Application of diffusive gradient in thin films technique (DGT) to measurement of mercury in aquatic systems

The diffusive gradient in thin films (DGT) technique was investigated and used to measure mercury concentration in river water. Mercury ions are covalently bound to amide nitrogen groups of commonly used polyacrylamide, which makes this gel unsuitable as a diffusive medium. In contrast, agarose gel was found as the diffusive gel for mercury measurements. Basic performance tests of agarose DGT verified the applicability of Fick's first law for DGT measurements. Two selective resins, Chelex-100 with iminodiacetic groups and Spheron-Thiol with thiol groups were used. The measured diffusion coefficient in agarose gel was close to that in water. The concentration of mercury in Svitava river measured by DGT with Speron-Thiol resin gel was higher (0.0116 ± 0.0009 μg l⁻¹) than those obtained by Chelex-100 (0.0042 ± 0.0005 μg l⁻¹). Different capture efficiencies of two adsorbents enable to estimate fractions of mercury bonded in different complexes in the river water. The concentrations of mercury found by DGT both Chelex-100 and Speron-Thiol resin gels are much lower than that measured directly in the river water (0.088 ± 0.012 μg l⁻¹). This difference indicates that DGT concerns inorganic ions and labile species only, and that it is not able to include inert organic species and colloids.     

Effect of competitive cation binding on the measurement of Mn in marine waters and sediments by diffusive gradients in thin films

The possible adverse effect of competitive binding on DGT (diffusive gradients in thin films) measurements of metals in marine situations was investigated. Of the divalent transition metals, manganese binds most weakly to Chelex resin and is most likely to be affected by competition. In media resembling seawater, the Chelex within DGT devices becomes saturated with Ca and Mg within 2 h, and at pH 5–6 the sensitivity of the DGT measurement for Mn is substantially reduced, due to the appreciable concentration of Mn in contact with the resin. For media resembling freshwater DGT gives a near theoretical response for Mn. Iron was shown to be capable of displacing Mn and to a more limited extent Cd from the resin when its capacity for Fe is approached. Vertical profiles of Mn in a mesocosm sediment, obtained by deploying DGT for different times, could be explained by this displacement effect. The problem only occurs when Fe concentrations are exceptionally high and can be avoided by using short deployment times, typically less than 12 h. Whilst most trace metals can be simply measured by deploying DGT in marine systems, for Mn consideration should be given to possible effects associated with the capacity of the Chelex binding layer being approached by accumulation of the other cations present.     

新型薄膜扩散梯度技术定量采集高盐度水体中的铵离子

设计了一种基于铁氰化钴钠的新型薄膜扩散梯度(DGT)被动采样装置, 将其应用于高盐度水体中铵离子的定量采集. 采用双滴加法制备铁氰化钴钠, 并利用扫描电子显微镜(SEM)、 X射线衍射(XRD)仪和氮气吸 附-脱附测试对其表面形貌、 晶体结构和孔结构特征进行表征. 研究了铁氰化钴钠对铵离子的吸附速率和吸附容量. 建立了以琼脂糖凝胶为扩散相、 铁氰化钴钠为结合相的DGT被动采样装置. 研究了采集时间、 水体pH值和共存阳离子对基于铁氰化钴钠的DGT技术采集铵离子的影响. 实验结果表明, 铁氰化钴钠吸附铵离子在60 min时基本达到了吸附平衡; 当铵离子初始浓度为300 mg/L时其吸附容量为90 mg/g. DGT装置结合铵离子的质量随着布置时间的增加呈现线性增长(0~24 h, r²=0.994). 当pH=4~8, Na⁺浓度为0~10000 mg/L, K⁺浓度为0~25000 mg/L, Mg²⁺浓度为0~20000 mg/L, Ca²⁺浓度为0~25000 mg/L时, DGT装置累积的铵离子质量没有明显的变化. 实验结果表明, 使用基于铁氰化钴钠的DGT装置可以准确有效地采集高盐度水体中的铵离子.     

Characterization of mercury species in soils by HPLC-ICP-MS and measurement of fraction removed by diffusive gradient in thin films

The properties and behaviour of Hg depend on both the oxidation state and the chemical form: the bioavailability, toxicity, persistence and accumulation of mercury in the food web are strongly influenced by chemical speciation. The present work aims to determine the chemical forms of mercury present in soil and to evaluate the fraction of mercury in soil solution available to plants. In order to do this, we analyzed eight samples of contaminated soils with Hg concentrations ranging from 1.31 to 21.7 mg kg⁻¹, collected from different depths (0–10 and 40–50 cm) close to an abandoned industrial site in Val Basento (southern Italy). Two innovative analytical techniques were used: HPLC–ICP-MS and diffusive gradient in thin films (DGT). The analytical procedure was validated using ERM 580-certified sediment and spiked samples in the case of HPLC–ICP-MS, and by a performance test in the case of DGT. In all samples, the only species found in soil and soil solution was MeHg⁺ and Hg²⁺. In soil, the MeHg⁺/Hg_tot ratio ranged from 0.05% to 0.82%; total mercury in soil solution was less than 0.01% of total mercury in soil. The percentage of MeHg⁺ in soil solution varied considerably (from 0% to 50%), with a maximum concentration of 0.02 mg L⁻¹. The root available concentration evaluated by DGT is comparable to the total mercury content of the soil solution measured by HPLC–ICP-MS. The DGT results suggest that all mercury in solution is available for uptake in DGT, and that mercury is supplied from soil to solution. However, for all samples the soluble and root available (DGT-labile) fractions of mercury are generally very low with respect to the total mercury concentration. This study confirmed that both HPLC–ICP-MS and DGT techniques are suitable tools for the estimation of Hg root availability and in assessing the risk from contaminated soils.     

Peroxidase immobilized on Amberlite IRA-743 resin for on-line spectrophotometric detection of hydrogen peroxide in rainwater

The importance of atmospheric hydrogen peroxide (H₂O₂) in the oxidation of SO₂ and other compounds has been well established. A spectrophotometric method for the determination of hydrogen peroxide in rainwater is proposed. This method is based on selective oxidation of hydrogen peroxide using an on-line tubular reactor containing peroxidase immobilized on Amberlite IRA-743 resin. The hydrogen peroxide in the presence of phenol, 4-aminoantipyrine and peroxidase, produces a red compound (λ = 505 nm). Beer's law is obeyed in a concentration range of 1–100 μmol l⁻¹ hydrogen peroxide with an excellent correlation coefficient (r = 0.9991), at pH 7.0, with a relative standard deviation (R.S.D.) <2%. The detection limit of the method is 0.7 μmol l⁻¹ (4.8 ng of H₂O₂ in a 200 μl sample). Measurements of hydrogen peroxide in rain samples were carried out over the period from November 2003 to January 2005, in the central area of the Juiz de Fora city, Brazil. The concentration of H₂O₂ varied from values lower than the detection limit to 92.5 μmol l⁻¹. The effects of the presence of nonseasalt (NSS) SO₄²⁻, NO₃⁻ and H⁺ in the concentration of hydrogen peroxide in the rainwater had been evaluated. The average concentrations of H₂O₂, NO₃⁻, NSS SO₄²⁻ and SO₄²⁻ are 23.4, 18.9, 7.9 and 10.3 μmol l⁻¹, respectively. The pH values for 82% of the collected samples are greater than 5.0. The spectrophotometeric method developed in this work that uses enzyme immobilized on the resin ion-exchange compared with the amperometric method did not present any significant difference in the results.     

Application of the diffusive gradients in thin films technique for available potassium measurement in agricultural soils: Effects of competing cations on potassium uptake by the resin gel

The utilization of Amberlite (IRP-69 ion-exchange resin, 100–500 wet mesh) as the binding phase in the diffusive gradients in thin films (DGT) technique has shown potential to improve the assessment of plant-available K in soils. The binding phase has recently been optimized by using a mixed Amberlite and ferrihydrite (MAF) gel which results in linear K uptake over extended deployment periods and in solutions with higher K concentrations. As restriction of K uptake by Ca on the Amberlite based resin gel has been previously proposed, potential competing effects of Ca²⁺, Mg²⁺ and NH₄⁺ on K uptake by the MAF gel were investigated. These cations had no effect on K elution efficiency which was 85%. However, K uptake by the MAF gel was restricted in the presence of competing cations in solution. Consequently, the diffusion coefficient of K decreased in the presence of cations compared to previous studies but was stable at 1.12 × 10⁻⁵ cm² s⁻¹ at 25 °C regardless of cation concentrations. Uptake of K by the DGT device was affected by the presence of excessive Ca in more than 30% of twenty typical Australian agricultural soils. However, this problem could be circumvented by using a shorter deployment time than the normal 24 h. Moderate correlation of concentrations of K extracted by DGT with Colwell K (extracted by NaHCO₃, R² = 0.69) and NH₄OAc K (R² = 0.61) indicates that DGT measures a different pool of K in soils than that measured by the standard extractants used. In addition, the MAF gel has the ability to measure Ca and Mg simultaneously.     

A novel homocystine-agarose adsorbent for separation and preconcentration of nickel in table salt and baking soda using factorial design optimization of the experimental conditions

Homocystine was for the first time, chemically linked to a highly cross-linked agarose support (Novarose) to be employed as a chelating adsorbent for preconcentration and AAS determination of nickel in table salt and baking soda. Nickel is quantitatively adsorbed on a small column packed with 0.25 ml of the adsorbent, in a pH range of 5.5–6.5 and simply eluted with 5 ml of a 1 mol l⁻¹ hydrochloric acid solution.

A factorial design was used for optimization of the effects of five different variables on the recovery of nickel. The results indicated that the factors of flow rate and column length, and the interactions between pH and sample volume are significant.

In the optimized conditions, the column could tolerate salt concentrations up to 0.5 mol l⁻¹ and sample volumes beyond 500 ml. Matrix ions of Mg²⁺ and Ca²⁺, with a concentration of 200 mg l⁻¹, and potentially interfering ions of Cd²⁺, Cu²⁺, Zn²⁺ and Mn²⁺, with a concentration of 10 mg l⁻¹, did not have significant effect on the analyte's signal. Preconcentration factors up to 100 and a detection limit of 0.49 μg l⁻¹, corresponding to an enrichment volume of 500 ml, were obtained for the determination of the analyte by flame AAS. Application of the method to the determination of natural and spiked nickel in table salt and baking soda solutions resulted in quantitative recoveries. Direct ETAAS determination of nickel in the same samples was not possible because of a high background observed.     

Characterization of the low-oxidation-potential electrogenerated chemiluminescence of tris(2,2′-bipyridine)ruthenium(II) with tri-n-propylamine as coreactant

The electrogenerated chemiluminescence (ECL) of the Ru(bpy)₃²⁺ (bpy, 2,2′-bipyridine)/tri-n-propylamine (TPrA) system can be produced at an oxidation-potential well before the oxidation of Ru(bpy)₃²⁺. Here, we describe the unique features of the low-oxidation-potential (LOP) ECL. The LOP ECL exhibited strong dependence on solution pH with the maximum emission at pH  7.7. Compared with the conventional ECL, the LOP ECL was much more significantly diminished at high pH (>10), probably due to the short lifetime of TPrA cation radical which is a crucial intermediate for the LOP emission. It was also found that the preceding deprotonation step played an important role in TPrA oxidation at neutral pH and would remarkably influence the emission intensity. As excess intermediate radicals were produced upon rapid TPrA oxidation, only 5 mM TPrA was needed to achieve the maximum LOP ECL intensity in detecting trace Ru(bpy)₃²⁺ (<1 μM) and the LOP ECL response to Ru(bpy)₃²⁺ concentration was linear. Compared with the conventional Ru(bpy)₃²⁺/TPrA ECL, the LOP ECL technique not only produces higher emission intensity at lower oxidation-potential, but also significantly reduces the amount of the coreactant.     

Naked-eye detection of trace arsenic(V) in aqueous media using molybdenum-loaded chelating resin having beta-hydroxypropyl-di(beta-hydroxyethyl)amino moiety

A naked-eye detection method for a trace amount of arsenic in aqueous samples has been newly developed. The proposed method is based on the formation of a hetero poly acid in a chelating resin phase. Molybdenum loaded on a chelating resin having β-hydroxypropyl-di(β-hydroxyethyl) amino moiety reacts with arsenic(V) to form the hetero poly acid, which makes the resin beads greenish blue in the presence of a reducing agent under acidic conditions. It was also found that the intensity of the color of the resin depends on the concentration of arsenic(V) in the sample solutions. Since the development of the color occurs in 20 min by heating of the mixture at 40 °C, this system can provide a simple, rapid and low-cost detection method of a trace amount of arsenic(V) in an aqueous media. The detection limit of this method is 1 × 10⁻⁶ mol dm⁻³. A longer preconcentration time with the same resin gave the higher sensitivity of 1 × 10⁻⁷ mol dm⁻³ that is comparable with that of the instrumental analysis. The present method comprises both the concentration and detection step with the same solid material, and hence it gives higher sensitivity and easier handling than the ordinary colorimetric methods using a liquid medium.     

Electrochemiluminescent behavior of allopurinol in the presence of Ru(bpy)(3)(2+)

The electrochemiluminescent (ECL) response of allopurinol was studied in aqueous media over a wide pH range (pH 2–13) using flow injection (FI) analysis. It was revealed that allopurinol itself had no ECL activity, but could greatly enhance the ECL of Ru(bpy)₃²⁺ in alkaline media giving rise to a sensitive FI-ECL response. The effects of experimental conditions including the mode of applied voltage signal, the potential of working electrode, pH value, the flow rate of carrier solution, and the concentration of Ru(bpy)₃²⁺ and allopurinol on the ECL intensity were investigated in detail. The most sensitive FI-ECL response of allopurinol was found at pH 12.0, where the FIA-ECL intensity showed a linear relationship with concentration of allopurinol in the range 1 × 10⁻⁸ mol L⁻¹ to 5 × 10⁻⁷ mol L⁻¹, and the detection limit was 5 × 10⁻⁹ mol L⁻¹.     

Lability criteria in diffusive gradients in thin films

The penetration of metal complexes into the resin layer of DGT (diffusive gradients in thin films) devices greatly influences the measured metal accumulation, unless the complexes are either totally inert or perfectly labile. Lability criteria to predict the contribution of complexes in DGT measurements are reported. The key role of the resin thickness is highlighted. For complexes that are partially labile to the DGT measurement, their dissociation inside the resin domain is the main source of metal accumulation. This phenomenon explains the practical independence of the lability degree of a complex in a DGT device with respect to the ligand concentration. Transient DGT regimes, reflecting the times required to replenish the gel and resin domains up to the steady-state profile of the complex, are also examined. Low lability complexes (lability degree between 0.1 and 0.2) exhibit the longest transient regimes and therefore require longer deployment times to ensure accurate DGT measurements.     

Application of a new resin functionalised with 6-mercaptopurine for mercury and silver determination in environmental samples by atomic absorption spectrometry

Polystyrene–divinylbenzene (8%) has been functionalised by coupling it through an ---N=N--- group with 6-mercaptopurine. The resulting chelating resin has been characterised by using elemental analysis, thermogravimetric analysis and infrared spectra. The resin is highly selective for Hg(II) and Ag(I) and has been used for preconcentrating Hg(II) and Ag(I) prior to their determination by atomic absorption spectrometry. The maximum sorption capacity for Hg(II) and Ag(I) was found to be 1.74 and 0.52 mmol g⁻¹, respectively, over the pH range 5.5–6.0. The calibration range for Hg(II) was linear up to 10 ng ml⁻¹ with a 3σ detection limit of 0.02 ng ml⁻¹; the calibration range for Ag(I) was linear up to 5 μg ml⁻¹ with a detection limit of 29 ng ml⁻¹. The recoveries of the metals were found to be 99.7±3.8 and 101.3±4.1% at the 95% confidence level for both Hg(II) and Ag(I). In column operation, it has been observed that Hg(II) and Ag(I) in trace quantities can be selectively separated from geological, medicinal and environmental samples.     

Functionalization of chitosan with 3-nitro-4-amino benzoic acid moiety and its application to the collection/concentration of molybdenum in environmental water samples

A chitosan resin functionalized with 3-nitro-4-amino benzoic acid moiety (CCTS-NABA resin) was newly synthesized for the collection/concentration of trace molybdenum by using cross-linked chitosan (CCTS) as base material. The carboxyl group of the moiety was chemically attached to amino group of cross-linked chitosan through amide bond formation. The adsorption behavior of molybdenum as well as other 60 elements on the resin was examined by passing the sample solutions through a mini-column packed with the resin. After the elution of the elements collected on the resin with 1 M HNO₃, the eluates were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) and atomic emission spectrometry (ICP-AES).

The CCTS-NABA resin can adsorb several metal ions, such as vanadium, gallium, arsenic, selenium, silver, bismuth, thorium, tungsten, tin, tellurium, copper, and molybdenum at appropriate pHs. Among these metal ions, only molybdenum could be adsorbed almost completely on the resin at acidic regions. An excellent selectivity toward molybdenum could be obtained at pH 3–4. The adsorption capacity of CCTS-NABA resin for Mo(VI) was 380 mg g⁻¹ resin. Through the column pretreatment, alkali and alkaline earth metals in river water and seawater samples were successfully removed.

The CCTS-NABA resin was applied to the adsorption/collection of molybdenum in river water and seawater samples. The concentrations of molybdenum in river water samples were found in the range of 0.84 and 0.95 ppb (ng g⁻¹), whereas molybdenum in seawater was about 9 ppb. The validation of the proposed method was carried out by determining molybdenum in the certified reference materials of SLRS-4, CASS-4, and NASS-5 after passing through the CCTS-NABA resin; the results showed good agreement with the certified values.     

Flow injection determination of bismuth in urine by successive retention of Bi(III) and tetrahydroborate(III) on an anion-exchange resin and hydride generation atomic absorption spectrometry

Bismuth as BiCl₄⁻ and BH₄⁻ ware successively retained in a column (150 mm × 4 mm, length × i.d.) packed with Amberlite IRA-410 (strong anion-exchange resin). This was followed by passage of an injected slug of hydrochloric acid resulting in bismuthine generation (BiH₃). BiH₃ was stripped from the eluent solution by the addition of a nitrogen flow and the bulk phases were separated in a gas–liquid separator. Finally, bismutine was atomized in a quartz tube for the subsequent detection of bismuth by atomic absorption spectrometry. Different halide complexes of bismuth (namely, BiBr₄⁻, BiI₄⁻ and BiCl₄⁻) were tested for its pre-concentration, being the chloride complexes which produced the best results. Therefore, a concentration of 0.3 mol l⁻¹ of HCl was added to the samples and calibration solutions. A linear response was obtained between the detection limit (3σ) of 0.225 and 80 μg l⁻¹. The R.S.D.% (n = 10) for a solution containing 50 μg l⁻¹ of Bi was 0.85%. The tolerance of the system to interferences was evaluated by investigating the effect of the following ions: Cu²⁺, Co²⁺, Ni²⁺, Fe³⁺, Cd²⁺, Pb²⁺, Hg²⁺, Zn²⁺, and Mg²⁺. The most severe depression was caused by Hg²⁺, which at 60 mg l⁻¹ caused a 5% depression on the signal. For the other cations, concentrations between 1000 and 10,000 mg l⁻¹ could be tolerated. The system was applied to the determination of Bi in urine of patients under therapy with bismuth subcitrate. The recovery of spikes of 5 and 50 μg l⁻¹ of Bi added to the samples prior to digestion with HNO₃ and H₂O₂ was in satisfactory ranges from 95.0 to 101.0%. The concentrations of bismuth found in six selected samples using this procedure were in good agreement with those obtained by an alternative technique (ETAAS). Finally, the concentration of Bi determined in urine before and after 3 days of treatment were 1.94 ± 1.26 and 9.02 ± 5.82 μg l⁻¹, respectively.     

Assessment of trace metal binding kinetics in the resin phase of diffusive gradients in thin films

The dynamic technique of diffusive gradients in thin films (DGT), that measures metal speciation in situ, has found wide environmental application. Simple interpretation of the metal accumulation in terms of a solution concentration has assumed that trace metals do not penetrate beyond the surface of the binding layer, but penetration, although theoretically discussed has not yet been directly measured. Multiple binding layers were used to enable analysis of different depths of a DGT binding phase (Chelex-100 or iminodiacetate resins). In simple metal solution (no ligand) at pH 7, metal penetration to the back layer was low and similar for all metals. However, at lower pH up to 42% of an individual metal accumulated in the back resin layer. This was most noticeable for Mn at pH 4 and 5, but Cd and Co were also affected at pH 4. These results were consistent with rate limited binding, particularly for Mn. A kinetic model successfully fitted the data and allowed derivation of a binding rate constant and the mean distance that metals penetrate into a resin gel (λ_M). Only for Mn, Co and Cd were experimentally derived λ_M values greater than the diameter of a Chelex-100 resin bead. For most situations, then, the penetration into the binding layer is negligible and binding of trace metal ions can be regarded as instantaneous, validating the simple use and interpretation of DGT. For weakly binding metals at low pH the slower binding allows penetration, which may affect the DGT measurement.     

Performance characteristics of suspended particulate reagent-iminodiacetate as a binding agent for diffusive gradients in thin films

The performance characteristics of an alternative binding agent, suspended particulate reagent-iminodiacetate (SPR-IDA), for use with DGT methodology were investigated. The parameters investigated during this study included gel hydration, blank levels, elution factor (f_e), capacity, the effects of pH on the binding of trace metals by DGT. The novel application of this resin for use as a quantitative standard for laser ablation ICP-MS was also evaluated. To further constrain the results for the SPR-IDA binding agent, parallel experiments were performed using resin gel containing Chelex 100, which has been widely reported in the literature. Hydration results showed that the SPR-IDA resin gel reached a stable dimension and weight within ∼30 min and was dimensionally stable for ≤6 months. The measured DGT blanks for the SPR-IDA resin were 0.0023, 0.15, 0.21, 0.0033 and 0.011 ng disc⁻¹ for Co, Ni, Cu, Cd and Pb, respectively. The elution factor differed for the two resin types with the Chelex 100 recoveries slightly lower than previous reports and the SPR-IDA resin showing on average ∼5-9% better recoveries than DGT containing Chelex 100. The measured capacity of DGT discs containing the SPR-IDA binding agent was 0.26 mg Cd, similar to the calculated value of 0.29 mg Cd, indicating the entire resin layer was available for metal uptake.Both resin types performed equally well when deployed in 1 mM NaNO₃ solutions with DGT measurements of ∼100% of direct solution measurements for Co, Ni and Cd. However, DGT measurements of Cu and Pb systematically decreased with increasing solution pH down to ∼50% of solution values at pH 8.0, due to artifacts resulting from colloid formation during the addition of the metals. This was remedied by adding the metals as dilute salt standards and addition of Mg(NO₃)₂ to eliminate adsorption to the container walls. In the latter experiments, DGT measured concentrations of Co, Ni, Cu, Cd and Pb were in agreement with solution concentrations. Deployment of DGT in solutions with increasing concentrations of trace metals yielded linear results, suggesting that quantitative analysis using simplified laser ablation techniques should be possible using this newly characterized SPR-IDA resin gel.     

Capillary electrochromatographic separation of metal ion species with on-line detection by inductively coupled plasma mass spectrometry

A bonded phase capillary column containing macrocyclic polyamine, [28]ane-N₆O₂ functional groups was used for the electrophoretic separation of arsenic, chromium and selenium species. A simple device interfacing this capillary electrochromatography (CEC) systems to an inductively coupled plasma mass spectrometer (ICPMS) is described. The dimension of the capillary column was 160 cm×100 μm i.d. To accommodate this electrophoretic separation, an auxiliary capillary was used with nitric acid (0.05 M) as makeup liquid. With the electrokinetic method at –20 kV, 20 s and a nebulizer gas flow rate of 1 l min⁻¹, the sample injected was analyzed with an applied potential of −20 kV. The background electrolyte buffer for the separation of CrO₄²⁻–Cr³⁺ was phosphate (20 mM, pH 6.5). That for HAsO₄²⁻–Ph₄As⁺ was pyromellitate (20 mM, pH 6.0) and for SeO₄²⁻–SeO₃²⁻ was acetate (20 mM, pH 6.0). The role of the buffer’s anion was also discussed. The separation efficiency of the bonded phase was compared with the bare fused silica. Concentration detection limits for these metal ions were in the low ppb range. In addition, the matrix effect of the established system with the bonded phase was found smaller than that with the bare fused silica.     

Effect of pH on the characteristics of potassium permanganate–luminol CL reaction in the presence of trace aluminum(III) and its analytical application

At pHs ≥ 11.45, trace Al was found to enhance the CL from luminol–KMnO₄ system. However, at pHs ≤ 10.42, it was found to inhibit strongly the CL from luminol–KMnO₄ system. The effect of pH, luminol and potassium permanganate concentrations on the kinetic characteristics of CL system was investigated in the presence of trace Al. On this basis, a flow injection inhibition chemiluminescence method was established for the determination of trace Al in this study. Under optimized conditions, the CL decreased linearly with Al(III) concentration in the range of 8–500 μg L⁻¹ and the detection limit (3σ) of 2 μg L⁻¹. The relative standard deviation (R.S.D.) is 3.6% for 100 μg L⁻¹ Al(III) (n = 11). The method has been applied to the determination of trace Al in real water samples with satisfactory results without the pretreatment of samples. The results given by the proposed method are in good agreement with those given by ICP-AES detection method.     

Selective removal of Cu versus Ni, Zn and Mn by using a new carrier in a supported liquid membrane

A study on transport, kinetic selectivity and stability in SLM operations using a new carrier, the molecule 2-hydroxy-5-dodecylbenzaldehyde (2H5DBA) in kerosene, is described. A simple transport model is derived to evaluate the mass transfer coefficient in the membrane. Finally a comparison with the di-(2-ethylhexyl) phosphoric acid (D2EHPA) carrier in kerosene is made. The SLM system was employed and tested in the removal of Cu²⁺ from wastewater by using the operating conditions obtained from L–L extraction tests. Studies on the kinetics of copper extraction by using the 2H5DBA showed that complexation reaction is very fast. Transport tests were performed at different carrier concentrations (10%, 30%, 50% (v/v)) showing the improvement of SLM performance with increasing its concentration. Operating the SLM at optimum conditions (50% (v/v) 2H5DBA concentration in kerosene, feed pH 5, strip pH 2.2) final copper concentrations in the feed and strip phases were, respectively, 2.0 and 47.0 mg L⁻¹, starting from 50 mg L⁻¹ in the feed, meaning a significant up-hill transport. The fluxes (J) were calculated by fitting the experimental data of copper concentration in the feed by an exponential equation. They were used to calculate the transport (kinetic) selectivities of Cu²⁺ SLM separation over Ni²⁺, Zn²⁺ and Mn²⁺, given by the ratio J₀(Cu)/J₀(M), where M = Ni, Zn and Mn. The values were 37.4, 48.2 and 42.1, respectively. Transport and stability tests at the optimal carrier concentration by using the 2H5DBA and the D2EHPA in kerosene were carried out to compare them in terms of flux, lifetime and mass transfer coefficients. Experimental data evidenced for 2H5DBA a lower copper flux (8.67 mmol h⁻¹ m⁻² versus 36.71 mmol h⁻¹ m⁻²), a lower lifetime (20 h versus 57 h) and lower mass transfer coefficient in the membrane (3.00 × 10⁻⁷ m s⁻¹ versus 2.00 × 10⁻⁶ m s⁻¹) but the selectivity of the separation process can overcome the disadvantages.     

Efficiency of Cd(II) removal from aqueous media using chemically modified polystyrene foam

The removal of Cd(II) using polystyrene foam chemically modified with 2,2′-bipyridine has been investigated. The modified polystyrene foam has been characterized by FT-IR spectroscopy, thermogravimetry, elemental analysis and scanning electron microscopy. The solid was employed as a Cd(II) adsorption from aqueous solutions at room temperature. The effects of several variables (pH, shaking speed, agitation time, metal concentration and presence of other ions in the medium) have been studied using batch technique. Flame atomic absorption spectrometry was used to determine the Cd(II) ion concentration in the filtrate after the adsorption process. Maximum sorption 90% was achieved at pH 7 after 30 min of shaking time. Sorbed metal ions have been desorbed with 5 ml of 2 M HNO₃ with the detection limit of 16.7 ng ml⁻¹. The Langmuir, Freundlich and D–R isotherm equation were used to describe partitioning behavior of the system at room temperature. Kinetic and thermodynamic behavior of modified polystyrene foam for Cd(II) ion removal was also studied. Br⁻, PO₄³⁻, Pb²⁺, Ni²⁺ and Cr(VI) suppress the sorption to some extent. The possible sorption mechanism of Cd(II) ions onto modified sorbent is also discussed. Method was utilized to remove Cd(II) ions from aqueous media.