Trace metal measurements in low ionic strength synthetic solutions by diffusive gradients in thin films

In view of conflicting reports regarding the performance of DGT in low ionic strength solutions (I < 1 mM), further investigations have been carried out. Minimal washing of the diffusive gel and deployment in 1.0 and 10 mM NaNO3 solutions containing Cu and Cd gave the theoretical response of 1 for [C](DGT)/[C](SOLN), where [C](DGT) is the concentration of metal measured by DGT and [C](SOLN) is the concentration of metal measured directly in the solution by an appropriate analytical method. Erroneously high values for [C](DGT)/[C](SOLN) were obtained when these same gels were deployed at I = 0.1 mM, presumably due to a net negative charge on the gel, attributable to the presence of initiation products of polymerization. However, washing the diffusive gels completely, where the storage solution pH equaled that of deionized water, gave values of approximately 0.5 for [C](DGT)/[C](SOLN) from deployments at I = 0.1 mM, consistent with the lower measured value of the diffusion coefficients at this ionic strength. These results can be explained by the presence of a net positive charge on the gel when it is exhaustively washed, which reduces the effective diffusion coefficient of metal ions by changing their concentration at the gel-solution interface (Donnan partitioning). Diffusive gel equilibration experiments showed the presence of low capacity sites capable of binding metals irrespective of ionic strength. This binding within the diffusive gel does not affect most DGT measurements, as short (4 h) deployments at concentrations of 10 ppb gave theoretical results. Incomplete washing of the resin-gel caused a 5-15% measurement error and a decrease in precision, even at ionic strengths of 10 mM. A high level of accuracy and precision (typically <5%) was maintained during all aspects of this work, even at ionic strengths of 0.1 mM, in contrast to previous results. This is attributable to three factors: (1) exhaustive washing and conditioning protocols, (2) improvements to the DGT sampling device, and (3) low and reproducible blanks due to ultraclean handling procedures. Provided effective diffusion coefficients measured at the same ionic strength are used, the established DGT theory is obeyed irrespective of ionic strength.     

Performance study of diffusive gradients in thin films for 55 elements

The technique of diffusive gradients in thin films (DGT) is a fairly new and useful tool for in situ measurements of labile metal ions in water. The applicability of DGTs was investigated by comparing independently determined or estimated diffusion coefficients with DGT effective diffusion coefficients (D(DGT)) for 55 elements. The DGTs were exposed at a controlled fluid velocity of 0.1 m s(-1) and a concentration of 1 ng mL(-1) at four pH levels between 4.7 and 6.0, and the D(DGT) values were determined from the uptake by the sampler. The measured D(DGT) values for the elements Co, Ni, Cu, Zn, Cd, Pb, Al, Mn, and Ga were close to previously published values with some deviations for Pb and Zn. The uptake of V, Cr, Fe, U, Mo, Ti, Ba, and Sr varied with pH, and there were some experimental problems that require further investigations. A novel set of D(DGT) values for the lanthanides (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Tb, Yb, Lu, Y) was established. The D(DGT) values for these were about 10-15% lower than for free ions in water and indicate that diffusion coefficients of metal ions in the agarose polyacrylamide diffusive hydrogel are 10-15% lower than in water. The high consistency of the data for the lanthanides establishes these elements as new performance test metals for the DGT sampler. The accumulation of the elements Li, Na, K, Rb, Mg, Ca, B, Tl, P, S, As, Bi, Se, Si, Sn, Sb, Te, Zr, Nb, Hf, Ta, W, Th, and Ag was low (D(DGT) lower than 10% of theoretical values). A more efficient elution procedure using concentrated nitric acid for the absorbent gel was established, with elution efficiencies between 95 and 100% for most metals. For deployment times of 24 h, detection limits from 0.001 to 1 ng mL(-1) were achieved with moderate precautions to prevent contamination.     

Speciation of dissolved inorganic arsenic by diffusive gradients in thin films: selective binding of AsIII by 3-mercaptopropyl-functionalized silica gel

A diffusive gradients in thin films (DGT) technique for selectively measuring As(III) utilizes commercially available 3-mercaptopropyl-functionalized silica gel. Deployment of the new technique alongside the Metsorb-DGT for total inorganic arsenic allows the calculation of As(III) directly and As(V) by difference. Uptake of As(III) by mercapto-silica was quantitative and elution with a mixture of 1 mol L(-1) HNO(3) and 0.01 mol L(-1) KIO(3) gave a recovery of 85.6 ± 1.7%. DGT validation experiments showed linear accumulation of As(III) over time (R(2) > 0.998). Accumulation was unaffected by varying ionic strength (0.0001-0.75 mol L(-1) NaNO(3)) and pH (3.5-8.5). Deployment of mercapto-silica DGT and Metsorb DGT in seawater spiked with As(III) and As(V) demonstrated the ability of the combined approach to accurately quantify both species in the presence of potential competing ions. Ferrihydrite DGT, which has been previously reported for the measurement of total inorganic arsenic, was evaluated in seawater and shown to underestimate both As(III) and As(V) at longer deployment times (72 h). Reproducibility of the new mercapto-silica DGT technique was good (relative standard deviations < 9%), and the average method detection limit was sufficiently low to allow quantification of ultratrace concentrations of As(III) (0.03 μg L(-1); 72 h deployment).     

Development of the diffusive gradients in thin films technique for the measurement of labile gold in natural waters

Gold is a precious metal that exists in most soils, sediments, and natural waters at extremely low concentrations (<1 μg/kg). The diffusive gradients in thin films (DGT) technique, used extensively for measuring trace metal concentrations in soils, sediments, and waters, has potential for geochemical exploration for gold, but has not been developed for this metal. This work investigates the possibility of measuring labile gold using DGT by introducing a new binding layer based on activated carbon. The performance of this new technique was assessed using gold(III) chloride in solution by: (1) determining the diffusion coefficient of gold(III) in hydrogels; (2) determining the uptake of gold(III) chloride by the new activated carbon binding layer; (3) determining an elution methodology for the binding layer and evaluating its efficiency; (4) assessing the capacity of the activated carbon binding layer to adsorb gold; (5) determining the effect of pH and ionic strength (as NaCl) on performance, and (6) assessing the selectivity of the new binding layer for gold. It was found that the diffusion coefficient of gold(III) increased as solution pH decreased. The diffusion coefficient also increased at high ionic strength (≥0.1 M NaCl). Accounting for these phenomena, the DGT technique behaved predictably under all tested conditions. The technique can potentially be used as a geochemical exploration tool for gold in soils and in aqueous environments, with method detection limits as low as 0.9 ng/L for a 7-day deployment.     

Analysis of polyacrylamide gels for trace metals using diffusive gradients in thin films and laser ablation inductively coupled plasma mass spectrometry

A simple method for the analysis of polyacrylamide diffusive gradients in thin film (DGT) gels by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), employing a novel use of (115)In internal standardization, has been developed. This method allows the determination of Co, Ni, Cu, Zn, Cd, and Pb concentrations (at the DGT filter face) or fluxes in sediments at a spatial resolution of 100 microm. Single-layered gels, using an optimized laser defocus of 4000 microm at 400 mJ power, showed high precision (generally approximately 10%) and a linear response during solution deployment. Of the elements Sc, In, Ba, La, Ce, and Tb, Ba most closely tracked variations in laser energy and showed the highest analytical precision but could not be used as an internal standard due to its elevated presence in natural sediments. Therefore, internal standardization, necessary to normalize data collected on different days, was carried out using (115)In contained within a second layer of backing gel and dried along with the analyte layer as a dual-gel disk. This multilayered gel standard required a laser defocus setting of 1000 microm and a laser power of approximately 800 mJ. Analytical precision for a 64-spot ablation grid at 100-microm spacing was approximately 10%. Verification of this method was carried out on DGT sediment probes deployed in Priest Pot (English Lake District). Results obtained by conventional slicing techniques and aqueous elution agreed with laser ablation results when the different sampling areas were considered. The elution results varied by a factor of <2, whereas the laser ablation technique showed a variability of approximately 4, indicating localized elevated concentrations of Co. This higher resolution LA-ICPMS method could ultimately lead to an improved understanding of the geochemical processes responsible for metal uptake and release in sediments.     

Direct in situ measurements of labile inorganic and organically bound metal species in synthetic solutions and natural waters using diffusive gradients in thin films

The emerging technique of DGT (diffusive gradients in thin films) is shown to be capable of performing new speciation measurements in situ in natural waters. In DGT, metals are bound to a resin layer after passing through a well-defined diffusion layer. Cd was measured in solutions containing glycine, EDTA, and fulvic (FA) and humic acids (HA) by atomic absorption spectroscopy (AAS), anodic stripping voltammetry (ASV), and DGT. DGT measured similar labile fractions to ASV, with detailed differences being consistent with a thicker diffusion layer allowing more dissociation of labile complexes and a slower diffusion of FA and HA complexes through the gel. When single measurements are made in complex solutions with DGT, precise quantification is impossible due to uncertainties concerning the distribution of species with different diffusion coefficients. A new procedure was proposed based on the advantage of DGT of being able to control the pore size of the diffusive gel layer. Small (inorganic) species diffuse freely through all gels but larger FA and HA (organic) complexes diffuse less freely in more constrained gels. When measurements were made on known solutions of Cu and FA or HA, it was possible to quantify the inorganic and organic species separately. They agreed well with predictions made using the WHAM speciation code. Multiple DGT units were also deployed in situ in a stream with high dissolved organic carbon (14.6 mg/L). The systematic differences between the devices with different gel compositions enabled determination, for the first time, of the in situ concentrations of both labile inorganic and organic species in natural water. A single DGT device with a constrained gel can be used to quantify inorganic species directly, providing absolute accuracy is not required. This ability of DGT to measure well-defined fractions of metals in situ using a simple device gives it considerable potential as a regulatory tool. A direct speciation measurement may be preferable to modeling approaches which require diverse input data that are difficult to determine.     

Application of a poly(4-styrenesulfonate) liquid binding layer for measurement of Cu2+ and Cd2+ with the diffusive gradients in thin-films technique

A diffusive gradients in thin films (DGT) technique for measuring Cd and Cu is described using, for the first time, a liquid phase binding layer and a dialysis membrane diffusive layer. The binding phase was a 0.020 M solution of poly(4-styrenesulfonate) (PSS) polyelectrolyte using a specially designed DGT deployment device. The binding properties of Cd2+, Cu2+, and a range of alkali and alkaline earth metal ions to the PSS solution were characterized. The PSS behaved like a cation exchanger with preferential binding to Cd2+ (6.0 micromol mL(-1), log K = 9.0) and Cu2+ (2.5 micromol mL(-1), log K = 8.1) under competitive binding conditions. PSS had a substantial binding capacity at pH > 3 and at competitive Na+ concentrations up to 1.0 M. The DGT devices were successfully validated for Cd2+ (accumulated mass vs time r2 = 0.969, recovery compared with predicted values = 98%) and Cu2+ (r2 = 0.980, recovery = 98%) in synthetic lake water (Windermere). Validation was also undertaken for Cu in a spiked local lake water (Parkwood Pond) (r2 = 0.981, recovery = 46%). The low recovery here was due to complexation of Cu by natural organic matter (14 mg C L(-1)). Field deployments of the DGT devices were successful at measuring Cu concentrations of 0.031-0.63 microg L(-1) in local fresh and salt waterways. These DGT-labile measurements were 0.05-39% of the 0.45-microm-filtered Cu values.     

Development and performance of the diffusive gradients in thin-films technique for the measurement of technetium-99 in seawater

A novel technique for obtaining time-integrated 99Tc concentrations in seawater has been developed, using diffusive gradients in thin films (DGT). The performance of TEVA resin as a binding agent for 99Tc was investigated via laboratory experiments. The accumulated 99Tc activity per unit area of resin-gel was proportional to both the bulk solution activity and the exposure time for deployments of up to 2 weeks. The response of DGT was found to be independent of solution chemistries over the pH range 3-8 and ionic strength range 0.01-1.3 M. Seawater has pH 8 and ionic strength of approximately 0.7 M; therefore, the potential of the technique for field deployment in seawater was demonstrated. Detection limits of 0.05 and 0.025 Bq L(-1), for 2- and 4-week DGT deployments, respectively, were calculated for 99Tc measurement by liquid scintillation spectrometry. Using quadrupole ICPMS to measure bound 99Tc could reduce these detection limits to 0.125 mBq L(-1) for a 4-week deployment. These detection limits are sufficiently low for monitoring contaminated environments, including the Irish Sea. This method is simpler and faster than other 99Tc analysis methods and represents the only means of obtaining time-integrated data.     

Low temperature preparation of nanocrystalline Sr0.5Ba0.5Nb2O6 powders using an aqueous organic gel route

Nano-sized Sr_0.5Ba_0.5Nb₂O₆ (SBN50) ceramic powders have been synthesized by an aqueous organic gel route. Homogeneous Sr-Ba-Nb precursor gels are prepared with Ba-EDTA, Sr-EDTA, and Nb-citrate complex as source of Sr, Ba, and Nb, respectively. Citric acid and ethylenediaminetetraacetic acid (EDTA) were used as the chelating agents. The structural variation of the SBN powder with annealing temperature was studied by TG-DTA, FT-IR and XRD. The precursor gel on calcination at 800 °C for 2 h produces a pure tungsten bronze SBN phase and the corresponding average particle size is 30-50 nm. The influences of the pH and the molar ratio of citric acid:Nb cation on the formation of homogeneous Sr-Ba-Nb precursor gels were also studied. The results show that a homogeneous Sr-Ba-Nb precursor gel with no precipitate is formed at pH 8 and the optimum molar ratio of citric acid and the metal cations is 3:1.     

Advanced prospects for the preparation of zirconium [<Superscript>99</Superscript>Mo]molybdate(VI) gel from diluted reactants and <Superscript>99<Emphasis Type="Italic">m</Emphasis> </Superscript>Tc elution performance

Zirconium [⁹⁹Mo]molybdate(VI) gel (ZrMo) was prepared from dilute mixed solutions of zirconium oxychloride and [⁹⁹Mo]molybdate at pH 4.7. Paramolybdate(VI) anions were attracted to the positively charged surface of zirconia(IV) particulates (PZC at pH 7.2). The postulated reaction mechanism and gel formula were verified by radiometric analysis, X-ray diffraction, scanning electron microscopy, TGA, DTA, IR spectroscopy, and X-ray fluorescence analysis. ^99mTc elution from ZrMo dried at 50 and 200°C was investigated. Reproducibly high ^99mTc elution yield with high levels of radionuclidic, radiochemical, and chemical purity was achieved from the gel dried at 50°C. Correlation between structural properties of ZrMo and ^99mTc elution performance was discussed.     

In situ measurements of labile Al and Mn in acid mine drainage using diffusive gradients in thin films

The technique of diffusive gradients in thin films (DGT) can be used for in situ measurements of labile metal species in water, but the application for this method on acid mine drainage (AMD) is complicated due to reduced sampler adsorption of metals at low pH. This study evaluates the use of DGT on labile Al and Mn in AMD (pH 3.1-4.2). DGT measurements were performed both in standard solutions in the laboratory and in situ in the field. Laboratory results show that DGT can be used in water with pH as low as 3.0 for Al and 4.0 for Mn without correcting for reduced adsorption. Below pH 4.0, the adsorption of Mn showed a linearly decrease with pH to approximately 55% at pH 3.0. Taking this correction into account revealed that 84-100% of the total dissolved Al and Mn measured in the field was DGT-labile. Measurements using DGT agreed well with predictions using the speciation program WHAM VI. This study shows that the use of DGT can be extended below the previously reported pH working range for Al, and for Mn using a simple linear correction with respect to pH, and demonstrates that the technique can be applied for monitoring time-integrated labile metal concentrations at AMD sites.     

Accuracy of the diffusive gradients in thin-films technique: diffusive boundary layer and effective sampling area considerations

When using the diffusive gradients in thin-films (DGT) technique in well-stirred solutions, the diffusive boundary layer has generally been ignored on the assumption that it is negligibly thin compared to the total thickness of delta g, i.e., the sum of the thickness of the prefilter and diffusive gel. Deployment of devices with different diffusive layer thicknesses showed that the thickness of the DBL was approximately 0.23 mm in moderate to well-stirred solutions, but substantially thicker in poorly or unstirred solutions. Measurement of the distribution of Cd in the DGT resin gel at high spatial resolution (100 microm) using laser ablation inductively coupled plasma mass spectrometry showed that the effective sampling window had a larger diameter (2.20 cm) than the geometric diameter of the exposure window (2.00 cm). Lateral diffusion in the gel, which had previously been neglected, therefore increased the effective surface area of the device by approximately 20%. The concentrations measured by DGT agreed well with the known concentrations in standard solutions for all diffusion layer thicknesses, when the effective area and the appropriate diffusive boundary layer (DBL) were used. The extent of the error associated with neglecting the DBL and using the geometric window area depends on the gel layer thickness and the true thickness of the DBL, as determined by the deployment geometry and flow regime. When DGT measurements were made in well-stirred solutions using a 0.80-mm diffusive gel, the effect of neglecting the DBL and using the inappropriate geometric area offset each other, with the error being <+/-10%. For precise measurements, and especially work involving speciation or kinetic measurements, where DGT devices with different diffusive gel layer thicknesses are deployed, it is necessary to use the effective area and the appropriate DBL thickness in the full DGT equation, which allows for the use of layer-specific diffusion coefficients.     

Evaluation of the percutaneous absorption of chlorpromazine from PLO gels across porcine ear and human abdominal skin

Objective: The overall objective of this work is to determine the percutaneous absorption of chlorpromazine hydrochloride from pluronic lecithin organogels (PLO gels) and verify the suitability of topically applied chlorpromazine hydrochloride PLO gels for use in hospice patients for relieving symptoms such as vomiting and nausea during the end stages of life.

Methods: PLO gels of chlorpromazine hydrochloride were prepared using isopropyl palmitate (IPP) or ricinoleic acid (RA) as oil phase. In vitro percutaneous absorption of chlorpromazine hydrochloride was assessed through porcine ear and human abdominal skin. Further, the theoretical steady state plasma concentration (C_ss) of chlorpromazine was calculated from the flux values.

Results: The pH, viscosity, and stability of both PLO gels prepared with IPP and RA were comparable. The thixotropic property of RA PLO gel was found to be better than that of IPP PLO gel. The permeation of chlorpromazine hydrochloride was higher from RA PLO gel than from IPP PLO gel and pure drug solution. Theoretical C_ss of chlorpromazine from pure drug solution, IPP PLO gel and RA PLO gel were found to be 1.05, 1.20, and 1.50?ng/ml, respectively. PLO gels only marginally increased the flux and theoretical C_ss of chlorpromazine.

Conclusion: From this study, it is clearly evident that PLO gels fail to achieve required systemic levels of chlorpromazine following topical application. Chlorpromazine PLO gel may not be effective in treating nausea and vomiting for hospice patients with swallowing difficulties.     

Sorption of Mo(VI) on zirconium molybdosilicate gel and potential application as a <Superscript>99</Superscript>Mo/<Superscript>99<Emphasis Type="Italic">m</Emphasis> </Superscript>Tc generator

Sorption of Mo(VI) from aqueous nitrate solutions onto zirconium molybdosilicate (ZrMoSi) gel was studied using ⁹⁹Mo radiotracer. The acid–base titration curve showed that the prepared ZrMoSi gel was an amphoteric material with the point of zero charge (PZC) at pH 2.5. The highest distribution coefficient (600 mL g^–1) of ⁹⁹Mo(VI) on ZrMoSi from nitrate media was achieved at pH 2.1. The sorption kinetics of ⁹⁹Mo(VI) onto ZrMoSi obeyed the pseudo-second-order model. The breakthrough sorption capacity of ZrMoSi gel was found to be 4.25 × 10^–2 [mmol Mo(VI)] g^–1. The prepared ⁹⁹Mo/^99mTc chromatographic column generator showed a good performance: The ^99mTc elution yield was 87.7%, pH of the eluate ranged from 5.6 to 7.2, and the radionuclidic purity of the eluted ^99mTc was >99.99% with a radiochemical purity of 98.31% (as ^99mTcO₄^–).     

Apatite and Portland/apatite composite cements obtained using a hydrothermal method for retaining heavy metals

Apatite and Portland/apatite composite cements containing steelwork dusts have been prepared using a low temperature hydrothermal method (200 degrees C, 48h). The produced solids were characterized by means of XRD, IR, and SEM-EDX, and the remaining liquid was analyzed by ICP. The results clearly show the capability of these cements to inertise the heavy metals contained in steelwork dusts, that is Fe, Pb, Mo, Cr, Mn, Ni, and Zn. In the case of apatitic cements, Fe, Mg, Cr, Mn, and Pb coming from steel dust replaced Ca in the divalent cation position of the apatite structure, while Si and Mo replaced P in tetrahedral position. The average crystal size of the apatite-containing dust is smaller than in pure apatite synthesized using the same procedure, which is related to the magnesium content of the dust, since magnesium seems to inhibit the crystal growth. XRD diagrams of composite cements show only peaks corresponding to phases observed in the single cements, and in that no new phases are found. However, EDX analysis reveals the introduction of cations coming from Portland cement into the apatite structure. From the results of water analysis it could be concluded that the capability of retention is higher in composite matrices than in the pure apatite one. In conclusion, the obtained data allow stating that the proposed method, the hydrothermal synthesis of steelwork dust containing cement, is a reliable one for immobilization of toxic residues containing heavy leachable cations.     

Selective adsorption of molybdenum(VI) from Mo-Re bearing effluent by chemically modified astringent persimmon

Astringent persimmon was chemically cross-linked by formaldehyde to obtain a novel kind of adsorption gel, which was named as APF gel. The adsorption behaviors of Mo(VI) and Re(VII) along with other coexisting metals onto the APF gel were studied in the present paper. The APF gel was found to be effective for the adsorption of Mo(VI) while the gel is almost completely inert toward rhenium and calcium over the whole hydrochloric acid concentration region. The APF gel has a low affinity for iron, copper, lead, nickel, manganese and zinc ions when the concentration of HCl is higher than 1 mol/L. The gel exhibited selectivity only for Mo(VI) with a remarkably high adsorption capacity 1.05 mol/kg, and the adsorption behavior obeys the Langmuir model. According to the thermodynamic and kinetic studies, the endothermic adsorption process followed pseudo-second order kinetics. Also, its excellent adsorption characteristics for Mo(VI) were confirmed by the adsorption and elution tests using a column packed with the APF gel. The result provides a new approach for the recovery of Mo(VI) from a industrial waste effluent.     

A density-functional study of the structures, binding energies and magnetic moments of the clusters Mo(N) (N = 2-13), Mo(12)Fe, Mo(12)Co and Mo(12)Ni

We report the results of density-functional calculations of the structures, binding energies and magnetic moments of the clusters Mo(N) (N = 2-13), Mo(12)Fe, Mo(12)Co and Mo(12)Ni that were performed using the SIESTA method within the generalized gradient approximation for exchange and correlation. For pure Mo(N) clusters, we obtain collinear magnetic structures in all cases, even when the self-consistent calculations were started from non-collinear inputs. Our results for these clusters show that both linear, planar and three-dimensional clusters have a strong tendency to form dimers. In general, even-numbered clusters are more stable than their neighbouring odd-numbered clusters because they can accommodate an integer number of tightly bound dimers. As a consequence, the binding energies of pure Mo(N) clusters, in their lowest-energy states, exhibit an odd-even effect in all dimensionalities. Odd-even effects are less noticeable in the magnetic moments than in the binding energies. When comparing our results for pure Mo clusters with those obtained recently by other authors, we observe similarities in some cases, but striking differences in others. In particular, the odd-even effect in three-dimensional Mo clusters was not observed before, and our results for some clusters (e.g.?for planar Mo(3) and Mo(7) and for three-dimensional Mo(7) and Mo(13)) differ from those reported by other authors. For Mo(12)Fe and Mo(12)Ni, we obtain that the icosahedral configuration with the impurity atom at the cluster surface is more stable than the configuration with the impurity at the central site, while the opposite occurs in the case of Mo(12)Co. In Mo(12)Co and Mo(12)Ni, the impurities exhibit a weak magnetic moment parallely coupled to the total magnetic moment of the Mo atoms, whereas in Mo(12)Fe the impurity shows a high moment with antiparallel coupling.     

Encapsulation of deoxyribonucleic acid molecules in silica and hybrid organic-silica gels

The encapsulation of small DNA molecules was attempted in pure silica and in hybrid polyvinyl alcohol-silica gels. The materials which were obtained were examined by nitrogen adsorption, and by ²⁹Si and ³¹P NMR spectroscopy. The extraction of the DNA molecules from the gels was examined in a buffer aqueous solution as well as in an acidic medium. The results suggested that the DNA molecules remained trapped inside the gels due to a permanent bonding to the gel network.     

Arsenate adsorption and desorption kinetics on a Fe(III)-modified montmorillonite

The adsorption-desorption kinetics of arsenate on a Fe(III)-modified montmorillonite (Fe-M) was studied at different arsenate concentrations, pH and stirring rates. The synthesized solid was a porous sample with Fe(III) present as a mix of monomeric and polymeric Fe(III) species in the interlayer and on the external surface. Adsorption took place in a two-step mechanism, with an initial fast binding of arsenate to Fe(III) species at the external surface (half-lives of 1 min or shorter) followed by a slower binding to less accessible Fe(III) species in pores and the interlayer (half-lives of around 1 h). Desorption kinetics also reflected the presence of externally and internally adsorbed arsenate. At pH 6 the maximum adsorbed arsenate was 52 μmol/g, a value that is low as compared to adsorption on ferrihydrite (700 μmol/g) and goethite (192-220 μmol/g). However, since the Fe(III) content of Fe-M is much lower than that of ferrihydrite and goethite, Fe(III) species in Fe-M are more efficient in binding arsenate than in ferrihydrite or goethite (one As atom is attached every 8.95 iron atoms). This high binding efficiency indicates that Fe(III) species are well spread on montmorillonite, forming small oligomeric species or surface clusters containing just a few iron atoms.     

Perfluorosulfonated ionomer-modified diffusive gradients in thin films: tool for inorganic arsenic speciation analysis

A new concept in speciation analysis based on the diffusive gradients in thin films (DGT) technique is described. By use of two sets of DGT devices, one set with perfluorosulfonated ionomer (Nafion) diffusive membranes and the other with polyacrylamide, anionic and uncharged analytes can be fractionated on the basis of charge. The dual device method is applied to speciation analysis of dissolved inorganic arsenic species. Over the environmentally significant pH range, inorganic As(III) exists as neutral H(3)AsO(3), whereas As(V) is present as anionic H(2)AsO(4)(-) and HAsO(4)(2-). The measured diffusion coefficient of As(III) through the negatively charged Nafion membrane is significantly larger than that of the As(V) species, whereas diffusion rates are similar through polyacrylamide diffusive gels. Hence, after simultaneously deploying DGT devices with and without Nafion membranes, measurement of the amount of accumulated As in each type of device enables the concentration of both oxidation states to be determined.