Preconcentration of anionic forms of chemical elements on filters with anchored quaternary ammonium groups

Sorption of silicomolybdic acid (SMA) and phosphovanadomolybdic acid (PVMA) and arsenic(V), vanadium(V), and chromium(VI) anionic species is studied on cellulose filters with bound quaternary ammonium groups. These heteropoly acids (HPAs) are recovered in quantity on filters from solutions with high salt backgrounds and with high mineral acid concentrations. AsO ₄ ^3? , CrO ₄ ^2? , and VO ₃ ^? anions are sorbed at pH of 3–9. In this case, the ionic strength considerably influences anion recovery. Conditions were found for preconcentrating vanadium, arsenic, and chromium from 250-mL aliquots of aqueous solutions (the preconcentration coefficient was 5 × 10³). A procedure was proposed for the sorption/X-ray fluorescence determination of these elements in high-purity water.     

Sorption of arsenic,antimony and bismuth on glycolmethacrylate gels with bound thiol groups for direct sampling in electrothermal atomic absorption spectrometry

Batch sorption of arsenic, antimony and bismuth from solutions in 1 M sulphuric acid has distribution coefficients of 10⁴–10⁵. Quantitative sorption on the hydrophilic methacrylate gel containing thiol groups (Spheron Thiol) is possible within 60 min for bismuth or arsenic and 120 min for antimony. Conditions for the electrothermal atomization of arsenic sorbed on Spheron Thiol and injected into the graphite tube as a suspension are optimized. The sensitivities possible are 3.2 ng As ml^-1, 13 ng Sb ml^-1 and 2.8 ng Bi ml^-1; the coefficient of variation for 10 ng of As is 4%. Complete recovery of 40 ng As ml^-1 added to solutions of 5% KCI or 5% MgCl₂ and to river water was obtained.     

Biomethylation and biotransformation of arsenic in a freshwater food chain: Green alga (chlorella vulgaris)→shrimp (neocaridina denticulata)→killifish (oryzias iatipes)

Tolerance, bioaccumulation, biotransformation and excretion of arsenic compounds by the fresh–water shrimp (Neocaridina denticulata) and the killifish (Oryzias latipes) (collected from the natural environment) were investigated. Tolerances (LC₅₀) of the shrimp against disodium arsenate [abbreviated as As(V)], methylarsonic acid (MAA), dimethylarsinic acid (DMAA), and arsenobetaine (AB) were 1.5, 10, 40, and 150μg As ml^?1, respectively. N. denticulata accumulated arsenic from an aqueous phase containing 1 μg As ml^?1 of As(V), 10 μg As ml^?1 of MAA, 30 μg As ml^?1 of DMAA or 150 μg As ml^?1 of AB, and biotransformed and excreted part of these species. Both methylation and demethylation of the arsenicals were observed in vivo. When living N. denticulata accumulating arsenic was transferred into an arsenic–free medium, a part of the accumulated arsenic was excreted. The concentration of methylated arsenicals relative to total arsenic was higher in the excrement than in the organism. Total arsenic accumulation in each species via food in the food chain Green algae (Chlorella vulgaris) → shrimp (N. denticulata) → killifish (O. latipes) decreased by one order of magnitude or more, and the concentration of methylated arsenic relative to total arsenic accumulated increased successively with elevation in the trophic level. Only trace amounts of monomethylarsenic species were detected in the shrimp and fish tested. Dimethylarsenic species in alga and shrimp, and trimethylarsenic species in killifish, were the predominant methylated arsenic species, respectively.     

Structural studies on some antimonate exchangers

The possibility of simultaneous extraction of palladium and technetium from nitrate solutions was investigated using tri-n-octylamine (TOA) solutions in carbon tetrachloride as a heavy, non-flammable diluent. Conditions of technetium extraction being essentially known, the main attention was focussed on the extraction of palladium which was studied in dependence on the concentration of nitric acid, salts (nitrates, chlorides, nitrites), urea and palladium. A strong decrease of Pd extraction with 10% TOA in CCl₄ has been found above a palladium concentration of 10⁻⁴M but in the presence of chlorides and nitrites a satisfactory high distribution can be preserved. Both Tc and Pd extracted with TOA/CCl₄ can be stripped into dilute ammoniacal solutions. An extraction procedure for the simultaneous isolation of Pd (80% yield) and Tc (99%) from fission product waste solutions (0.20 g Tc and 0.17 g Pd/dm³ 0.5–1.0M HNO₃) is proposed.     

Extraction of arsenic species from airborne particulate filters—Application to an industrial area of Greece

In the present study, the extraction of the arsenic species arsenite (As(III)), arsenate (As(V)), monomethyarsonic (MMA) and dimethylarsinic acid (DMA) from airborne particulate filters was investigated and optimized. For this purpose, total suspended particulate matter as well as size fractionated aerosol samples were collected from the industrial area of Aspropyrgos, Greece, in glass fibre and polycarbonated filters, respectively. Among H₃PO₄ and HCl, tested in various concentrations, concentrated HCl was found to be the most effective extractant for arsenic from both polycarbonated and glass fibre filters, without provoking any arsenic species transformation. However, the quantitative extraction of arsenic species from glass fibre filters required the subsequent washing of the filters with ultrapure water after their leaching with concentrated HCl. The developed procedure was applied to airborne particulate filters for arsenic speciation in Aspropyrgos' atmosphere. The results showed an enrichment of As in the fine (PM_2.5) compared with the coarse (PM_10–2.5) fraction of airborne particulates, while As(V) was found to be the predominant arsenic species in all samples. Finally, As concentration in the PM₁₀ fraction, for the investigated area and time period from December 2004 to June 2006, was below the target value of 6 ng As m^− 3, referred in the Directive 2004/107 of European Union.     

A comparative study on acute toxicity of methylarsonic acid,dimethylarsinic acid and trimethylarsine oxide in mice

The acute toxicity of methylarsonic acid, CH₃AsO(OH)₂ (MAA), dimethylarsininc acid, (CH₃)₂AsO(OH) (DMAA), and trimethylarsine oxide, (CH₃)₃AsO (TMAO), were examined in mice with oral administration. The LD₅₀ values of MAA, DMAA and TMAO were 1.8, 1.2 and 10.6 g kg^?1 respectively. The toxicity of MAA and DMAA was very much lower than that for inorganic arsenic compounds. It was shown that TMAO has a similar acute toxicity to arsenobetaine. On the other hand, when the mice were administered 14.4 g kg^?1 of TMAO once only orally, a garlic-like odor (trimethylarsine, (CH₃)₃As) was definitely detectable in the exhalation of the animals by the human olfactory sense within about a few minutes.     

Extraction procedures for chemical speciation of arsenic in atmospheric total suspended particles

An arsenic chemical speciation study was performed in 2000, using air filters on which total suspended particles (TSP) were collected, from the city of Huelva, a medium size city with huge industrial influence in SW Spain. Different procedures for extraction of the arsenic species were performed using water, NH₂OH.HCl, and H₃PO₄ solutions, with either microwave or ultrasonic radiation. The best optimised extraction methods were use of 100 mmol L^–1 NH₂OH.HCl and 10 mmol L^–1 H₃PO₄ and microwave radiation for 4 min. High-performance liquid chromatography coupled with hydride generation and atomic fluorescence spectrometry (HPLC–HG–AFS) was employed for determination of the arsenic species. The results from 12 TSP air filters collected on a monthly basis showed extraction was quantitative (94% with NH₂OH.HCl and 86% H₃PO₄). Only inorganic arsenic species (arsenite and arsenate) were detected. The mean arsenite concentration was 1.2±0.3 ng m^–3 (minimum 0.3 ng m^–3, maximum 1.8 ng m^–3). The mean arsenate concentration was 10.4±1.8 ng m^–3, with greater monthly variations than arsenite (minimum 2.1 ng m^–3, maximum 30.6 ng m^–3). The high level of arsenic species in the TSP samples can be related to a copper smelter located in the region.     

Kinetic and thermodynamic studies of cesium(I) sorption on hydrous silica

Summary Batch sorption experiments of cesium, Cs⁺, on SiO₂ ^. xH₂O (silica gel) have been conducted with variable times of equilibration, amounts of silica gel (0.10-1.00 g), cesium concentrations (5.00 ^. 10^-5-2.40 ^. 10^-3M), ionic strengths (0.20-1.40M NaClO₄), pH (2.50-7.70), and temperatures (273-333 K). The diffusion coefficient of Cs⁺ ion was calculated to be (9.19±0.86) ^. 10^-11 m^{2 .} s^-1 under particle diffusion-controlled conditions. The sorption rate was (3.94±0.65) ^. 10^-3 s^-1 at 298 K, pH 7.70±0.05 in 0.20M NaClO₄. The sorption data fits the Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. Cesium sorption on 0.20 g silica gel decreased with ionic strength from (40.42±0.34)% in 0.20M NaClO₄ to (6.35±0.40)% in 1.40M NaClO₄, at pH_(initial) 8.20±0.05. A gradual decrease in pH with increased ionic strength is consistent with a cation-exchange mechanism. Sorption of Cs⁺ on silica gel decreased with increased temperature, indicating an exothermic enthalpy. The presence of anions such as fluoride, carbonate, phosphate and oxalate in the aqueous medium did not influence the cesium sorption profile.     

Preparation of Sorbents Containing Straetlingite Phase from Zeolitic By-Product and Their Performance for Ammonium Ion Removal

In this study, straetlingite-based sorbents were used for NH₄⁺ ion removal from a synthetic aqueous solution and from the wastewater of an open recirculation African catfish farming system. This study was performed using column experiments with four different filtration rates (2, 5, 10, and 15 mL/min). It was determined that breakthrough points and sorption capacity could be affected by several parameters such as flow rate and mineral composition of sorption materials. In the synthetic aqueous solution, NH₄⁺ removal reached the highest sorption capacity, i.e., 0.341 mg/g with the S30 sorbent at a filtration rate of 10 mL/min and an initial concentration of 10 mg/L of NH₄⁺ ions. It is important to emphasize that, in this case, the Ce/C0 ratio of 0.9 was not reached after 420 min of sorption. It was also determined that the NH₄⁺ sorption capacity was influenced by phosphorus. In the wastewater, the NH₄⁺ sorption capacity was almost seven times lower than that in the synthetic aqueous solution. However, it should be highlighted that the P sorption capacity reached 0.512 mg/g. According to these results, it can be concluded that straetlingite-based sorbents can be used for NH₄⁺ ion removal from a synthetic aqueous solution, as well as for both NH₄⁺ and P removal from industrial wastewater. In the wastewater, a significantly higher sorption capacity of the investigated sorbents was detected for P than for NH₄⁺.     

Use of hydride generation-atomic absorption spectrometry to determine the effects of hard ions, iron salts and humic substances on arsenic sorption to sorghum biomass

At present, there is a great interest in studying new sorbent materials for the removal of arsenic from aqueous solutions because of its high toxicity and adverse effects on human health. In previous research, sorghum biomass was found to be an efficient and economic sorbent for the removal of arsenic from aqueous solutions. In this investigation, the effects of CaCl₂, MgCl₂, FeSO₄, MgSO₄, Fe(NO₃)₃, and humic substances (peat moss, humin and humic acids) on arsenic binding to sorghum biomass were evaluated. Among these compounds, only iron salts were found to positively increase the sorption of arsenic to sorghum biomass. In addition, the sorption equilibrium was reached faster when the reaction mixture contained iron salts. However, an overall reduction of 21% of arsenic sorption to sorghum biomass was observed in the presence of MgSO₄. This interference may be due to the presence of sulfate ions, instead of the hard cations, that could be in competition with As for the same interaction sites or ligands. Peat moss, humins and humic acid, extracted from sphagnum peat moss, significantly decreased the arsenic sorption to sorghum biomass.     

Gold sorption on weak base anion exchangers with aminoguanidyl groups

Two resins with different matrices, both bearing aminoguanidyl ligands, were obtained and used for gold sorption from hydrochloric acidic and from alkali solutions. Resin 1 was a aminoguanidine derivative of poly(acrylonitril-co-vinyl acetat-co-divinyl benzene) terpolymer (AN/VA/DVB), (67:27:10 wt.%), and Resin 2 the same derivative of gel expanded poly(vinylbenzyl chloride-co-divinylbenzene) copolymer (VBC/DVB). The resins sorption capacity and sorption isotherms of both resins were determined for AuCl₄⁻ and Au(CN)₂⁻ anions. Resin 2 revealed the best sorption of gold from acidic and alkali solutions: 68 and 23 mg/g, respectively. The effect of the HCl concentration on AuCl₄⁻ removal from solution was investigated. Gold was recovered quantitatively from both resins using a 5% thiourea solution in 0.1 HCl. Both resins remained ability of multiple gold sorption and desorption under acidic conditions.     

Nickel(II) sorption on hydrous silica: A kinetic and thermodynamic study

Summary Sorption of nickel, Ni²⁺, on SiO₂ ^. xH₂O (silica gel) has been studied as a function of time conditions: amount of silica gel: 0.10-1.00 g, nickel concentration: 5.00 ^. 10^-5-1.20 ^. 10^-3M, ionic strength: 0.20-1.40M NaClO₄, pH 6.50 to 8.50, and temperature 273-318 K. From the kinetic data, the diffusion coefficient of Ni²⁺ ion was calculated to be 1.28(±0.07) ^. 10^-11 m^{2 .} s^-1 under particle diffusion-controlled conditions. The sorption rate was determined as 3.79(±0.35) ^. 10^-3 s^-1 at 298 K, pH 8.40 in 0.20M (NaClO₄). The sorption data were fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. Nickel sorption on 0.20 g silica gel decreased with ionic strength from 77.70±0.70% (0.20M NaClO₄) to 16.12±0.37% (1.40M NaClO₄) at intial pH of 8.50±0.05. A gradual decrease in pH with increasing ionic strength suggests an ion exchange mechanism and the sorption of Ni²⁺ on silica gel increasing with temperature indicates an endothermic enthalpy. The effect of different ligands such as fluoride, carbonate, phosphate and oxalate on Ni²⁺ sorption on silica gel was studied.     

Kinetic and thermodynamic sorption study of radiocobalt by magnetic hydroxyapatite nanoparticles

A novel composite adsorbent, magnetite/hydroxyapatite (Fe₃O₄/HAP) composites, was prepared by biowaste chicken eggshell for the purpose of removing radiocobalt from aqueous solutions. It highlighted that more than 92% Co(II) could be removed by using the developed composites under the experimental conditions. The maximum sorption capacity of Co(II) on Fe₃O₄/HAP composites was 6.9 × 10⁻⁴ mol/g. The coexisted foreign ions, e.g., ClO₄ ⁻, NO₃ ⁻, Cl⁻, Na⁺ and K⁺, did not interfere the elimination of Co(II) from aqueous solutions, while Mg²⁺ did. The sorption process was found to be controlled well by pseudo-second-order and intra-particle diffusion models, and the equilibrium data were simulated by Langmuir model very well with high correlation coefficients. The thermodynamic parameters confirmed the spontaneity and endothermic nature of Co(II) sorption processes. After sorption, the Fe₃O₄/HAP composites could be effectively and fleetly separated from aqueous solutions by magnetic separation technique in large scale. The Fe₃O₄/HAP composites are suitable materials in the preconcentration of Co(II) from large volumes of aqueous solutions.     

Arsenic sorption and redox transformation on iron‐impregnated ordered mesoporous carbon

Ordered mesoporous carbon has been actively investigated for its potential applications as catalyst supports, electrochemical materials and gas separation media. In this study, we tested an iron‐modified ordered mesoporous carbon (FeOMC) for its ability to adsorb arsenic from the aqueous phase. The FeOMC synthesis involved the preparation of an ordered silica template SBA‐15, in situ polymerization of acrylic acid in the template, carbonization and template removal to obtain the ordered mesoporous carbon, and iron impregnation. Batch experiments showed that the pH level of the solution had a major impact on arsenic sorption. Further, we found that the presence of anions (i.e. PO₄^3? and SiO₃^2?) could significantly decrease the sorption of both arsenate and arsenite. Arsenite oxidation to arsenate was observed in alkaline solutions, with or without anions being present. The oxidation of arsenite was attributed to both direct and catalytic reactions with the surface functional groups on the ordered mesoporous carbon. Adsorption of arsenic on FeOMC could be well explained by the surface complexation model. Copyright © 2007 John Wiley & Sons, Ltd.     

Sorption of neptunyl(V) cations on suspended silicate: Effects of pH, ionic strength, complexing anions, humic acid, and metal ions

Sorption of NpO₂ ⁺ on silicate (10.00 g/l) particles dispersed in sodium perchlorate media was studied as a function of pcH and ionic strength at 298 K. The sorption increased with increased pcH in the range of ∼6.5 to 9.2, above which saturation was observed. An increase in ionic strength from 0.20M to 1.00M (NaClO₄), increased the NpO₂ ⁺ sorption, which then decreased at 1.50M (NaClO₄) for 7<pcH<8.5. The effects of different types of ligands on the sorption of NpO₂ ⁺ to suspended silicate were investigated. The types of ligands included: (i) inorganic anions (fluoride, carbonate, phosphate (ii) N-donors (ethylenediamine, 1,10 phenanthroline (iii) carboxylic acids (oxalic acid, citric acid, iminodiacetic acid, ethylenediaminetetraacetic acid) and (iv) humic acid. A synergistic enhancement in sorption to the suspended silicate was observed for phosphate, oxalate, ethylenediaminetetraacetic acid, ethylenediamine, 1,10 phenanthroline (5<pcH<8) and humic acid (6.5<pcH<8.8). This behavior was attributed to the formation of ternary NpO₂ ⁺/silicate/ligand complexes. The effects of Ca(II) (1.00·10⁻³M) and Eu(III) (1.00·10⁻⁴ and 1.00·10⁻³M) ions on NpO₂ ⁺ sorption to suspended silicate were also investigated. On leave from Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai-400 085, India.     

Iron-modified light expanded clay aggregates for the removal of arsenic(V) from groundwater

Iron modified materials have been proposed as a filter medium to remove arsenic compounds from groundwater. This research investigated the removal of arsenate, As(V) from aqueous solutions by iron-coated light expanded clay aggregates (Fe-LECA). Arsenic is effectively adsorbed by Fe-LECA in the optimum pH range 6-7 by using a 10 mg mL^− 1 adsorbent dose. Kinetics experiments were performed to investigate the adsorption mechanisms. Electrostatic attraction and surface complexation were proposed to be the major arsenic removal mechanisms. The experimental data fitted the pseudo-first-order equation of Lagergren. For an arsenic concentration of 1 mg L^− 1, the rate constant (k₁) of pseudo-first-order was 0.098 min^− 1, representing a rapid adsorption in order to reach equilibrium early. Equilibrium sorption isotherms were constructed from batch sorption experiments and the data was best described by the Langmuir isotherm model. Large scale column experiments were conducted under different bed depths, flow rates, coating duration and initial iron salts concentration to determine the optimal arsenic removal efficiency by Fe-LECA column. Volumetric design as well as higher hydraulic detention time was proposed to optimize the efficiency of the column to remove arsenic. In addition, concentrated iron salts and longer coating duration were also found to be crucial parameters for arsenic removal. The maximum arsenic accumulation was 3.31 mg of As g^− 1 of Fe-LECA when the column was operated at a flow rate of 10 mL min^− 1 and the LECA was coated with 0.1 M FeCl₃ suspension for a 24 h coating duration.     

Sorption of Th(IV) ions onto TiO2: Effects of contact time, ionic strength, thorium concentration and phosphate

Summary The sorption of Th(IV) onto TiO₂ was studied by the batch technique as a function of pH and ionic strength at moderate concentration (10^-4-10^-5 mol/l) and in the presence and absence of phosphate. It was found that the sorption rate of Th(IV) was relatively slow, the sorption percent was abruptly increased from pH 2 to 4, and the sorption was decreased with increasing ionic strength as a whole. In the concentration range of Th(IV) from trace concentration to 1.4 ^. 10^-4 mol/l and in the absence of phosphate, the sorption isotherms were roughly fitted the Freundlich equation at different ionic strengths and approximately constant pH. These sorption characteristics of Th(IV) onto TiO₂ were compared with those of uranyl on the same sorbent. In addition, the positive effect of phosphate on the sorption of Th(IV) onto TiO₂ was demonstrated obviously and can be attributed to strong surface binding of phosphate, and the subsequent formation of ternary surface complexes of Th(IV). The difference between the sorption characteristics of Th(IV) ions and uranyl ions onto TiO₂ is discussed.     

Cesium sorption on mylonite

As part of the laboratory support program for the field migration experiment at the Grimsel Test Site (GTS) in the Swiss Alps, the sorption behaviour of cesium on Grimsel mylonite was studied. Batch sorption experiments were carried out in N₂ atmosphere (<3 ppm O₂). The adsorption isotherms were reversible and non-linear for cesium concentrations of between 3.2·10^–8 and 5.0·10^–4M. Two different sites appear to be involved in sorption depending on whether Cs loading was high (10^–6–10^–3 meq/g) or low (10^–7–10^–6 meq/g). At low Cs loadings adsorption was considered to occur mainly at the crystal edges of mica particles. Selectivity coefficients for exchange between cesium and potassium were calculated for different Cs loadings. It was suggestd that by varying the potassium concentration of the solution and by making some assumptions, a K_d value for cesium at the migration site could be estimated. Data were fitted to both Freundlich and Dubinin-Radushkevich isotherms. The empirical Freundlich parameters enabled a site distribution function to be calculated and a mean energy of sorption of about 12 kJ/mol was found using Dubinin-Radushkevich isotherms approach.     

Efficiency of a novel nitrogen-doped Fe3O4 impregnated biochar (N/Fe3O4@BC) for arsenic (III and V) removal from aqueous solution: Insight into mechanistic understanding and reusability potential

Worldwide, arsenic contamination has become a matter of extreme importance owing to its potential toxic, carcinogenic and mutagenic impact on human health and the environment. The magnetite-loaded biochar has received increasing attention for the removal of arsenic (As) in contaminated water and soil. The present study reports a facile synthesis, characterization and adsorption characteristics of a novel magnetite impregnated nitrogen-doped hybrid biochar (N/Fe₃O₄@BC) for efficient arsenate, As(V) and arsenite, As(III) removal from aqueous environment. The as-synthesized material (N/Fe₃O₄@BC) characterization via XRD, BET, FTIR, SEM/EDS clearly revealed magnetite (Fe₃O₄) impregnation onto biochar matrix. Furthermore, the adsorbent (N/Fe₃O₄@BC) selectivity results showed that such a combination plays an important role in targeted molecule removal from aqueous environments and compensates for the reduced surface area. The maximum monolayer adsorption (Q_max) of developed adsorbent (N/Fe₃O₄@BC) (18.15 mg/g and 9.87 mg/g) was significantly higher than that of pristine biochar (BC) (9.89 & 8.12 mg/g) and magnetite nano-particles (MNPs) [7.38 & 8.56 mg/g] for both As(III) and As(V), respectively. Isotherm and kinetic data were well fitted by Langmuir (R² = 0.993) and Pseudo first order model (R² = 0.992) thereby indicating physico-chemical sorption as a rate-limiting step. The co-anions (PO₄^3-) effect was more significant for both As(III) and As (V) removal owing to similar outer electronic structure. Mechanistic insights (pH and FTIR spectra) further demonstrated the remarkable contribution of surface groups (OH^–, –NH₂ and –COOH), electrostatic attraction (via H- bonds), surface complexation and ion exchange followed by external mass transfer diffusion and As(III) oxidation into As(V) by (N/Fe₃O₄@BC) reactive oxygen species. Moreover, successful desorption was achieved at varying rates up to 7th regeneration cycle thereby showing (N/Fe₃O₄@BC) potential practical application. Thus, this work provides a novel insight for the fabrication of novel magnetic biochar for As removal from contaminated water in natural, engineering and environmental settings.     

Radiochemical studies on the extraction of arsenic(III) by trilaurylamine oxide and benzene from aqueous iodide solutions and its determination in water samples by spectrophotometry

An extraction system consisting of trilaurylamine N-oxide and benzene has been identified as a possible extractant for tracer arsenic (<10^–3 M) from hydrochloric or sulfuric acid solutions with or without iodide. Benzene alone is less efficient as an extractant for arsenic when compared with trilaurylamine oxide dissolved in benzene. The mechanism of extraction is attributed to the formation of hydrated AsCl₃, while the iodide complex is most probably AsI ₄ ^– . The role of the solvent and the other parameters affecting the extraction have been investigated. The results have been employed to determine arsenic in water samples by spectrophotometry using the molybdenum blue method. The extraction procedure was used for the analysis of 10 ml water samples containing 0.2–0.5 g of arsenic.