Estimation of platinum in environmental water samples with solid phase extraction technique using inductively coupled plasma mass spectrometry

A solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectromA solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectrometry (ICP-MS) was developed. The method was based on retention of platinum in a sample on silica gel modified with aminepropyl groups. The retention of platinum(IV) from the sample solution and the recovery of platinum with 1.0 mol L⁻¹ thiourea solution were quantitative. The relative standard deviation (RSD) was calculated as 5% (n = 7) at the 10 ng L⁻¹ level. The enrichment factor was found to be (50-fold) for 250 mL of water sample. Under optimum conditions, the method detection limit (MDL) was found to be 1 ng L⁻¹ for platinum in water matrices. Recoveries of Pt from spike addition to atmospheric water samples were quantitative (80–95%). The present method was used for the determination of platinum in precipitation, throughfall and runoff water samples.      

Preparation and utilization of a molecularly imprinted polymer for solid phase extraction of tramadol

In this paper, a highly selective molecularly imprinted polymer (MIP) for tramadol hydrochloride, a drug used to treat moderate to severe pain, was prepared and its use as solid-phase extraction (SPE) sorbent was demonstrated. The molecularly imprinted solid-phase extraction procedure followed by high performance liquid chromatography with ultraviolet detector (MISPE-HPLC) was developed for selective extraction and determination of tramadol in human plasma and urine. The optimal conditions for molecularly imprinted solid-phase extraction (MISPE) consisted of conditioning with 1 mL methanol and 1 mL of deionized water at neutral pH, loading of tramadol sample (50 μg L⁻¹) at pH 7.5, washing using 1 mL acetone and elution with 3 × 1 mL of 10% (v/v) acetic acid in methanol. The MIP selectivity was evaluated by checking several substances with similar molecular structures to that of tramadol. Results from the HPLC analyses showed that the calibration curve of tramadol (using MIP from human plasma and urine) is linear in the ranges of 6–100 and 3–120 μg L⁻¹ with good precisions (1.9% and 2.9% for 5.0 μg L⁻¹), respectively. The recoveries for plasma and urine samples were higher than 81%.      

Selective separation of some ecotoxic transition metal ions from aqueous solutions using immobilized macrocyclic material containing solid phase extraction system

A simple flow-based method was developed for the simultaneous separation of certain transition metal ions (Co, Ni, Cu, Zn, Cd) from aqueous systems, which ions show ecotoxic effects when present at elevated concentrations. A silica-gel-bonded macrocycle system, commonly known as molecular recognition technology (MRT) gel, was used for solid phase extraction (SPE) of the target analytes. The collection behavior of the MRT-SPE system was studied based on pH. Fortified deionized water samples containing 250 μg L⁻¹ of each of the elements were treated at the flow rate of 1 mL min⁻¹. The collected analytes were then eluted by 3 M HNO₃ and analyzed using inductively coupled plasma spectrometry. Detection limits of the proposed technique were in the range of 0.004–0.040 μg L⁻¹ for the studied metal ions. The validity of this separation technique was checked with spiked ‘real’ water samples, which produced satisfactory recoveries of 96–102%. The non-destructive nature and highly selective ion-extraction capability of the SPE material are the most important aspects of the proposed method and they are the main focus of this paper.      

Removal of Pb and Cd from aqueous media and fish liver using novel polyurethane foam functionalized with pyrazolone as a new metal ion collector

In the present paper, an off-line preconcentration procedure for the determination of cadmium and lead by flame atomic absorption spectrometry (FAAS) is proposed. Polyurethane foam (PUF) functionalized with o-aminophenol (o-AP) followed by Pyrazolone (Pyr) packed in a minicolumn was used as a sorbent material. The metals were retained on the modified PUF, from which it could be eluted and effectively preconcentrated. The detection limits were 0.072 and 0.016 μg L⁻¹ for Pb and Cd respectively. Enrichment factors were 250 and 319 for lead and cadmium respectively. The procedure has been applied successfully to metal determination in water samples, fish liver and reference material.      

Determination of europium by using the chemical oscillating system of Ce(IV)-KBrO<Subscript>3</Subscript>-acetone-oxalic acid-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>

A sensitive and convenient method for the determination of trace europium ions using an oscillating chemical reaction involving Ce(IV) - KBrO₃ - acetone - oxalic acid - H₂SO₄ was proposed. The results indicated that the changes in oscillating period (T) was linearly proportional to the negative logarithmic concentration of Eu³⁺ (-log C) in the range of 1.41 × 10⁻⁸ ˜ 1.41 × 10⁻⁴ mol L⁻¹ (r = 0.9982) with a detection limit of 1.04 × 10⁻⁹ mol L⁻¹. The recoveries were limited to the range of 99.5% to 100.8%. Under the same conditions, other rare earth ions did not interfere with the determination of Eu³⁺. In addition, a perturbation mechanism was also discussed briefly.      

Determination of cobalt in water samples by atomic absorption spectrometry after pre-concentration with a simple ionic liquid-based dispersive liquid-liquid micro-extraction methodology

A rapid dispersive liquid-liquid micro-extraction (DLLME) methodology based on the application of 1-hexylpyridinium hexafluorophosphate [C₆py][PF₆] ionic liquid (IL) as an extractant solvent was applied for the pre-concentration of trace levels of cobalt prior to determination by flame atomic absorption spectrometry (FAAS). 1-Phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) was employed as a chelator forming a Co-PMBP complex to extract cobalt ions from aqueous solution into the fine droplets of [C₆py][PF₆]. Some effective factors that influence the micro-extraction efficiency include the pH, the PMBP concentration, the amount of ionic liquid, the ionic strength, the temperature and the centrifugation time which were investigated and optimized. In the optimum experimental conditions, the limit of detection (3s) and the enrichment factor were 0.70 μg L⁻¹ and 60, respectively. The relative standard deviation (RSD) for six replicate determinations of 50 μg L⁻¹ Co was 2.36%. The calibration graph using the pre-concentration system was linear at levels 2–166 μg L⁻¹ with a correlation coefficient of 0.9982. The applicability of the proposed method was evaluated by the determination of trace amounts of cobalt in several water samples.      

Dispersive liquid-liquid microextraction and liquid chromatographic determination of pentachlorophenol in water

A simple and sensitive dispersive liquid-liquid microextraction method for extraction and preconcentration of pentachlorophenol (PCP) in water samples is presented. After adjusting the sample pH to 3, extraction was performed in the presence of 1% W/V sodium chloride by injecting 1 mL acetone as disperser solvent containing 15 μL tetrachloroethylene as extraction solvent. The proposed DLLME method was followed by HPLC-DAD for determination of PCP. It has good linearity (0.994) with wide linear dynamic range (0.1–1000 μg L⁻¹) and low detection limit (0.03 μg L⁻¹), which makes it suitable for determination of PCP in water samples.      

Properties of naproxen ion-selective electrodes

Naproxen membrane electrodes based on different plasticizers and the quaternary ammonium salts (QASs) dimethyldidecylammonium bromide, methyltrioctylammonium chloride, or tetraoctylammonium chloride, were prepared. The following basic parameters were investigated for the optimal electrode: measurement range (10⁻⁴ − 10⁻¹ mol L⁻¹), slope of the linear range of the calibration curve (−58.3 mV decade⁻¹), limit of detection (6.0 × 10⁻⁵ mol L⁻¹), lifetime (2.5 months), dependence of the electrode potential on pH (5.5 − 9.0), reproducibility of potential (1.2 mV) and selectivity coefficients in relation to selected organic and inorganic anions. The electrode was utilized for determination of naproxen in tablets by the calibration curve method and the standard addition method.      

Solid phase selective separation and green preconcentration of Cu, Zn, Pb and Cd in drinking water by using novel functionalized resin

A new solid — phase extraction sorbent was developed based on stepwise anchoring of two ligand molecules for the determination of copper, zinc, lead and cadmium in drinking water by flame AAS. Amberlite XAD-2 functionalized with 4′-(2-hydroxyphenylazo)-3′-methyl-1′-phenyl-2′-pyrazolin-5′-one (HPAPyr) was utilized for preconcentration/separation of these elements. The sorbent was prepared by two successive azo coupling reactions. First, 2-aminophenol was anchored to the amino groups in the resin resulted from nitration followed by reduction. Then, the resulted 2-aminophenol functionalized resin was further diazotized and coupled to the pyrazolone compound and the final product HPAPyr-XAD-2 was characterized by IR and elemental analysis. The optimum pH range for sorption, shaking time, exchange capacity, sample flow rate, preconcentration factor and interference from co-existing ions were investigated. All metal ions were quantitatively desorbed from the resin by 4.5 mol L⁻¹ nitric acid solution. The sorbent provides limit of detection within the range 0.9–3.3 μg L⁻¹ and concentration factor up to 250. The procedure was validated by analysis of certified material NIST-SRM 1577b. Application to drinking water showed satisfactory results with relative standard deviation RSD ≤ 8.5%.      

Properties of ibuprofen ion-selective electrodes based on the ion pair complex of tetraoctylammonium cation

Ibuprofen membrane electrodes based on different plasticizers: diisobutyl phthalate (DIBP), o-nitrophenyloctyl ether (o-NPOE), dioctyl sebacate (DOS) and tetraoctylammonium 2-(4-isobutylphenyl)propionate were prepared. All electrodes show: a near Nernstian slope of characteristic (58.3–60.9 mV decade⁻¹) in the measurement range (10⁻⁴–10⁻¹ mol L⁻¹), limit of detection (5.0×10⁻⁵ mol L⁻¹), really long lifetime (12 months), dependence of the electrode potential on pH (5.5–9.0), reproducibility of potential (0.6–1.2 mV) and selectivity coefficients in relation to some organic and inorganic anions. The electrodes were applied for the determination of ibuprofen in tablets by the calibration curve method and the standard addition method.      

Nanosized centers for mercury(II) ions adsorption on a surface of modified silica

The present work investigates the adsorptive interactions of Hg(II) ions in aqueous medium with hydroxylated silica, aminopropylsilica and silica chemically modified by β-cyclodextrin. Batch adsorption studies were carried out with various agitation times and mercury(II) concentrations. The maximum adsorption was observed within 15–30 min of agitation. The kinetics of the interactions, tested with the model of Lagergren for pseudo-first and pseudo-second order equations, showed better agreement with first order kinetics (k₁ = 3.4 ± 0.2 to 5.9 ± 0.3 min⁻¹). The adsorption data gave good fits with Langmuir isotherms. The results have shown that β-cyclodextrin-containing adsorbent has the largest adsorption specificity to Hg(II): K _L = 4125 ± 205 mmol⁻¹. “β-cyclodextrin-NO3-” inclusion complexes with ratio 1: 1 and super molecules with composition C₄₂H₇₀O₃₅ ⊎ 3 Hg(NO₃)₂ are formed on the surface of β-cyclodextrin-containing silica.      

Determination of penicillin V potassium in pharmaceuticals and spiked human urine by chemiluminescence

A simple and selective method for penicillin V potassium (PVK) determination by chemiluminescence (CL) was developed. Oxidation of PVK by alkaline hydrogen peroxide produces CL, which is greatly enhanced by N, N-dimethyl formamide (DMF) and N-cetyl-N,N,N-trimethylammonium bromide (CTMAB). Optimum conditions were established using luminometry. There is a linear relationship between the chemiluminescent peak height and the amount of PVK within the range 0.5–129.5 mg L⁻¹, with a detection limit of 0.2 mg L⁻¹. The coefficient of variation was 1.2% for 40 mg L⁻¹ PVK solution (n = 7). The method is very simple, has high sensitivity and good selectivity, and is usable for process control. It was successfully utilized for the determination of PVK in pharmaceuticals and spiked human urine.      

Spatial trends of petroleum hydrocarbons in water and sediments

Seasonal changes in petroleum hydrocarbons in water and streambed sediment from selected oil-related areas of Ondo State, Nigeria have been examined using gravimetric and infrared methods. The highest and lowest total petroleum hydrocarbon concentrations (TPH) in water (sediments in brackets) gravimetrically were 3.49 mg L⁻¹ (199.3) mg kg⁻¹ and 0.003 mg L⁻¹ (81.0) mg kg⁻¹ while the concentrations found by IR were 24.0 mg L⁻¹ (135.0 mg kg⁻¹) and 14.0 mg L⁻¹ (33.0 mg kg⁻¹) respectively. The two seasons were positively correlated (α = 0.01) by both methods. The TPH level was well correlated with the sediment organic carbon (OC) during both seasons. The characteristic carbonyl (C=O) vibrations at 1650 cm⁻¹ and 1700 cm⁻¹ indicate oxidation of the oil residue. The study recommends further investigation into the type of organics present to evaluate their toxicity and appropriate remediation.      

Determination of ultra-trace amounts of inorganic selenium species in natural water by ion chromatography-inductively coupled plasma-mass spectrometry coupled with nano-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> solid phase extraction

This work presents a nano-Al₂O₃ solid phase extraction technique for the determination of ultra-trace amounts of inorganic selenium species in aqueous systems using ion chromatography inductively coupled plasma-mass spectrometry (IC-ICP-MS). In this experiment, the inorganic selenium species were successfully extracted on a nano-Al₂O₃ solid phase column and then quantitative eluted with a 100 mmol L⁻¹ NaOH solution. Extraction conditions such as solvent identity, solvent concentration, solvent volume, solvent pH and salt addition were optimized. Under the optimum extraction conditions (elute solvent: 100 mmol L⁻¹ NaOH, solvent volume: 4 mL, pH: 7.0), low detection limits (Se (IV): 6 ng L⁻¹, Se (VI): 11 ng L⁻¹; RSD<5.0%) and good linear range (0.5–100 ng mL⁻¹, R² > 0.999) were obtained for all of the analytes. Good spiked recoveries over the range of 80–98% were obtained by applying the proposed method on real environmental water samples. These results indicated that this method is very sensitive and reliable when monitoring trace levels of inorganic selenium species in aqueous samples.      

Determination of p-nitroaniline by the tartrate-acetone-Mn2+-KBrO3-H2SO4 double organic substrate oscillating system using non-equilibrium stationary state

This paper described the determination of p-nitroaniline in a double organic substrate oscillating system of tartrate-acetone-Mn²⁺-KBrO₃-H₂SO₄. Under the optimum conditions, temperature was chosen as a control parameter to design the bifurcation point and proposed a convenient method for determination of p-nitroaniline. Results showed that the system consisting of 3.5 mL 0.06 mol L⁻¹ tartrate, 4.0 mL 0.7 mol L⁻¹ H₂SO₄, 1.5 mL 1.5×10⁻⁴ mol L⁻¹ MnSO₄, 4.0 mL 0.4 mol L⁻¹ acetone and 7.0 mL 0.05 mol L⁻¹ KBrO₃ was very sensitive to the surrounding at 33.5°C. A good linear relationship between the potential difference and the negative logarithm concentration of p-nitroaniline was obtained to be in the range of 2.50×10⁻⁷∼3.75×10⁻⁵ mol L⁻¹ with a lower detection limit of 2.50×10⁻⁸ mol L⁻¹.      

Hollow fibre liquid phase microextraction of parabens

A hollow fibre liquid phase microextraction for gas chromatographic determination of some p-hydroxybenzoic acid esters has been developed. Chlorobenzene containing tetradecane as internal standard was used for the extraction. Optimized extraction was carried out at room temperature for 40 min in the presence of 0.4 g mL⁻¹ NaCl in the sample solution. Calibration was linear up to 30 mg L⁻¹. Correlation coefficients were 0.996–0.998. Enrichment factors were 21, 95 and 154, and detection limits were 0.20, 0.03 and 0.01 μg mL⁻¹ for methylparaben, ethylparaben and propylparaben, respectively. Reproducibility was acceptable with relative standard deviations up to 11.7%. The technique was tested for water and urine analysis.      

Isocratic liquid chromatographic determination of three paraben preservatives in hygiene wipes using a reversed phase core-shell narrow-bore column

The first HPLC method for the separation of three paraben preservatives (methyl-, ethyl- and propyl parabens) using a core-shell analytical column is reported in this study. The separation was completed in less than 8 min at a low flow rate of 0.4 mL min⁻¹ and an isocratic mobile phase containing 20% acetonitrile as organic modifier. The backpressure was < 200 bar in all cases, enabling the usage of conventional HPLC equipment. The proposed analytical procedure was validated for linearity (0.5–20 μg L⁻¹), limits of detection (15–43 μg L⁻¹) and quantification (50–142 μg L⁻¹), selectivity, within day (1.3–1.5%) and day-to-day (3.4–4.6%) precision and accuracy. The proposed method has been applied to the determination of the selected paraben preservatives in commercially available hygiene wipes. The mean percent recoveries were found to be in the range of 98.0–98.4%.      

Cobalt(II) ion-selective electrode with solid contact

A new all plastic sensor for Co²⁺ ions based on 2-amino-5 (hydroxynaphtyloazo-1′)-1,3,4 thiadiazole (ATIDAN) as ionophore was prepared. The electrode exhibits a low detection limit of 1.5 × 10⁻⁶ mol L⁻¹ and almost theoretical Nernstian slope in the activity range 4.0 × 10⁻⁶–1 × 10⁻¹ mol L⁻¹ of cobalt ions. The response time of the sensor is less than 10 s and it can be used over a period of 6 months without any measurable divergence in potential. The proposed sensor shows a fairly good selectivity for Co(II) over other metal ions. The electrode was successfully applied for determination of Co²⁺ in real samples and as an indicator electrode in potentiometric titration of Co²⁺ ions with EDTA.      

Determination of diclofenac in pharmaceuticals and urine samples using a membrane sensor based on the ion associate of diclofenac with Rhodamine B

The potentiometric response characteristics of a diclofenac selective electrode, based on ion association in different plasticizers, were compared. The sensitivity, working range, detection limit and selectivity of membrane sensors demonstrated significant dependence on the type of plasticizers. The potentiometric unit presented a linear response toward diclofenac concentrations between 1 × 10⁻⁵ − 5 × 10⁻² mol L⁻¹, with slopes of approximately 60 mV dec⁻¹, and exhibited a response time of 3 s. The potentiometric analysis of sodium diclofenac in pharmaceutical formulations was perfomed by the membrane electrode proposed and compared with the results of potentiometric titration given by the Pharmacopoeia of Ukraine.      

Preliminary results of a quick,simple method of detecting antimony in water samples

Preliminary results of development of a direct and fast method of determination of antimony in samples of tap water using GFAAS are presented. The found levels of antimony were lower than permitted for human consumption. A mixture of Pd and Mg(NO₃)₂ (concentrations in the injected solution: 8.6 μg mL⁻¹ and 5.8 μg mL⁻¹ respectively) was used as the chemical modifier. The pyrolysis and atomization temperatures were 1000 and 1700°C, respectively and the mean analytical recovery 98.2%.