (Whatman P81) as the binding phase in DGT analysis. The cellulose phosphate-based Whatman P81 membrane is a strong cation exchange membrane. Its performance characteristics as a new binding phase in DGT measurement of Cu2+ and Cd2+ were systematically investigated. Several advantages over the conventional ion exchange resin-embedded hydrogel binding phases used in DGT were observed including simple preparation, ease of handling, and reusability. The binding capacities of the material to various metal ions were examined both collectively and individually. The binding phase preferentially binds to transition metal ions rather than matrix ions such as potassium, sodium, calcium and magnesium, which are competitive species in natural waters. Within the optimum pH range (pH 4.0-9.0), the maximum non-competitive binding capacities of the membrane for Cu2+ and Cd2+ were 3.22 and 3.07 μmol cm−2, respectively. The suitability of the new membrane-based binding phase for DGT applications was validated experimentally. The experimental results demonstrated excellent agreement with theoretically predicted trends. The measurement was not degraded after four consecutive reuses of the cellulose phosphate binding phase.  相似文献   

17.
A diffusive gradients in thin films (DGT) device for the analysis of free Cd(II) species, based on Cd(II) ion-imprinted sorbent (IIS) as the binding agents and commercial polyethersulfone membrane (PES) as diffusion layer, was developed (PES/IIS-DGT). DGT time-series experiments showed that the mass of free Cd(II) species accumulated by PES/IIS-DGT was linear vs. time (R2 = 0.9953) and the concentration of free Cd(II) species by PES/IIS-DGT was in good agreement with the total dissolved concentrations of free Cd(II) species in simple synthetic solutions where free ionic species dominated. PES/IIS-DGT performance was independent in the range of pH 4.5–7.5 and ionic strength range from 1.0 × 10−3 to 0.7 mol L−1. The measurement of free Cd(II) species in synthetic solution containing different concentrations of ligands by PES/IIS-DGT showed an excellent agreement with the value measured by Cd(II) ion selective electrodes (Cd-ISE), indicating that PES/IIS-DGT method is more suitable than Cd-ISE for the measurement of low concentration of free Cd(II) species due to the enrichment of IIS for the analytes.  相似文献   

18.
Hongtao Fan  Weijia Li  Shuang Jin 《Talanta》2009,79(5):1228-35
An aqueous solution containing sodium polyacrylate (PA, 0.0030 M) was used in diffusive gradients in thin-films technique (DGT) to measure DGT-labile Cu2+ and Cd2+ concentrations. The DGT devices (PA DGT) were validated in four types of solutions, including synthetic river waters containing metal ions with or without complexing EDTA, natural river water (Hun River, Shenyang, China) spiked with Cu2+ and Cd2+, and an industrial wastewater (Shenyang, China). Results showed that only free metal ions were measured by PA DGT, recovery = 98.79% for Cu2+ and recovery = 97.80% for Cd2+ in solutions containing only free metal ions, recovery = 51.02% for Cu2+ and recovery = 51.92% for Cd2+ in solution with metal/EDTA molar ratio of 2:1 and recovery = 0 in solutions with metal/EDTA molar ratio of 1:1 and 1:2. These indicated that the complexes of Cu-EDTA and Cd-EDTA were DGT-inert or not DGT-labile. The DGT performance in spiked river water (recovery = 8.47% for Cu2+ and recovery = 27.48% for Cd2+) and in industrial wastewater (recovery = 14.16% for Cd2+) were also investigated. Conditional stability constants (log K) of PA-Cu and PA-Cd complexes were determined as 6.98 and 5.61, respectively, indicating strong interaction between PA and the metals.  相似文献   

19.
A new binding agent, consisting of the yeast Saccharomyces cerevisiae immobilized in agarose, is proposed for use in diffusive gradients in thin films (DGT). Different gel compositions, containing from 4.5% to 20% (m/v) of S. cerevisiae and 1.5-5.0% (m/v) of agarose, were prepared and tested for uptake of Cd(II). For gels containing 20% (m/v) of S. cerevisiae, a mass of 14,900 ng has been attributed as the uptake limit of Cd for each disk. Determination of the Cd retained in the binding agent was readily carried out using a slurry of the agarose-yeast disk introduced directly into the inductively coupled plasma optical emission spectrometer. The performance characteristics of the DGT samplers, which were assembled with the proposed binding agent (25 mm disk containing 20% of S. cerevisiae and 1.5% of agarose) and a diffusive layer of cellulose (chromatographic paper 3MM Chr of 25 mm diameter), were evaluated by measuring the Cd(II) uptake at various pH values and ionic strengths. Very consistent results were found within the pH range 4.5-7.5 and at ionic strengths ≥0.005 mol L−1. The precision of DGT measurements was characterized by relative standard deviations of <8%. No changes in the uptake of Cd(II) were observed in the samplers that were assembled with recently prepared disks or 35-day-old stored disks. The proposed material has been applied to the analyses of river and sea water samples. For determination of Cd(II), excellent agreement between the results obtained from devices assembled with the proposed material and those assembled with conventional material (Chelex-100 resin) were obtained, strongly validating the use of the agarose-yeast gel disk as a new binding agent for DGT.  相似文献   

20.
Docekalová H  Divis P 《Talanta》2005,65(5):1174-1178
The diffusive gradient in thin films (DGT) technique was investigated and used to measure mercury concentration in river water. Mercury ions are covalently bound to amide nitrogen groups of commonly used polyacrylamide, which makes this gel unsuitable as a diffusive medium. In contrast, agarose gel was found as the diffusive gel for mercury measurements. Basic performance tests of agarose DGT verified the applicability of Fick's first law for DGT measurements. Two selective resins, Chelex-100 with iminodiacetic groups and Spheron-Thiol with thiol groups were used. The measured diffusion coefficient in agarose gel was close to that in water. The concentration of mercury in Svitava river measured by DGT with Speron-Thiol resin gel was higher (0.0116 ± 0.0009 μg l−1) than those obtained by Chelex-100 (0.0042 ± 0.0005 μg l−1). Different capture efficiencies of two adsorbents enable to estimate fractions of mercury bonded in different complexes in the river water. The concentrations of mercury found by DGT both Chelex-100 and Speron-Thiol resin gels are much lower than that measured directly in the river water (0.088 ± 0.012 μg l−1). This difference indicates that DGT concerns inorganic ions and labile species only, and that it is not able to include inert organic species and colloids.  相似文献   

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