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1.
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   

2.
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   

3.
The dynamic technique of diffusive gradients in thin films (DGT), that measures metal speciation in situ, has found wide environmental application. Simple interpretation of the metal accumulation in terms of a solution concentration has assumed that trace metals do not penetrate beyond the surface of the binding layer, but penetration, although theoretically discussed has not yet been directly measured. Multiple binding layers were used to enable analysis of different depths of a DGT binding phase (Chelex-100 or iminodiacetate resins). In simple metal solution (no ligand) at pH 7, metal penetration to the back layer was low and similar for all metals. However, at lower pH up to 42% of an individual metal accumulated in the back resin layer. This was most noticeable for Mn at pH 4 and 5, but Cd and Co were also affected at pH 4. These results were consistent with rate limited binding, particularly for Mn. A kinetic model successfully fitted the data and allowed derivation of a binding rate constant and the mean distance that metals penetrate into a resin gel (λM). Only for Mn, Co and Cd were experimentally derived λM values greater than the diameter of a Chelex-100 resin bead. For most situations, then, the penetration into the binding layer is negligible and binding of trace metal ions can be regarded as instantaneous, validating the simple use and interpretation of DGT. For weakly binding metals at low pH the slower binding allows penetration, which may affect the DGT measurement.  相似文献   

4.
The performance characteristics of an alternative binding agent, suspended particulate reagent-iminodiacetate (SPR-IDA), for use with DGT methodology were investigated. The parameters investigated during this study included gel hydration, blank levels, elution factor (fe), capacity, the effects of pH on the binding of trace metals by DGT. The novel application of this resin for use as a quantitative standard for laser ablation ICP-MS was also evaluated. To further constrain the results for the SPR-IDA binding agent, parallel experiments were performed using resin gel containing Chelex 100, which has been widely reported in the literature. Hydration results showed that the SPR-IDA resin gel reached a stable dimension and weight within ∼30 min and was dimensionally stable for ≤6 months. The measured DGT blanks for the SPR-IDA resin were 0.0023, 0.15, 0.21, 0.0033 and 0.011 ng disc−1 for Co, Ni, Cu, Cd and Pb, respectively. The elution factor differed for the two resin types with the Chelex 100 recoveries slightly lower than previous reports and the SPR-IDA resin showing on average ∼5-9% better recoveries than DGT containing Chelex 100. The measured capacity of DGT discs containing the SPR-IDA binding agent was 0.26 mg Cd, similar to the calculated value of 0.29 mg Cd, indicating the entire resin layer was available for metal uptake.Both resin types performed equally well when deployed in 1 mM NaNO3 solutions with DGT measurements of ∼100% of direct solution measurements for Co, Ni and Cd. However, DGT measurements of Cu and Pb systematically decreased with increasing solution pH down to ∼50% of solution values at pH 8.0, due to artifacts resulting from colloid formation during the addition of the metals. This was remedied by adding the metals as dilute salt standards and addition of Mg(NO3)2 to eliminate adsorption to the container walls. In the latter experiments, DGT measured concentrations of Co, Ni, Cu, Cd and Pb were in agreement with solution concentrations. Deployment of DGT in solutions with increasing concentrations of trace metals yielded linear results, suggesting that quantitative analysis using simplified laser ablation techniques should be possible using this newly characterized SPR-IDA resin gel.  相似文献   

5.
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   

6.
7.
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   

8.
The agarose hydrogel has been increasingly used as a diffusive layer in diffusive gradients in thin films (DGT) measurements. However its diffusive characteristics have not been examined in detail. In this study, the performance of agarose gel was tested in DGT measurements of eight cations (Fe(II), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), and Cd(II)) and eight anions (P(V), As(V), Cr(VI), Mo(VI), Sb(V), Se(VI), V(V), and W(VI)). It was found that the thickness of agarose, a key parameter in the calculation of DGT measured concentration, remained unchanged after hydration followed by storage under the following conditions: pH 2–11, ionic strength 0–1.0 M, temperature 4–40 °C, and with the storage time extending to 300 d. Enrichment of cations and repelling of anions were observed in the gel under the ionic strengths of < 2–3 mM and <1 mM (NaNO3), respectively, which was attributed to the electrostatic interactions of these ions with the fixed negatively charged groups (mainly pyruvate) in the gel. The diffusion coefficients of cations and anions through the agarose gel (plus a PVDF filter membrane) were on average 1.10 ± 0.04 times of the reported diffusion coefficients through the agarose cross-linked polyacrylamide (APA) hydrogel, typically used in DGT technique. The working pH ranges for the agarose gel-assembled DGTs were 4–10 and 5–9 for anions and cations, respectively. The use of agarose gel, either individually or along with different filter membranes, affected the overall diffusion rates of cations and anions. The measured DGT concentrations of cations and anions in filtered natural freshwater and seawater were mostly in line with those measured directly. The results showed that the agarose gel can be used as one of the standard diffusive layers in DGT measurements for a wide range of inorganic and organic analytes.  相似文献   

9.
Measurements of the major cations Ca and Mg by the technique of diffusive gradients in thin films (DGTs) were systematically evaluated. The concentration in solution was calculated using Fick’s first law of diffusion from the directly measured flux to the DGT device. A selective cation exchange resin (Bio-Rad Chelex®100), which has been used extensively with DGT for trace metals, such as Cd2+, Cu2+ and Ni2+, was used for this work.

Elution of Ca and Mg from the resin with 1 M HNO3 was very reproducible. Measurements of Ca and Mg concentrations in synthetic solutions agreed well with the theoretical predictions. The negative response on uptake caused by lowered pH was investigated. Uptake was found to decline below pH 5. The capacity of the DGT device for Ca and Mg was also investigated to establish maximum deployment times for given concentrations.

Experiments with filtered and modified lake water show that DGT can be used to measure Ca and Mg when trace metals are present in the solution. An in situ deployment of DGT combined with an ultrafiltration study suggest that the Mg concentration measured by DGT is similar to the concentration found in the fraction <1 kDa.  相似文献   


10.
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   

11.
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   

12.
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   

13.
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   

14.
The utilization of Amberlite (IRP-69 ion-exchange resin, 100–500 wet mesh) as the binding phase in the diffusive gradients in thin films (DGT) technique has shown potential to improve the assessment of plant-available K in soils. The binding phase has recently been optimized by using a mixed Amberlite and ferrihydrite (MAF) gel which results in linear K uptake over extended deployment periods and in solutions with higher K concentrations. As restriction of K uptake by Ca on the Amberlite based resin gel has been previously proposed, potential competing effects of Ca2+, Mg2+ and NH4+ on K uptake by the MAF gel were investigated. These cations had no effect on K elution efficiency which was 85%. However, K uptake by the MAF gel was restricted in the presence of competing cations in solution. Consequently, the diffusion coefficient of K decreased in the presence of cations compared to previous studies but was stable at 1.12 × 10−5 cm2 s−1 at 25 °C regardless of cation concentrations. Uptake of K by the DGT device was affected by the presence of excessive Ca in more than 30% of twenty typical Australian agricultural soils. However, this problem could be circumvented by using a shorter deployment time than the normal 24 h. Moderate correlation of concentrations of K extracted by DGT with Colwell K (extracted by NaHCO3, R2 = 0.69) and NH4OAc K (R2 = 0.61) indicates that DGT measures a different pool of K in soils than that measured by the standard extractants used. In addition, the MAF gel has the ability to measure Ca and Mg simultaneously.  相似文献   

15.
The diffusive gradients in thin films (DGT) technique, utilizing resin gel with ion-exchange resin Duolite GT73 and new ion-exchange resin Ambersep GT74, was investigated for the accumulation of four mercury species (Hg2+, CH3Hg+, C2H5Hg+, C6H5Hg+). The diffusion coefficients of mercury species in agarose gel calculated on the basis of Fick’s Law were mercury species-specific. The diffusion coefficients of Hg2+ and CH3Hg+ at 25 °C (9.07 ± 0.23 × 10−6 cm2 s−1 and 9.06 ± 0.30 × 10−6 cm2 s−1, respectively) were very similar, but the diffusion coefficients of C2H5Hg+ (6.87 ± 0.23 × 10−6 cm2 s−1) and C6H5Hg+ (3.86 ± 0.19 × 10−6 cm2 s−1) were significantly lower. Influence of experimental conditions (pH, selected cations, chlorides and humic substance) on mercury species accumulation by DGT was studied. The DGT technique was applied to river water spiked with mercury species.  相似文献   

16.
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   

17.
For the first time, a diffusive gradients in thin films (DGT) device using molecularly imprinted polymer (MIP) as the binding agent and nylon membrane (NM) as the diffusive layer (NM-MIP-DGT) has been developed for sampling 4-chlorophenol (4-CP) in water. The MIP was prepared by precipitation polymerization with methacrylic acid as monomer and ethyleneglycoldimethacrylate as cross-linker. The diffusion coefficient of 4-CP through NM was obtained to be 0.788 ± 0.040 μ cm2 s−1 by diffusion cell method. The ratio was 1.01 ± 0.05 (mean ± standard deviation) for the concentration of 4-CP sampled by NM-MIP-DGT and analyzed by HPLC method to the total concentration of 4-CP in the synthetic solution where free 4-CP species dominated. The results showed that NM-MIP-DGT could sample 4-CP in synthetic solution accurately. The performance of NM-MIP-DGT for sampling 4-CP was independent of pH in the range of 3–7 and ionic strength in the range of 0.0001–0.1 mol L−1 NaCl solution. The concentration of free form of 4-CP sampled by NM-MIP-DGT decreased with the increasing concentration of dissolved organic carbon in different water samples due to the electrostatic interaction of natural organic compounds with 4-CP. 1.8 mg L−1 of the free form of 4-CP was determined by HPLC which was sampled by NM-MIP-DGT in an intermediate untreated industrial effluent. The NM-MIP-DGT can be a potential passive tool for sampling the free form of 4-CP in water.  相似文献   

18.
Diffusive equilibrium (DET) and diffusive gradient in thin film (DGT) techniques with an inductively coupled plasma mass spectrometry detection of elements were applied to characterize uranium, manganese, iron and 238U/235U isotopic ratio depth profiles in sediment pore water at high spatial resolution and to monitor uranium uptake/remobilization processes in uranium spiked sediment core samples under laboratory, well controlled conditions. Modified constrained sediment DGT probes, packed with Spheron-Oxin® resin gel, were employed for selective uranium measurements. Spatially resolved DET and DGT responses were indicative of local redistribution of uranium in naturally uranium poor and rich sediments.  相似文献   

19.
Diffusive gradients in thin films (DGT) and tangential-flow ultrafiltration (TF-UF) were combined for fractionation of Al and Cu in river water containing high content of dissolved organic carbon. A procedure based on ultrafiltration data is proposed to determine diffusion coefficients of the analytes in water samples and model solutions containing both free metal (M) and complex (metal - humic substance). Aiming to evaluate the accuracy of the proposed approach, the DGT results were compared with those from a protocol for determination of labile Al and Cu based on solid phase extraction (SPE). Good agreement between data from DGT and SPE were attained for model solutions. For analysis of real organic-rich water samples, differences between DGT and SPE measurements were consistent with the time-scales of the techniques. The concentration of labile Al determined by DGT were lower than the total dissolved concentrations (determined by inductively coupled plasma mass spectrometry) and exceeded the ultrafiltered concentration, indicating that inorganic Al species (species small enough to pass through 1 kDa membrane) were minor species as compared with Al organic complexes. For both Al and Cu, there were species not measured by DGT as they are not sufficiently labile.  相似文献   

20.
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   

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