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A zirconium oxide binding gel-based diffusive gradients in thin films (Zr-oxide DGT) was developed for simultaneous measurements of P(V), As(V), Cr(VI), Mo(VI), Sb(V), Se(VI), V(V), and W(VI). All of the oxyanions were rapidly bound to Zr-oxide gel with differences in binding affinity. The eight bound oxyanions were successfully recovered by one-step elution using a mild reagent of 0.2 M NaOH-0.5 M H2O2 by overcoming the problems in analyses of the oxyanions. The optimized elution time was reduced to 3-5 h from 24-48 h required by other DGTs. DGT uptakes of all the oxyanions were independent of pH (4.42-8.45) and ionic strength (0.1-500 mM). The DGT capacities for six oxyanions detected in multioxyanion solution were only 0.19 to 0.35 times of those detected in single-oxyanion solution, reflecting a strong competition among the oxyanions during DGT uptake. Except for Se(VI) in seawater, Zr-oxide DGT accurately measured all of the oxyanions in synthetic freshwater and seawater, with the capacities ~29 to >2397 times and ~7.5 to 232 times those of two commonly used DGTs (Metsorb and precipitated ferrihydrite (PF) DGTs) in freshwater and seawater, respectively. Measurements by Zr-oxide DGT in contaminated sediments were in agreement with only two oxyanions with the two commonly used DGTs; the two DGTs accumulated less or no mass of other oxyanions. This study demonstrates significant advantage of Zr-oxide DGT over the other DGTs in simultaneous measurements of the eight oxyanions due to the former's high capacity and a wide tolerance to environmental interferences, together with a high efficiency in elution. [ABSTRACT FROM AUTHOR]

We report a highly promising technique for the high-resolution imaging of labile phosphorus (P) in sediments and soils in combination with the diffusive gradients in thin films (DGT). This technique was based on the surface coloration of the Zr-oxide binding gel using the conventional molybdenum blue method following the DGT uptake of P to this gel. The accumulated mass of the P in the gel was then measured according to the grayscale intensity on the gel surface using computer-imaging densitometry. A pretreatment of the gel in hot water (85 °C) for 5 d was required to immobilize the phosphate and the formed blue complex in the gel during the color development. The optimal time required for a complete color development was determined to be 45 min. The appropriate volume of the coloring reagent added was 200 times of that of the gel. A calibration equation was established under the optimized conditions, based on which a quantitative measurement of P was obtained when the concentration of P in solutions ranged from 0.04 mg L-1 to 4.1 mg L-1 for a 24 h deployment of typical DGT devices at 25 °C. The suitability of the coloration technique was well demonstrated by the observation of small, discrete spots with elevated P concentrations in a sediment profile. [ABSTRACT FROM AUTHOR]

The reassessments of environmental processes in sediments rely upon capturing the heterogeneous features of elements at a small scale and at the same location. In this study, a diffusive gradients in thin films (DGT) technique was developed for the high-resolution simultaneous measurements of dissolved reactive phosphorus (DRP) and dissolved sulfide. A new binding gel was used in this DGT technique, which was prepared by incorporating AgI particles into the zirconium oxide binding gel previously used in the DGT measurement of DRP. The concentrations of the DRP and sulfide loaded into the binding gel were determined by a routine procedure and a computer-imaging densitometry (CID) technique, respectively. The performance of this DGT technique was tested under laboratory conditions and applied to in situ measurements in sediments of a shallow lake. Simultaneous release of DRP and dissolved sulfide was observed in a sulfide microniche with a diameter of 3 mm and in locally aggregated zones with a length over 1 cm, which was attributed to the simultaneous reductions of Fe(III) and sulfate and the associated release of Fe-bound P in the zones of the reactive organic matter in sediments. The good performance of this technique implies that there is a great potential for the development of new DGT techniques capable of simultaneous measurements of more analytes. [ABSTRACT FROM AUTHOR]

Dissolved reactive phosphorus (DRP) is the most available P form in sediments and often directly controls phytoplankton blooms in aquatic systems. In this study, a novel procedure was developed for two-dimensional (2D) measurement of DRP in sediments at a spatial resolution of 0.45 mm using the diffusive gradients in thin films (DGT) technique with a revised high-capacity binding phase (Zr oxide gel). This procedure involves DGT uptake of P in sediments, 2D slicing of the binding gel on a 0.45 × 0.45-mm grid system, elution of P from each gel square with 1 M NaOH, and microcolorimetric determination of DRP in each eluted solution using 384-microwell plates. Measurements of DRP via this procedure were tested in homogeneous solutions and sediments and produced an acceptable error (<20% relative standard deviation) for the analysis once the accumulated mass of P in each gel square reached 1.2 μg cm-2. This method was successfully applied to produce 2D images of the DRP distribution in sediments with and without the influence of tubificid worm bioturbation, revealing a much more pronounced and localized impact from tubificid worms than that found using a one-dimensional measurement of pore water DRP concentrations at 1-cm resolution. [ABSTRACT FROM AUTHOR]

Measurement of dissolved reactive phosphorus (DRP) by the diffusive gradients in thin films (DGT) technique was investigated using a new binding phase. Half-dried amorphous zirconium oxide (with 50 ± 5% of water content) was mixed with acrylamide solution for the preparation of the new binding phase. The resulting binding gel had a high binding capacity (223 μg P cm-2) for phosphate. The solution of NaOH (1 M) was used for elution of phosphate from the gel, and an elution efficiency of 0.95 was obtained. A test of DGT uptake with this gel showed its dependence on temperature, and there was no influence of pH (3 to 10) and ionic strength (10 nM to 0.1 M). Its capacity for DGT response exceeded 100 μg P cm-2, corresponding to a DRP concentration of more than 20 mg L-1 for a 24 h deployment with a standard DGT device at 25 °C, which was at least 50 times of the Fe-oxide gel commonly used in the present DGT technique. Measurements with this high-capacity DGT technique in a laboratory microcosm of homogeneously mixed sediments gave smooth and reproducible mass-depth profiles. This technique was well demonstrated by in situ measurements in algal- and macrophyte-dominated regions of Lake Taihu. The DGT-measured concentrations of DRP were on average 20% and 40% of the DRP concentrations in pore waters, respectively, indicating a partial resupply of the sediments to the pore waters with DRP. [ABSTRACT FROM AUTHOR]

Solution 31P nuclear magnetic resonance (NMR) spectroscopy is currently the main method for the characterization of phosphorus (P) forms in environment samples. However, identification and quantification of P compounds may be hampered by poor resolution of spectra caused by paramagnetic Fe and Mn. In this study, a novel technique was developed to improve spectral resolution by removing paramagnetic Fe and Mn from alkaline extracts via 8-hydroxyquinoline (8-HOQ) precipitation. Batch experiments showed that both Fe and Mn were effectively removed by the precipitation at pH 9.0, with the removal efficiencies of 83-91% for Fe and 67-78% for Mn from the extracts of five different environmental samples, while little effect was found on concentration of total P. The 31P NMR analysis of a model P solution showed that addition of 8-HOQ and its precipitation with metal ions did not alter P forms. Further analyses of the five extracts with 31P NMR spectroscopy demonstrated that the 8-HOQ precipitation was an ideal method compared with the present postextraction techniques, such as bicarbonate dithionate (BD), EDTA and Chelex-100 treatments, by improving spectral resolution to a large extent with no detrimental effects on P forms. [ABSTRACT FROM AUTHOR]

Fractionations of rare earth elements (REEs) in wheat (Triticum aestivum L.) were observed through application of exogenous mixed REEs under hydroponic conditions. Middle REE (MREE), light REE (LREE), and heavy REE (HREE) enrichments were found in roots, stems, and leaves, respectively, accompanied by the tetrad effect (an effect that can cause a split of REE patterns into four consecutive segments) in these organs. Investigations into REE speciation in roots and in the xylem sap with X-ray absorption spectroscopy (XAS) and nanometer-sized TiO2 adsorption techniques, associated with other controlled experiments, demonstrated that REE fractionations in wheat were caused by the combined effects of chemical precipitation, cell wall absorption, and solution complexation by organic ligands in the xylem vessels. REE fractionations in wheat, which were derived from the small differences of chemical properties across REE series, may reflect a sensitive internal chemical environment that influences plant accumulation for REEs and their analogues actinide radionuclides. [ABSTRACT FROM AUTHOR]