An evaluation of ferrihydrite- and Metsorb™-DGT techniques for measuring oxyanion species (As,Se, V,P): Effective capacity,competition and diffusion coefficients

This study investigated several knowledge gaps with respect to the diffusive gradients in thin films (DGT) technique for measurement of oxyanions (As(III), As(V), Se(IV), Se(VI), PO₄³⁻, and V(V)) using the ferrihydrite and Metsorb™ binding layers. Elution efficiencies for each binding layer were higher with 1:20 dilutions, as analytical interferences for ICP-MS were minimised. Diffusion coefficients measured by diffusion cell and by DGT time-series experiments were found to agree well and generally agreed with previously reported values, although a range of diffusion coefficients have been reported for inorganic As and Se species. The relative binding affinity for both ferrihydrite and Metsorb™ was PO₄³⁻ ≈ As(V) > V(V) ≈ As(III) > Se(IV) ? Se(VI) and effective binding capacities were measured in single ion solutions, and spiked synthetic freshwater and seawater, advising practical decisions about DGT monitoring. Under the conditions tested the performance of both ferrihydrite and Metsorb™ binding layers was directly comparable for As(V), As(III) Se(IV), V(V) and PO₄³⁻ over a deployment spanning ≤2 days for both freshwater and seawater. In order to return quantitative data for several analytes we recommend that the DGT method using either ferrihydrite or Metsorb™ be deployed for a maximum of 2 days in marine waters likely to contain high levels of the most strongly adsorbing oxyanions contaminants. The high pH, the competitive ions present in seawater and the identity of co-adsorbing ions affect the capacity of each binding layer for the analytes of interest. In freshwaters, longer deployment times can be considered but the concentration and identity of co-adsorbing ions may impact on quantitative uptake of Se(IV). This study found ferrihydrite-DGT outperformed Metsorb-DGT while previous studies have found the opposite, with variation in binding materials masses used being a likely reason. Clearly, preparation of both binding layers should always be optimised to produce the highest capacity possible, especially for seawater deployments.     

碱式碳酸镁为新结合相的薄膜梯度扩散技术原位富集测定富营养水体中的磷

薄膜扩散梯度技术(Diffusive gradients in thin films technique, DGT)是近年来应用于自然水体、沉积物和土壤中活性磷原位测定的一种新技术。利用含碱式碳酸镁的聚丙烯酰胺凝胶膜为 DGT 新结合相,探讨了初始浓度、放置时间、pH 值及离子强度对组装后 DGT 吸附性能的影响。用10 mL 0.25 mol/ L H2 SO4对结合相进行洗脱,洗脱率为85%±5%。组装后 DGT 对磷的测定不受溶液 pH 值(4.10~9.15)和离子强度(0.001~0.05 mol/ L)的影响。在温度25℃,pH 7.00,磷初始浓度为2 mg/ L 时, DGT 对磷的最大吸附容量为20.4μg。初始磷浓度为0.001~20 mg/ L 时,新 DGT 测定值与磷钼蓝比色法测定值一致。本方法对磷的检出限为102.4 ng/ L。将碱式碳酸镁-DGT 和商品化的 Ferrihydrite-DGT 应用于合成海水、厦门近岸海水、易海、巢湖水和南淝河中的对比检测,结果表明,碱式碳酸镁-DGT 能更准确测定不同水体中磷浓度。     

Simultaneous measurements of As, Mo, Sb, V and W using a ferrihydrite diffusive gradients in thin films (DGT) device

The ferrihydrite-backed DGT (diffusive gradients in thin films), recently developed for arsenic and phosphate measurements was, for the first time, characterized with respect to molybdate, antimonate, vanadate and tungstate determination. Arsenate was included in the characterization to allow comparison with literature data and thus provide quality control of the measurements. In addition to laboratory experiments, field measurements were carried out in a natural stream in northern Sweden affected by mine drainage. It was shown that ferrihydrite-DGT is suitable for simultaneous determination of labile arsenic, molybdate, antimonate, vanadate and tungstate over a wide pH range. Diffusion coefficients were estimated using two different methods; diffusion cell and direct uptake to DGT devices in synthetic solutions. Estimations of the coefficients using the direct uptake method were performed between pH 4 and 8. The results from the two methods agreed well irrespective of pH, except for molybdate and antimonate that showed decreased values at pH 8. Adsorption of the analytes to ferrihydrite gel-discs was rapid at all pH values. However, there was a tendency toward lower adsorption affinity for antimonate compared to the other anions. 100% recovery of accumulated analytes was achieved through complete dissolution of the ferrihydrite adsorbent using 1.4 molL(-1) HNO(3) with 0.1 molL(-1) HF. From field sampling it was concluded that the opportunities for accurate antimonate and molybdate determination decrease at pH≥8.7. DGT-labile concentrations were generally lower than dissolved concentrations. Relatively lower DGT concentrations, compared to dissolved (<0.45 μm), were observed under a period when ferric oxide precipitations were detected on the DGT protective filter.     

Evaluation of DGT techniques for measuring inorganic uranium species in natural waters: Interferences,deployment time and speciation

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.     

Investigating chemical constraints to the measurement of phosphorus in soils using diffusive gradients in thin films (DGT) and resin methods

The effect of potential chemical constraints on the performance of two relatively new soil P testing methods, anion exchange membrane (AEM) and diffusive gradients in thin films (DGT), were evaluated. Exposures to ranges of anion (Cl(-), NO(3)(-), SO(4)(2-) and HCO(3)(-)) concentrations relevant to agricultural soils had minimal effect on P recoveries using DGT. It has also been shown previously that DGT P recoveries are unaffected by varying pH (3-9). In contrast, increasing NO(3)(-) and SO(4)(2-) concentrations in solution reduced the recovery of P using the resin method (anion exchange membrane, AEM) by 24% at 50mgL(-1) NO(3)(-) and by 47% at 12mgL(-1) SO(4)(2-) when the P concentration of the test solution was 2mgL(-1). Phosphorus sorption by the resin decreased with increasing Cl(-) concentrations until there was a 100% decrease at 300mgL(-1) Cl(-) when the P concentration of the test solution was 2mgL(-1) and a 92% reduction at 700mgL(-1) Cl(-) when the P concentration of the test solution was 0.2mgL(-1). There was also a small but significant effect of carbonate species on P sorption to the resin at carbonate concentrations that can occur in agricultural soils. Changing the pH of the solution had minimal effects on the resin P measurements in solutions above pH 4, but below pH 4, resin P measurements decreased dramatically. A poor coefficient of determination for the regression fit between DGT and resin measurements on eight agricultural soils suggested that these two methods are measuring different amounts of P for different soils. Resin P measurements increased significantly, but non-uniformly across soils, when the soil:water ratio was decreased but this did not result in an improved relationship with DGT P. There was a minimal effect on measured P using either Cl(-) or HCO(3)(-) as counter ions on the resin.     

Speciation of lead in seawater and river water by using Saccharomyces cerevisiae immobilized in agarose gel as a binding agent in the diffusive gradients in thin films technique

Saccharomyces cerevisiae immobilized in agarose gel is proposed as a binding agent for the diffusive gradients in thin films (DGT) technique for determination of Pb in river water and seawater. DGT samplers were assembled with the proposed binding agent (25-mm disk containing 20%, m/v, S. cerevisiae and 3.0%, m/v, agarose) and a diffusive layer of cellulose (3MM Chr chromatography paper of 25-mm diameter). The effects of some DGT parameters (e.g., immersion time, ionic strength, and pH) were evaluated. Elution of Pb from the binding agent was effectively done with 1.75 mol L(-1) HNO(3). The deployment curve (between 2 and 24 h) was characterized by a significant uptake of Pb (346 ng Pb h(-1)) and good linear regression (R(2) = 0.9757). The experimental results are in excellent agreement with the predicted theoretical curve for mass uptake. Consistent results were found for solutions with ionic strengths of 0.005 mol L(-1) or greater and within a pH range of 4.5-8.5. Interferences from Cu (20:1), Mn (20:1), Fe (20:1), Zn (20:1), Ca (250:1), and Mg (250:1) in Pb retention were negligible. Determination of Pb in spiked river water samples (from the Corumbataí and Piracicaba rivers) performed using the proposed device was in agreement with total dissolved Pb, whereas measurements in seawater suggest that of the various species of Pb present in the samples, only cationic Pb species are adsorbed by the agarose-yeast gel disks. The in situ concentration of Pb obtained at two different sites of the Rio Claro stream (Corumbataí basin) were 1.13 ± 0.01 and 1.34 ± 0.04 μg L(-1). For 72-h deployments, a detection limit of 0.75 μg L(-1) was calculated. The combination of inductively coupled plasma optical emission spectroscopy and in situ deployments of DGT samplers during the 72-h period makes possible the determination of labile Pb in river water.     

One-step synthesis of mesoporous two-line ferrihydrite for effective elimination of arsenic contaminants from natural water

Mesoporous two-line (2-lines) ferrihydrite is successfully synthesized by a facile one-step method. The ferrihydrite is characterized by X-ray diffraction (XRD), Raman spectrum, N(2) adsorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The 2-lines ferrihydrite with mesoporous structure possesses excellent adsorption performance for arsenic (As(III)) contamination. Experimental results show that As(III) contamination can be effectively removed within 2 h by this 2-lines ferrihydrite, which is attributed to the special mesoporous structure and large surface area (133 m(2) g(-1)). The As(III) loading capacity of our obtained mesoporous 2-lines ferrihydrite is up to 128 mg(As) g(-1)(Fe). In addition, As(III) can be easily desorbed from 2-lines ferrihydrite by simple heat treatment in alkali solution. After reusage for 10 times, it still presents good adsorption performance, indicating the excellent stability of the 2-lines ferrihydrite. Furthermore, the mesoporous 2-lines ferrihydrite is also effective for As(III) removal when some natural water constituents are present. Therefore, the high adsorption capability of the mesoporous 2-lines ferrihydrite makes it a potentially attractive adsorbent for the removal of As(III) contamination from natural water.     

Crystallographic controls on uranyl binding at the quartz/water interface

Molecular dynamics methods were used to simulate UO(2)(OH)(2)(0) binding to pairs of oxo sites (O(S)) on three low-index planes of α-SiO(2) in contact with water. Differences in binding site distributions on the (001), (010) and (101) planes produced distinct sets of stable U inner-sphere species. Steric constraints prevented bidentate coordination to the (001) surface, resulting in a mononuclear monodentate complex, [UO(2)(OH)(2)(H(2)O)(n)O(S)] (90% for n=1 and 10% for n=2 over 5 ns production runs). Binuclear bidentate coordination, [UO(2)(OH)(2)(H(2)O)(n)(O(S))(2)], was however favored on the (010) (99% for n=0 and 1% for n=1) and the (101) (72% for n=0 and 28% for n=1) planes. These results underscore a predominant four-coordinated equatorial shell for U when complexed to the quartz/water interface. Potential of mean force calculations uncovered a diversity of metastable outer- and inner-sphere complexes at local energy minima up to ～0.4 nm from the surface. These calculations point to important differences in both energetic requirements and mechanisms for the approach of UO(2)(OH)(2)(0) to different quartz surfaces. Binding strengths are affected by binding site distribution, steric freedom, U hydration and OH orientation, and increase in the order (001) (3.7 kJ mol(-1)) < (101) (5.6 kJ mol(-1)) < (010) (6.5 kJ mol(-1)). A general binding mechanism involves (1) formation of monodentate outer-sphere complexes, (2) removal of oxo-bound waters, (3) formation of one (monodentate), then two (bidentate) direct U-O(S) bonds (inner-sphere), and (4) expulsion of excessive waters from the equatorial shell of U.     

Infrared and infrared emission spectroscopy of nesquehonite Mg(OH)(HCO3)·2H2O-implications for the formula of nesquehonite

The mineral nesquehonite Mg(OH)(HCO(3))·2H(2)O has been analysed by a combination of infrared (IR) and infrared emission spectroscopy (IES). Both techniques show OH vibrations, both stretching and deformation modes. IES proves the OH units are stable up to 450°C. The strong IR band at 934 cm(-1) is evidence for MgOH deformation modes supporting the concept of HCO(3)(-) units in the molecular structure. Infrared bands at 1027, 1052 and 1098 cm(-1) are attributed to the symmetric stretching modes of HCO(3)(-) and CO(3)(2-) units. Infrared bands at 1419, 1439, 1511, and 1528 cm(-1) are assigned to the antisymmetric stretching modes of CO(3)(2-) and HCO(3)(-) units. IES supported by thermoanalytical results defines the thermal stability of nesquehonite. IES defines the changes in the molecular structure of nesquehonite with temperature. The results of IR and IES supports the concept that the formula of nesquehonite is better defined as Mg(OH)(HCO(3))·2H(2)O.     

Utilization of a benzyl functionalized polymeric ionic liquid for the sensitive determination of polycyclic aromatic hydrocarbons; parabens and alkylphenols in waters using solid-phase microextraction coupled to gas chromatography-flame ionization detection

The functionalized polymeric ionic liquid poly(1-(4-vinylbenzyl)-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide (poly(VBHDIm(+)NTf(2)(-))) has been used as successful coating in solid-phase microextraction (SPME) to determine a group of fourteen endocrine disrupting chemicals (ECDs), including polycyclic aromatic hydrocarbons (PAHs), alkylphenols, and parabens, in several water samples. The performance of the PIL fiber in direct immersion mode SPME followed by gas chromatography (GC) with flame-ionization detection (FID) is characterized with average relative recoveries higher than 96.1% from deionized waters and higher than 76.7% from drinking bottled waters, with precision values (RSD) lower than 13% for deionized waters and lower than 14% for drinking bottled waters (spiked level of 1 ng mL(-1)), when using an extraction time of 60 min with 20 mL of aqueous sample. Detection limits varied between 9 ng L(-1) and 7 ng mL(-1). A group of real water samples, including drinking waters, well waters, and swimming pool waters, have been analyzed under the optimized conditions. A comparison has also been carried out with the commercial SPME coatings: polydimethylsyloxane (PDMS) 30 μm, and polyacrylate (PA) 85 μm. The functionalized PIL fiber (～12 μm) demonstrated to be superior to both commercial fibers for the overall group of analytes studied, in spite of its lower coating thickness. A normalized sensitivity parameter is proposed as a qualitative tool to compare among fiber materials, being higher for the poly(VBHDIm(+)NTf(2)(-)) coating. Furthermore, the partition coefficients of the studied analytes to the coating materials have been determined. A quantitative comparison among the partition coefficients also demonstrates the superior extraction capability of the functionalized PIL sorbent coating.     

Selective inclusion of PO4(3-) within persistent dimeric capsules of a tris(thiourea) receptor and evidence of cation/solvent sealed unimolecular capsules

A tren-based tris(thiourea) receptor, L with electron-withdrawing p-nitrophenyl terminals has been established as a competent hydrogen-bonding scaffold that can selectively encapsulate PO(4)(3-) within persistent and rigid dimeric capsules, assembled by aromatic π-stacking interactions between the receptor side-arms. A quaternary ammonium salt of PO(4)(3-) capsules (complexes 1 and 1b, 2:1 host-guest) can reproducibly be obtained in quantitative yields by a solution-state deprotonation of [HL](+) moieties and a bound HPO(4)(2-) anion of complex 1a (HPO(4)(2-) complex of protonated L, 2:1 host-guest), induced by the presence of a large excess of anions such as HCO(3)(-), CH(3)CO(2)(-), and F(-). Qualitative as well as quantitative (1)H and (31)P NMR experiments (DMSO-d(6)) have been carried out in detail to demonstrate the selective and preferential inclusion of PO(4)(3-) by L in solution-states. Competitive crystallization experiments performed in the presence of an excess of anions such as HCO(3)(-), HSO(4)(-), CH(3)CO(2)(-), NO(3)(-) and halides (F(-) and Cl(-)) further establish the phenomenon of selective PO(4)(3-) encapsulation as confirmed by (1)H NMR, (31)P NMR, FT-IR and powder X-ray diffraction patterns of the isolated crystals. X-ray structural analyses and (31)P NMR studies of the isolated crystals of phosphate complexes (1, 1a and 1b) provide evidence of the binding discrepancy of inorganic phosphates with protonated and neutral form of L. Furthermore, extensive studies have been carried out with other anions of different sizes and dimensions in solid- and solution-states (complexes 2a, 3, 4 and 5). Crystal structure elucidation revealed the formation of a solvent (DMSO) sealed unimolecular capsule in the F(-) encapsulated complex, 2a (1:1 host-guest), a CO(3)(2-) encapsulated centrosymmetric molecular capsule in 3 (2:1 host-guest) and a cation (tetrabutylammonium) sealed SO(4)(2-) encapsulated unimolecular capsule in 4 (1:1 host-guest). 2D-NOESY NMR experiments carried out on these capsule complexes further confirm the relevant binding stoichiometry of complexes (2a-4) except for the PO(4)(3-)-encapsulated complex (1b) which showed a 1:1 host-guest stoichiometry in solution.     

Development and application of the diffusive gradients in thin films technique for the measurement of total dissolved inorganic arsenic in waters

The diffusive gradients in thin films (DGT) technique, utilizing an iron-hydroxide adsorbent, has been investigated for the in situ accumulation of total dissolved inorganic As in natural waters. Diffusion coefficients of the inorganic As(V) and As(III) species in the polyacrylamide gel were measured using a diffusion cell and DGT devices and a variety of factors that may affect the adsorption of the As species to the iron-hydroxide adsorbent, or the diffusion of the individual As species, were investigated. Under conditions commonly encountered in environmental samples, solution pH and the presence of anions, cations, fulvic acid, Fe(III)-fulvic acid complexes and colloidal iron-hydroxide were demonstrated not to affect uptake of dissolved As. To evaluate DGT as a method for accumulation and pre-concentration of total dissolved inorganic As in natural waters, DGT was applied to two well waters and a river water that was spiked with As. For each sample, the concentration obtained with use of DGT followed by measurement by hydride generation atomic absorption spectrometry with a Pd modifier (HG-AAS) was compared with the concentration of As measured directly by HG-AAS. The results confirmed that DGT is a reliable method for pre-concentration of total dissolved As.     

巯基改性聚乙烯醇为结合相的薄膜扩散梯度技术

利用巯基乙酸改性了聚乙烯醇,制得了巯基聚乙烯醇(PVA-SH).研究了以1.0 mmol/L PVA-SH溶液为结合相的薄膜扩散梯度(DGT)装置(PVA-SH DGT)对Cd2+测量的有效性; 考察了pH值、离子强度对PVA-SH DGT累积Cd2+的影响; 测量了PVA-SH DGT对Cd2+的饱和累积容量.实验表明: 巯基乙酸成功地接枝到PVA上,巯基含量为1.65%(wt%); PVA-SH DGT对Cd2+的饱和累积容量为0.234 mol/L;当pH值在5.5～9.9范围内、离子强度在0.0001～0.7 mol/L内基本不影响PVA-SH DGT对Cd2+的累积; PVA-SH DGT能够定量测定水中的Cd2+,回收率为100.7%,线性相关系数r=0.9812.结果表明: PVA-SH可以作为DGT技术新的液态结合相.     

Increase in intrinsic anion conductance upon inhibition of the electroneutral Cl(-)/HCO(3)(-) exchanger: effect of CO(2)/HCO(3)(-).

The electroneutral Cl(-)/HCO(3)(-) exchange, present at the apical membrane of rabbit gallbladder epithelium, apparently is converted into a stilbene- and dipyridamole-sensitive, nonrectifying, approximately 5-pS anion channel after the exchange is directly inhibited (inhibitors tested: hydrochlorothiazide (HCTZ), phlorizin, phenylglyoxal and diphenylamine-2-carboxylic acid (DPC)). In intact tissue, in the absence of CO(2)/HCO(3)(-) in the media, the opening of these channels causes an approximately 7-mV depolarization of the apical membrane. This has been shown to be a constant index of the total Cl(-) conductance (G(Cl)) activated. The effect of exogenous and endogenous CO(2)/HCO(3)(-) on the depolarization has now been investigated in the intact tissue by conventional microelectrodes. The anion exchange has been measured radiochemically. The presence of exogenous or endogenous CO(2)/HCO(3)(-) reduces the depolarization induced by HCTZ, phlorizin and DPC from approximately 7 to 3 mV, but 10(-4) mol/l acetazolamide restores the full depolarization. Response time, S(0.5) and Hill number are unchanged in each case. The way of bicarbonate replacement is irrelevant. The depolarization generated by phenylglyoxal, which covalently binds to the transport site of the exchanger and prevents HCO(3)(-) binding, is unaffected by CO(2)/HCO(3)(-) presence. HCO(3)(-) binding to the transport site is suggested to partially hinder the conversion of the exchanger into the channel.     

Solution and mechanochemical syntheses, and spectroscopic and structural studies in the silver(I) (bi-)carbonate: triphenylphosphine system

Syntheses of a number of adducts of silver(I) (bi-)carbonate with triphenylphosphine, both mechanochemically, and from solution, are described, together with their infra-red spectra, (31)P CP MAS NMR and crystal structures. Ag(HCO(3)):PPh(3) (1:4) has been isolated in the ionic form [Ag(PPh(3))(4)](HCO(3))·2EtOH·3H(2)O. Ag(2)CO(3):PPh(3) (1:4) forms a binuclear neutral molecule [(Ph(3)P)(2)Ag(O,μ-O'·CO)Ag(PPh(3))(2)](·2H(2)O), while Ag(HCO(3)):PPh(3) (1:2) has been isolated in both mononuclear and binuclear forms: [(Ph(3)P)(2)Ag(O(2)COH)] and [(Ph(3)P)(2)Ag(μ-O·CO·OH)(2)Ag(PPh(3))(2)] (both unsolvated). A more convenient method for the preparation of the previously reported copper(I) complex [(Ph(3)P)(2)Cu(HCO(3))] is also reported.     

Dependences of Water Permeation through Cyclic Octa-peptide Nanotubes on Channel Length and Membrane Thickness

Effects of the channel length and membrane thickness on the water permeation through the transmembrane cyclic octa-peptide nanotubes (octa-PNTs) have been studied by molecular dynamics (MD) simulations. The water osmotic permeability (p(f)) through the PNTs of k × (WL)(4)/POPE (1-palmitoyl-2-oleoyl-glycerophosphoethanolamine; k = 6, 7, 8, 9, and 10) was found to decay with the channel length (L) along the axis (～L(-2.0)). Energetic analysis showed that a series of water binding sites exist in these transmembrane PNTs, with the barriers of ～3k(B)T, which elucidates the tendency of p(f) well. Water diffusion permeability (p(d)) exhibits a relationship of ～L(-1.8), which results from the novel 1-2-1-2 structure of water chain in such confined nanolumens. In the range of simulation accuracy, the ratio (p(f)/p(d)) of the water osmotic and diffusion permeability is approximately a constant. MD simulations of water permeation through the transmembrane PNTs of 8 × (WL)(4)/octane with the different octane membrane thickness revealed that the water osmotic and diffusion permeability (p(f) and p(d)) are both independent of the octane membrane thickness, confirmed by the weak and nearly same interactions between the channel water and octane membranes with the different thickness. The results may be helpful for revealing the permeation mechanisms of biological water channels and designing artificial nanochannels.     

Kinetics and mechanism of peroxymonocarbonate formation

The kinetics and mechanism of peroxymonocarbonate (HCO(4)(-)) formation in the reaction of hydrogen peroxide with bicarbonate have been investigated for the pH 6-9 range. A double pH jump method was used in which (13)C-labeled bicarbonate solutions are first acidified to produce (13)CO(2) and then brought to higher pH values by addition of base in the presence of hydrogen peroxide. The time evolution of the (13)C NMR spectrum was used to establish the competitive formation and subsequent equilibration of bicarbonate and peroxymonocarbonate following the second pH jump. Kinetic simulations are consistent with a mechanism for the bicarbonate reaction with peroxide in which the initial formation of CO(2) via dehydration of bicarbonate is followed by reaction of CO(2) with H(2)O(2) (perhydration) and its conjugate base HOO(-) (base-catalyzed perhydration). The rate of peroxymonocarbonate formation from bicarbonate increases with decreasing pH because of the increased availability of CO(2) as an intermediate. The selectivity for formation of HCO(4)(-) relative to the hydration product HCO(3)(-) increases with increasing pH as a consequence of the HOO(-) pathway and the slower overall equilibration rate, and this pH dependence allows estimation of rate constants for the reaction of CO(2) with H(2)O(2) and HOO(-) at 25 °C (2 × 10(-2) M(-1) s(-1) and 280 M(-1) s(-1), respectively). The contributions of the HOO(-) and H(2)O(2) pathways are comparable at pH 8. In contrast to the perhydration of many other common inorganic and organic acids, the facile nature of the CO(2)/HCO(3)(-) equilibrium and relatively high equilibrium availability of the acid anhydride (CO(2)) at neutral pH allows for rapid formation of the peroxymonocarbonate ion without strong acid catalysis. Formation of peroxymonocarbonate by the reaction of HCO(3)(-) with H(2)O(2) is significantly accelerated by carbonic anhydrase and the model complex [Zn(II)L(H(2)O)](2+) (L = 1,4,7,10-tetraazacyclododecane).     

New resin gel for uranium determination by diffusive gradient in thin films technique

A new resin gel based on Spheron-Oxin(?) chelating ion-exchanger with anchored 8-hydroxyquinoline functional groups was tested for application in diffusive gradient in thin film technique (DGT) for determination of uranium. Selectivity of uranium uptake from model carbonate loaded solutions of natural water was studied under laboratory conditions and compared with selectivity of the conventional Chelex 100 based resin gel. The affinity of Spheron-Oxin(?) functional groups enables determination of the overall uranium concentration in water containing carbonates up to the concentration level of 10(2) mg L(-1). The effect of uranium binding to the polyacrylamide (APA) and agarose diffusive gels (AGE) was also studied. Uranium is probably bound in both gels by a weak interaction with traces of acrylic acid groups in the structure of APA gel and with pyruvic and sulfonic acid groups in the AGE gel. These sorption effects can be eliminated to the negligible level by prolonged deployment of DGT probes or by disassembling probes after the 1-2 days post-sampling period that is sufficient for release of uranium from diffusive gel and its sorption in resin gel.     

Metal speciation measurement by diffusive gradients in thin films technique with different binding phases

Since its invention in the mid-1990s, the diffusive gradients in thin films (DGT) technique has rapidly become one of the most promising in situ sampling techniques for trace metal measurement in natural waters. We investigated here the possibility of using DGT devices with different binding phases to determine different DGT labile fractions of Cd and Cu in laboratory solutions and in natural waters. Several binding phases were studied, including conventional Chelex 100 resin imbedded polyacrylamide hydrogel (Chelex) and several recently developed binding phases, poly(acrylamide-co-acrylic acid) (PAM-PAA) gel, poly(acrylamidoglycolic acid-co-acrylamide) (PAAG-PAM) gel, Whatman P81 cellulose phosphate ion-exchange membrane (P81), and poly(4-styrenesulfonate) (PSS) aqueous solution. Laboratory testing in metal solutions spiked with EDTA or humic acid suggested that all the DGT devices measured only free metal ions and inorganic metal complexes. Upon field testing at both freshwater and seawater sites it was found that the DGT labile metal concentrations measured by different binding phases can be significantly different, suggesting that the DGT labile metal fractions were dependent on binding strength of the binding phase. By designing binding phases that can compete with different natural water complexing ligands to varying extents, it is possible to use these different DGT devices to measure metal speciation in natural waters.     

Mononuclear and dinuclear manganese compounds stabilized by supramolecular interactions

New manganese compounds [Mn(HphpzMe)(2)(H(2)phpzMe)(HCO(2))] (1), [Mn(2)(phpzMe)(2)(HphpzMe)(2)(OCH(3))]·2CH(3)OH (2), Na{[Mn(HphpzPh)(phpzPh)(MeOH)(2)](2)}(HCO(2)) (3), [Mn(HphpzPh)(2)(EtOH)(2)]ClO(4)·2EtOH (4) and [Mn(HphpzPh)(2)N(3)] (5) were synthesized and characterized with various techniques. 1, 4 and 5 are mononuclear manganese(iii) compounds, 2 is a mixed-valence dinuclear manganese(iii/iv) compound, and 3 is a trinuclear compound containing two manganese(iii) ions and a sodium(i) ion. A remarkable feature is the spontaneous formation of the formate ion as a result of the methanol or methoxide oxidation in compounds 1 and 3. Using ethanol precludes the formation of the formate and compound 4 is obtained. The molecular structure of all compounds is stabilized by supramolecular interactions, including strong hydrogen bonding and π-π interactions.