Determination of butyl- and phenyltin compounds in biological material by gas chromatography-flame photometric detection after ethylation with sodium tetraethylborate

A reliable and rapid speciation method for the simultaneous determination of butyl- and phenyltin species in biological samples has been developed. Three extraction procedures are compared: enzymatic hydrolysis and solubilization by ethanoic and hydrochloric acids. Derivatization is performed by the one-step ethylation/extraction procedure using the sodium tetraethylborate reagent directly in the aqueous phase in the presence of an isooctane layer. Analysis is performed using capillary gas chromatography coupled to flame photometric detection. The detection limits are in the range of a few ng(Sn)/g. Analysis of the environmental samples and the certified reference material demonstrates the accuracy of the analytical method.     

Evaluation of diffusive gradients in thin-films using a Diphonix resin for monitoring dissolved uranium in natural waters

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.     

The measurement of organically complexed Fe in natural waters using competitive ligand reverse titration

Whilst there is increasing evidence for the presence of stabilized Fe^II associated with organic matter in aquatic environments, the absence of a reliable method for determining Fe^II speciation in solution has inhibited the study of this aspect of Fe biogeochemistry. A technique is described here for the determination of Fe^II organic complexation in natural waters that is based on competitive ligand reverse titration and a model fit to experimental results, from which ligand concentration and a conditional stability constant can be obtained. Spectrophotometry was used to detect the Ferrozine (FZ) complex with reactive Fe^II, which in combination with a liquid waveguide capillary cell (LWCC) enabled high sensitivity and precision measurements of Fe^II to be made. A series of samples was collected in the Itchen River in Southampton, UK to test the method at a wide range of salinities including river water. Levels of Fe^II and total dissolved Fe were within previously reported values for this system. Fe^II was found to occur organically complexed with values for log K^′_FeIIL$\log {K^{\prime }}_{{\text{Fe}}^{\text{II}}\text{L}}$ (conditional stability constant for Fe^II-natural ligand complexes) of ≈8 at salinities between 0 and 21, whilst no measurable complexation was detected at a salinity of 31. This work demonstrates that spectrophotometry can be used in combination with ligand competition to investigate metal speciation in natural waters.     

An amperometric method for the detection of amitrole, glyphosate and its aminomethyl-phosphonic acid metabolite in environmental waters using passive samplers

The herbicides amitrole and glyphosate, and its metabolite aminomethyl-phosphonic acid (AMPA), in water samples have been directly analysed by high-performance liquid chromatography using an electrochemical (EC) detector. Limits of detection of 0.3 μg mL⁻¹ for glyphosate, 0.05 μg mL⁻¹ for AMPA and 0.03 μg mL⁻¹ for amitrole were comparable to those obtained by other authors using EC and also by liquid chromatography coupled to mass spectrometry, but the latter method requires derivatisation and pre-concentration of the sample whereas EC methods show similar sensitivity without the need of any derivatisation. The method was specifically designed to analyse extracts from passive samplers used for monitoring of polar herbicide residues in waters. To this purpose, three types of Empore^® disks were tested for their ability to adsorb and desorb these ionic, polar analytes. A procedure for their extraction from the membranes and reducing the interferences from other substances present in natural waters (i.e. humic acids) is described. The method is simple, does not require sophisticated equipment and is valid for the analysis and monitoring of herbicides residues using passive samplers.     

Evaluation and optimization of solid adsorbents for the sampling of gaseous methylated mercury species

This study evaluates the suitability of commercially available adsorbents for the measurement of gaseous organic mercury species namely monomethylmercury (MMHg) and dimethylmercury (DMHg).     

Determination of dissolved organic nitrogen in natural waters using high-temperature catalytic oxidation

Studies on nitrogen in natural waters have generally focussed on dissolved inorganic nitrogen (DIN), primarily because of relative ease of analysis and the important influence of DIN on water quality. Advances in analytical techniques now permit the systematic study of dissolved organic nitrogen (DON), and this work has shown that DON is quantitatively significant in many waters. This article describes the sampling and analytical protocols required for rapid, precise and reliable determinations of DON, involving high-temperature catalytic oxidation (HTCO), coupled to chemiluminescence detection. This approach simultaneously determines dissolved organic carbon (DOC) and total dissolved nitrogen (TDN), and DON is derived by subtraction of DIN measured by colorimetry. The DON determination is simple to perform, exhibits excellent precision (<1% for C and 1.5% for N) and is applicable to a wide range of natural waters.     

A composite thin film optical sensor for dissolved oxygen in contaminated aqueous environments

A robust optical composite thin film dissolved oxygen sensor was fabricated by ionically trapping the dye ruthenium(II) tris(4,7-diphenyl-1,10-phenanthroline) dichloride in a blended fluoropolymer matrix consisting of Nafion^® and Aflas^®. Strong phosphorescence, which was strongly quenched by dissolved oxygen (DO), was observed when the sensor was immersed in water. The sensor was robust, optically transparent, with good mechanical properties. Fast response, of a few seconds, coupled with sensitivity of about 0.1 mg L⁻¹ (DO) over the range 0-30 mg L⁻¹ and resistance to leaching, were also exhibited by this system. The Stern-Volmer (SV) plot exhibited slight downward turning at all oxygen concentrations. A linear plot was obtained when the SV equation was modified to account for the varying sensitivity of dye molecules in the matrix to the quencher. Good long term stability was observed.     

Determination of calcium and total hardness in natural waters using a potentiometric sensor array

The determination of calcium and total hardness in natural waters is carried out with a potentiometric sensor array which consists of a series of ion-selective electrodes (ISEs) for Ca²⁺, Mg²⁺, NH₄⁺, K⁺, Na⁺, Li⁺, and H⁺. The selectivity of the calcium and magnesium ISEs is not fully achieved as other cation species may interfere with the analysis. The proposed sensor array device can overcome this drawback since it can take advantage of the cross-selectivities of cation species towards each ISE. In this approach, the multivariate data generated by the sensor array results in a richer source of analytical information which allows the quantification of calcium and total hardness in the water samples by means of chemometric methods. Results obtained are in reasonable concordance with those given by the standard method based on complexometry.     

The room temperature preparation of metastable fluorides and potent oxidizers

The low electronegativity of an oxidation state in an anion enables high oxidation states, e.g. Ni^IV, and Ag^III, to be easily attained in liquid anhydrous HF (aHF), made basic with fluoride-ion donors. The oxidation state can be enhanced if elemental fluorine is photo-dissociated. Teflon^® valves and lines, especially transparent and kinetically stable fluorocarbon containers for the aHF solutions, provide for this. Binary fluorides that are of low solubility in aHF, can be displaced by stronger F⁻ acceptors from their high oxidation-state anions. NiF₄, NiF₃, and AgF₃, which can be made in this manner, are thermodynamically unstable with respect to loss of fluorine. The electronegativity of the oxidation state in the binary fluoride is higher than in the anion (hence the metastability) and when a strong F⁻ acceptor converts the binary fluoride into a cationic species, the electronegativity is further enhanced. Thus cationic Ag^III and Ni^IV are superior to KrF⁺, as one-electron oxidizers and are the most potent oxidizers known thus far. They are able to remove the electron from all platinum-metal hexafluoro-anions, MF₆⁻, to liberate the hexafluorides. All of this chemistry can be achieved at or below room temperature.     

New superporous hydrogels composites based on aqueous Carbopol solution (SPHCcs): synthesis, characterization and in vitro bioadhesive force studies

In this investigation new superporous hydrogels composites based on aqueous Carbopol^® solution (SPHCcs) were prepared. SEM images indicated that the inner surface of SPHCcs contained a lot of pores connected each other and the outer surface of them was non-porous. The swelling ratio decreased with increasing the content of aqueous Carbopol^® solution, and the final swelling ratio was similar to that of the SPH although the initial swelling ratio was lower. The density measurement revealed that the porosity increased when aqueous Carbopol^® solution was incorporated. It was observed from in vitro bioadhesive force study that SPHCcs adhered to the intestinal mucosal more quickly and exhibited higher mucoadhesion as compared with SPH. It is evident that the hydrogels synthesized in this study could be a potential candidate for transmucosal drug delivery system.     

Electrochemical behavior of hexafluoroniobate, heptafluorotungstate, and oxotetrafluorovanadate anions in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide room temperature ionic liquid

Electrochemical behavior of hexafluoroniobate (Nb(V)F₆⁻), heptafluorotungstate (W(VI)F₇⁻), and oxotetrafluorovanadate (V(V)OF₄⁻) anions has been investigated in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPyrTFSA) ionic liquid at 298 K by means of cyclic voltammetry and chronoamperometry. Cyclic voltammograms at a Pt electrode showed that Nb(V)F₆⁻ anion is reduced to Nb(IV)F₆²⁻ by a one-electron reversible reaction. Electrochemical reductions of W(VI)F₇⁻ and V(V)OF₄⁻ anions at a Pt electrode are quasi-reversible and irreversible reactions, respectively, according to cyclic voltammetry. The diffusion coefficients of Nb(V)F₆⁻, W(VI)F₇⁻ and V(V)OF₄⁻ determined by chronoamperometry are 1.34 × 10⁻⁷, 7.45 × 10⁻⁸ and 2.49 × 10⁻⁷ cm² s⁻¹, respectively. The Stokes radii of Nb(V)F₆⁻, W(VI)F₇⁻, and V(V)OF₄⁻ in BMPyrTFSA have been calculated to be 0.23, 0.38, and 0.12 nm, from the diffusion coefficients and viscosities obtained.     

Uranium aqueous speciation in the vicinity of the former uranium mining sites using the diffusive gradients in thin films and ultrafiltration techniques

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.     

Determination of volatile organic compounds in contaminated air using semipermeable membrane devices

Semipermeable membrane devices (SPMDs) were evaluated as passive samplers for the determination of 26 volatile organic compounds (VOCs) in contaminated air of occupational environments. A direct methodology based on the use of head-space-gas chromatography-mass spectrometry (HS-GC-MS) was developed for VOCs determinations in SPMDs, without any sample pre-treatment and avoiding the use of solvents. A desorption temperature of 150 °C for 10 min was sufficient for a sensitive VOCs determination providing limits of detection in the range of 15 ng SPMD⁻¹ for 21 of 26 studied compounds. Linear and equilibrium uptake models were established for each VOC from compound isotherms. Highly volatile compounds were slightly absorbed and moderately volatile compounds were strongly absorbed by SPMDs. This study is the first precedent of the use of SPMDs for the simultaneous sampling of a wide number of VOCs. The use of SPMDs is a simple and low cost alternative to ordinary sampling devices such as Radiello^® diffusive samplers or badge-type solid-phase supports.     

Spectroscopic characterization of the stabilising activity of migrating HALS in a pigmented PP/EPR blend

In previous work, the FT-IR maximum of absorption of a low molecular weight HALS containing a sebacate structure was reported to shift from 1738 to 1732 cm⁻¹ during the photo-aging of polypropylene. Previous studies have shown that the reduced mobility of the molecule caused the absorption to shift towards lower frequencies while decreasing its stabilizing activity. This paper presents further results evidencing the loss of activity of the low molecular weight HALS and proposes a novel mechanistic interpretation for the observed spectral shift.     

Interactions and stability of silver nanoparticles in the aqueous phase: Influence of natural organic matter (NOM) and ionic strength

The rapid development of nanotechnology and the related production and application of nanosized materials such as engineered nanoparticles (ENP) inevitably lead to the emission of these products into environmental systems. So far, little is known about the occurrence and the behaviour of ENP in environmental aquatic systems. In this contribution, the influence of natural organic matter (NOM) and ionic strength on the stability and the interactions of silver nanoparticles (n-Ag) in aqueous suspensions was investigated using UV–vis spectroscopy and asymmetrical flow field-flow fractionation (AF⁴) coupled with UV–vis detection and mass spectrometry (ICP-MS). n-Ag particles were synthesized by chemical reduction of AgNO₃ with NaBH₄ in the liquid phase at different NOM concentrations. It could be observed that the destabilization effect of increasing ionic strength on n-Ag suspensions was significantly decreased in the presence of NOM, leading to a more stable n-Ag particle suspension. The results indicate that this behaviour is due to the adsorption of NOM molecules onto the surface of n-Ag particles (“coating”) and the resulting steric stabilization of the particle suspension. The application of AF⁴ coupled with highly sensitive detectors turned out to be a powerful method to follow the aggregation of n-Ag particle suspensions at different physical–chemical conditions and to get meaningful information on their chemical composition and particle size distributions. The method described will also open the door to obtain reliable data on the occurrence and the behaviour of other ENP in environmental aquatic systems.     

Determination of organophosphorus pesticides in aqueous samples by on-line membrane disk extraction and capillary gas chromatography

Summary A fast and simple procedure for the analysis of aqueous samples by on-line membrane disk extraction and capillary gas chromatography (GC) is presented. As an example, organophosphorus pesticides are preconcentrated from aqueous samples on three 0.5 mm thick, 4.2 mm diameter extraction disks. The layers are dried by a stream of nitrogen (10–15 min; ambient temperature). Desorption of the analytes is carried out with ethyl acetate which is directly introduced into a retention gap under partially concurrent solvent evaporation conditions, using an early solvent vapour exit. The final analysis is carried out by GC with thermionic detection. The technique is applied to the determination of a series of organophosphorus pesticides in tap water and water from two European rivers. With a sample volume of only 2.5 ml, detection limits of 10–30 ppt are achieved in tap water and of 50–100 ppt in river water.     

Evaluation and application of Diffusive Gradients in Thin Films (DGT) technique using Chelex-100, Metsorb™ and Diphonix binding phases in uranium mining environments

A new resin- Diphonix^® in Diffusive Gradients in Thin Films (DGT) technique for the determination of uranium was investigated and compared with previously used binding phases for uranium, Chelex^®-100 and Metsorb™. The DGT gel preparation and the elution procedure were optimized for the new resin. The U uptake on Diphonix^® resin gel was 97.4 ± 1.5% (batch method; [U] = 20 μg L⁻¹; 0.01 M NaNO₃; pH = 7.0 ± 0.2). The optimal eluent was found to be 1 M 1-hydroxyethane-1, 1-diphosphonic acid (HEDPA) with an elution efficiency of 80 ± 4.2%. Laboratory DGT study on U accumulation using a DGT samplers with Diphonix^® resin showed a very good performance across a wide range of pH (3–9) and ionic strength (0.001–0.7 M NaNO₃). Diffusion coefficients of uranium at different pH were determined using both, a diffusion cell and the DGT time-series, demonstrating the necessity of the implementation of the effective diffusion coefficients into U-DGT calculations. Diphonix^® resin gel exhibits greater U capacity than Chelex^®-100 and Metsorb™ binding phase gels (a Diphonix^® gel disc is not saturated, even with loading of 10.5 μmol U). Possible interferences with Ca²⁺ (up to 1.33 × 10⁻² M), PO₄³⁻${{\text{PO}}_4}^{3\mathrm{-}}$ (up to 1.72 × 10⁻⁴ M), SO₄²⁻${{\text{SO}}_4}^{2\mathrm{-}}$ (up to 4.44 × 10⁻³ M) and −HCO₃${{\text{HCO}}_3}^{\mathrm{-}}$ (up to 8.20 × 10⁻³ M) on U-DGT uptake ([U] = 20 μg L⁻¹) were investigated. No effect or minor effect of Ca²⁺, PO₄³⁻${{\text{PO}}_4}^{3\mathrm{-}}$, SO₄²⁻${{\text{SO}}_4}^{2\mathrm{-}}$, and −HCO₃${{\text{HCO}}_3}^{\mathrm{-}}$ on the quantitative measurement of U by Diphonix^®-DGT was observed. The results of this study demonstrated the DGT technique with Diphonix^® resin is a reliable and robust method for the measurement of labile uranium species under laboratory conditions.     

Determination of nanomolar concentrations of phosphate in natural waters using flow injection with a long path length liquid waveguide capillary cell and solid-state spectrophotometric detection

A flow injection manifold incorporating a 1 m liquid waveguide capillary cell and a miniature fibre-optic spectrometer for the determination of low phosphorus concentrations in natural waters is reported. The limit of detection (blank + 3 S.D.) was 10 nM using the molybdenum blue chemistry with tin(II) chloride reduction. The sensitivity of the flow injection manifold was improved by 100-fold compared with a conventional 1 cm flow cell. The response was measured at 710 nm and background corrected by subtracting the absorbance at 447 nm. Interference from silicate was effectively masked by the addition of 0.1% (m/v) tartaric acid and results were in good agreement (P = 0.05) with a segmented flow analyser reference method for freshwater samples containing 1 μM phosphate.     

Kinetic study of uranium speciation in model solutions and in natural waters using Competitive Ligand Exchange Method

Kinetic speciation of uranium in model solutions containing uranium and humic acid (HA) and in natural waters has been investigated by Competitive Ligand Exchange Method (CLEM). In alkaline freshwaters, most of uranium species were uranium-carbonate species, which were labile in the CLEM experiment. The uranium speciation of every sample was characterized either as “labile” or “non-labile” uranium complexes depending on the dissociation rate coefficients of the complexes. The results showed that as the U(VI)/HA ratio was decreased, the dissociation rate coefficients decreased and the labile fraction decreased as well. When the U(VI)/HA ratio was 0.1, the labile fraction of the U(VI)-HA increased with increasing pH; however, there was no pH effect on the dissociation of U(VI)-HA complexes at lower U(VI)/HA ratios. Chelex-100 had some limitations in its use for the study of dissociation of U(VI)-HA complex at very low U(VI)/HA ratios. By developing an analytical method and procedure for quantitative determination of kinetic parameters for the dissociation of uranium-HA complexes in model solutions and natural waters, this work has made a substantial contribution to analytical chemistry.