Preparation, characterization, and application of a new thiol-functionalized ionic liquid for highly selective extraction of Cd(II)

A highly selective thiol-functionalized ionic liquid (thiol-FIL) was synthesized and characterized by FT-IR and ESI mass spectroscopy. The capability of thiol-FIL to extract Cd(II), Ni(II), Cr(III) and Pb(II) was evaluated. It is found that thiol-FIL possesses high selectivity for Cd(II), and this has led to a method for determination of Cd(II) by flame atomic absorption spectrometry that is free of interferences by up to a 1,000-fold excess of Na(I), Mg(II), Ca(II), Mn(II), Fe(III), Al(III), Cu(II), Zn(II), Ni(II), Cr(III), Co(II), As(III), Pb(II), and Hg(II). With extraction equilibrium time of 1 min, a good linearity (r = 0.9998) and a detection limit of 0.39 μg?L^?1 were obtained. The precision (RSD) for 11 replicate measurements of 10 μg?L^?1 Cd was 1.6%. The method was validated using certified reference materials. The recoveries of cadmium in spiked real samples ranged from 97% to 102%.     

Use of Surfactant as Mobile Phase Additive in LC for Simultaneous Determination of Metal-Pyrrolidine Dithiocarbamate Chelates

Reversed phase liquid chromatography using UV detection was developed for the simultaneous analysis of Hg(II), Pb(II), Cd(II), Ni(II), Fe(III) and V(V) ions after their complexation with pyrrolidine-dithiocarbamate (PDC). Optimum chromatographic conditions were a μ-Bondapak C₁₈ column and an isocratic mobile phase consisting of 40 mmol L^?1 SDS, 34 mmol L^?1 TBABr and 68% acetonitrile in 10 mmol L^?1 phosphate buffer pH 3.5. The separation of six PDC complexes was achieved within 8 min. Analytical performances and method validation were investigated. The detection limits ranged from 0.16 μg L^?1(Fe(III)) to 5.40 μg L^?1(Pb(II)). Recoveries obtained for all the studied samples including tap water, whole blood and vegetables were 72–98%. The results obtained from the proposed method were not significantly different compared to those obtained from atomic absorption spectrometry (P = 0.05).     

Schiff base-functionalised styrofoam resin for preconcentration of metal ions in wastewater and wastewater-irrigated vegetables samples

Polystyrene (PS) was extracted from styrofoam waste and functionalised with schiff base, N,N-bis(salicylidene)cyclohexanediamine (SCHD) through an azo spacer. The resin was characterised and used for preconcentration of Pb(II), Ni(II) and Cd(II) ions prior to their trace determinations by microsample injection system–coupled flame atomic absorption spectrometry (MIS-FAAS). The recoveries of studied metal ions were achieved ≥96.0% with relative standard deviation (RSD) ≤4.5 at optimum parameters: pH 8; resin amount 300 mg; flow rates 3.0 mL min^?1 of sample solution; and 2.0 mL min^?1 of eluent (2.0 mol L^?1 HNO₃). The limits of detection (LODs) and limits of quantification (LOQs) were found to be 0.32, 0.23 and 0.21 and 1.10, 0.78 and 0.69 μg L^?1, respectively, with preconcentration factors (PFs) of 500, 800 and 1000, respectively. The linear ranges of the method were 1–40, 1–25 and 1–20 μg L^?1 for Pb(II), Ni(II) and Cd(II) ions, respectively. The accuracy and validation of the method were evaluated by analysis of certified reference materials (CRMs). The method was successfully applied for preconcentration of studied metal ions in wastewater and wastewater-irrigated vegetable samples.     

Water hyacinth modified carbon paste electrode for simultaneous electrochemical stripping analysis of Cd (II) and Pb (II)

In this study, we demonstrated a highly sensitive electrochemical sensor for the simultaneous detection of Pb (II) and Cd (II) in aqueous solution using carbon paste electrode modified with Eichhornia crassipes powder by square wave anodic stripping voltammetry. The effect of modifier composition, pH, preconcentration time, reduction potential and time, and type of supporting electrolyte on the determination of metal ions were investigated. Pre-concentration on the modified surface was performed at open circuit. The modified electrode exhibited well-defined and separate stripping peaks for Pb (II) and Cd (II). Under optimum experimental conditions, a linear range for both metal ions was from 10 to 5000 μg L^?1 with the detection limits of 4.9 μg L^?1, 2.1 μg L^?1 for Cd(II) and Pb (II), respectively. The modified electrode was found to be sensitive and selective when applied to determine trace amounts of Cd (II) and Pb (II) in natural water samples.     

Graphene oxide-packed micro-column solid-phase extraction combined with flame atomic absorption spectrometry for determination of lead (II) and nickel (II) in water samples

A sensitive and simple method has been established for simultaneous preconcentration of trace amounts of Pb (II) and Ni (II) ions in water samples prior to their determination by flame atomic absorption spectrometry. This method was based on the using of a micro-column filled with graphene oxide as an adsorbent. The influences of various analytical parameters such as solution pH, adsorbent amount, eluent type and volume, flow rates of sample and eluent, and matrix ions on the recoveries of the metal ions were investigated. Using the optimum conditions, the calibration graphs were linear in the range of 7–260 and 5–85 μg L^?1 with detection limits (3S_b) of 2.1 and 1.4 μg L^?1 for lead and nickel ions, respectively. The relative standard deviation for 10 replicate determinations of 50 μg L^?1 of lead and nickel ions were 4.1% and 3.8%, respectively. The preconcentration factors were 102.5 and 95 for lead and nickel ions, respectively. The adsorption capacity of the adsorbent was also determined. The method was successfully applied to determine the trace amounts of Pb (II) and Ni (II) ions in real water samples. The validation of the method was also performed by the standard reference material.     

Synthesis of a New Cu(II)-Ion Imprinted Polymer for Solid Phase Extraction and Preconcentration of Cu(II)

A new Cu(II)-ion imprinted polymer (IIP) has been synthesized by copolymerizing salicylic acid and formaldehyde as a monomer and crosslinker, respectively in the presence of Cu(II)-4-(2-pyridylazo) resorcinol complex. The imprinted Cu(II) ions were completely removed by leaching the IIP with 0.05 M EDTA. The maximum adsorption capacity for Cu(II) ions was 310 μg g^?1 at pH 6. The IIP was repeatedly used in adsorption–desorption experiments for seven times with recoveries ~95%. The relative selectivity factor (α _r) values of Cu(II)/Zn(II), Cu(II)/Cd(II), Cu(II)/Ni(II) and Cu(II)/Co(II) are 3.17, 2.90, 2.47 and 3.37, respectively. The detection limit corresponding to three times the standard deviation of the blank was found to be 3.0 μg L^?1. The developed IIP has also been tested for preconcentration and recovery of Cu(II) ions from water samples.     

Simultaneous preconcentration and determination of nickel and cobalt using functionalised mesoporous silica spheres by ICP-OES

In this work functionalised mesoporous silica spheres have been utilised for the simultaneous preconcentration of nickel and cobalt. The silica spheres (SiSPs) prepared by the sol-gel method were functionalised with sodium diethyldithiocarbamate (DDTC-SiSPs). They were characterised by SEM, TEM, XRD, FTIR, CHN and nitrogen adsorption. The adsorption efficiency of DDTC-SiSPs was examined by batch equilibrium technique. The DDTC-SiSPs showed 100% adsorption for Ni (II) and Co (II). The effect of changing variables such as pH, shaking time, sample volume, preconcentration factor, eluent type and volume were investigated so as to obtain maximum recovery with high selectivity over interfering ions. The maximum adsorption capacity was found to be 15.15 mg g^?1 and 11.80 mg g^?1 for Ni (II) and Co (II) respectively using DDTC-SiSPs. 100% recovery was achieved with 5 mL of 2 M HNO₃. The maximum preconcentration factor was 400 and the 3σ limits of detection were 0.201 µg L^?1 and 0.198 µg L^?1 for Ni (II) and Co (II) respectively. Thermodynamic studies showed that adsorption of Ni (II) and Co (II) on DDTC-SiSPs is exothermic with enthalpy changes of –0.514 KJ mol^?1 and –0.854 KJ mol^?1 for Ni (II) and Co (II) respectively. The method was applied to the preconcentration and determination of Ni (II) and Co (II) from tap, river and sea water.     

Solid phase extraction and diffusive gradients in thin films techniques for determination of total and labile concentrations of Cd(II), Cu(II), Ni(II) and Pb(II) in Black Sea water

Total dissolved and labile concentrations of Cd(II), Cu(II), Ni(II) and Pb(II) were determined at six locations of the Bourgas Gulf of the Bulgarian Black Sea coast. Solid phase extraction procedure based on monodisperse, submicrometer silica spheres modified with 3-aminopropyltrimethoxysilane followed by the electrothermal atomic absorption spectrometry (ETAAS) was developed and applied to quantify the total dissolved metal concentrations in sea water. Quantitative sorption of Cd, Cu, Ni and Pb was achieved in the pH range 7.5–8, for 30?min, adsorbed elements were easily eluted with 2?mL 2?mol?L^?1 HNO₃. Since the optimal pH for quantitative sorption coincides with typical pH of Black Sea water (7.9–8.2), on-site pre-concentration of the analytes without any additional treatment was possible. Detection limits achieved for total dissolved metal quantification were: Cd 0.002?µg?L^?1, Cu 0.005?µg?L^?1, Ni 0.03?µg?L^?1, Pb 0.02?µg?L^?1 and relative standard deviations varied from 5–13% for all studied elements (for typical Cd, Cu, Ni and Pb concentrations in Black Sea water). Open pore diffusive gradients in thin films (DGT) technique was employed for in-situ sampling and pre-concentration of the sea water and in combination with ETAAS was used to determine the proportion of dynamic (mobile and kinetically labile) species of Cd(II), Cu(II), Ni(II) and Pb(II) in the sea water. Obtained results showed strong complexation for Cu and Pb with sea water dissolved organic matter. The ratios between DGT-labile and total dissolved concentrations found for Cu(II) and Pb(II) were in the range 0.2–0.4. For Cd and Ni, these ratios varied from 0.6 to 0.8, suggesting higher degree of free and kinetically labile species of these metals in sea water.     

Use of clinoptilolite loaded with 1-(2-pyridylazo)-2-naphthol as a sorbent for preconcentration of Pb(II), Ni(II), Cd(II) and Cu(II) prior to their determination by flame atomic absorption spectroscopy

A solid phase extraction system for separation and preconcentration of trace amounts of Pb(II), Ni(II), Cd(II) and Cu(II) is proposed. The procedure is based on the adsorption of Pb²⁺, Ni²⁺, Cd²⁺ and Cu²⁺ ions on a column of 1-(2-pyridylazo)-2-naphthol (PAN) immobilised on surfactant-coated clinoptilolite prior to their determinations by Flame Atomic Absorption Spectroscopy (FAAS). The effective parameters including pH, sample volume, sample flow rate and eluent flow rate were also studied. The analytes collected on the column were eluted with 5 mL of 1 mol L^?1 nitric acid. A concentration factor of 180 can be achieved by passing 900 mL of sample through the column. The detection limits (3 s) for Cd, Cu, Pb and Ni were found to be 0.28, 0.12, 0.44 and 0.46 µg L^?1, respectively. The relative SDs at 10 µg L^?1 (n = 10) for analytes were in the range of 1.2–1.4%. The method was applied to the determination of Pb, Ni, Cd and Cu in water samples.     

Adsorptive stripping voltammetry of nickel at a bare glassy carbon electrode

A bare glassy carbon electrode is applied to nickel determination by adsorptive stripping voltammetry in the presence of dimethylglyoxime as a complexing agent. A procedure of nickel determination and electrode regeneration was proposed. The calibration graph for Ni(II) for an accumulation time of 120?s was linear from 2?×?10^?9 to 1?×?10^?7?mol?L^?1. The detection limit was 8.2?×?10^?10?mol?L^?1. The relative standard deviation for a solution containing 2?×?10^?8?mol?L^?1 of Ni(II) was 4.1%. The proposed procedure was applied for Ni(II) determination in certified water reference materials.     

Development of a green effervescence-assisted dispersive liquid–liquid microextraction method using a home-made tablet disperser for trace analysis of Cd(II) and Pb(II)

An analytical approach for the determination of trace amounts of Cd(II) and Pb(II) has been developed using a home-made tablet-based effervescence-assisted dispersive liquid–liquid microextraction (DLLME) method which was performed in a narrow-bore tube, followed by flame atomic absorption spectrometry. In this method, a mixture of tartaric acid, sodium bicarbonate and NaCl was used to make the disperser tablet. Then, microlitre level of an extraction solvent was added in the tablet, and then, it was released into a narrow-bore tube containing sample solution and a complexing agent. An acid–base reaction immediately occurred between tartaric acid and sodium bicarbonate, and the produced CO₂ led to the dispersion of the extraction solvent into the solution as tiny droplets and subsequent extraction of the analytes. The method made possible the determination of Cd(II) and Pb(II) in the ranges of 0.1–10 and 1.0–20 µg L^?1, respectively. The limits of detection were obtained 0.43 and 0.05 µg L^?1 for Pb(II) and Cd(II), respectively. The limits of quantifications were 0.80 and 0.09 µg L^?1 for Pb(II) and Cd(II), respectively. Repeatability of the method, which is expressed as relative standard deviation, was obtained 3.1% (n = 6, C = 2 µg L^?1) and 1.3% (n = 6, C = 0.2 µg L^?1) for Pb(II) and Cd(II), respectively. The accuracy of the developed method was verified by analysing a certified reference material, namely SPS-WW2 Batch 108. Relative recoveries (84–107%, obtained at three fortification levels) confirmed the usefulness of the method for analysis of the analytes in the environmental water samples and fruit juices. The method was shown to be fast, reliable and environmentally friendly with low organic solvent consumption.     

Synthesis and application of a novel magnetic nanosorbent for determination of trace Cd(II), Ni(II), Pb(II), and Zn(II) in environmental samples

In this work for the first time, Fe₃O₄@SiO₂ core–shell nanoparticles functionalized with isatin groups as a magnetic nanosorbent was applied for the simultaneous extraction of trace amounts of cadmium(II), nickel(II), lead(II), and zinc(II). The characterization of this nanosorbent was studied using Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectrometry, X-ray diffraction, vibrating sample magnetometer and thermogravimetric analysis. The effect of several factors such as pH, amount of sorbent, extraction time, type and volume of the eluent, sample volume, sorption capacity, and potentially interfering ions was investigated. In the selected conditions, it was observed that the limits of detection were 0.11 ng mL^?1 for Cd(II), 0.28 ng mL^?1 for Ni(II), 0.47 ng mL^?1 for Pb(II), and 0.21 ng mL^?1 for Zn(II), and the maximum sorption capacity of this suggested magnetic nanosorbent was 120, 112, 100, and 100 mg g^?1 for Cd(II), Ni(II), Pb(II), and Zn(II), respectively. Also, the precision of the method (RSD%) for ten replicate measurements was found 2.5, 2.5, 2.8, and 3.1%, for Cd(II), Ni(II), Pb(II), and Zn(II) ions, respectively. Finally, the suggested procedure was applied for determination of cadmium(II), nickel(II), lead(II), and zinc(II) at trace levels in different water and agricultural products with satisfactory results.     

Application of Ni(II)-imprinted cross-linked poly(methacrylic acid) synthesised through double-imprinting method for the on-line preconcentration of Ni(II) ions in aqueous media

The present paper describes the feasibility of on-line preconcentration of nickel ions from aqueous medium on Ni(II)-imprinted cross-linked poly(methacrylic acid) (IIP) synthesised through a double-imprinting method and their subsequent determination by FAAS. The proposed method consisted in loading the sample (20.0 mL, pH 7.25) through a mini-column packed with 50 mg of the IIP for 2 min. The elution step was performed with 1.0 mol L^?1 HNO₃ at a flow rate of 7.0 mL min^?1. The following parameters were obtained: quantification limit (QL) – 3.74 µg L^?1, preconcentration factor (PF) – 36, consumption index (CI) – 0.55 mL, concentration efficiency (CE) – 18 min^?1, and sample throughput – 25 h^?1. The precision of the procedure assessed in terms of repeatability for ten determinations was 5.6% and 2.5% for respective concentrations of 5.0 and 110.0 µg L^?1. Moreover, the analytical curve was obtained in the range of 5.0–180.0 µg L^?1 (r = 0.9973), and a 1.64-fold increase in the method sensitivity was observed when compared with the analytical curve constructed for the NIP (non-imprinted polymer), thus suggesting a synergistic effect of the Ni(II) ions and CTAB on the adsorption properties of the IIP. The practical application of the adsorbent was evaluated from an analysis of tap, mineral, lake and river water. Considering the results of addition and recovery experiments (90.2–100 %), the efficiency of this adsorbent can be ensured for the interference-free preconcentration of the Ni(II) ions.     

The role of counter-anions in photocatalytic reduction of Ni(II) with a trace amount of titania nanoparticles

The reduction of Ni(II) ion, originated from nitrate or sulfate salts, was investigated based on photo-generated electrons in UV-irradiated TiO₂ aqueous suspensions. Design of experiments, modeling, and process optimization were performed using central composite design of response surface methodology. Influence of pH, temperature, and nickel concentration was investigated based on percentage of reduction efficiency (RE). Under operating conditions of pH = 9.3, T = 40 °C, [Ni(II)]_o = 5 mg L^?1, [TiO₂] = 100 mg L^?1 and after 90 min treatments, 64.8 and 76.1 % RE were achieved for nitrate and sulfate counter-anions, respectively. The higher efficiency obtained with sulfate anion was attributed to the more ionic strength and its interaction with titania nanoparticles. Rate of Ni(II) ions reduction, originated from both of the nickel salts, obeys pseudo-first-order kinetic model. As a relevant criterion, the electrical energy consumption and other criteria were evaluated and were compared with other previously reported processes.     

Ligandless-ultrasound-assisted emulsification microextraction followed by inductively coupled plasma-optical emission spectrometry for simultaneous determination of heavy metals in water samples

In this study, a simple and efficient method of ligandless-ultrasound-assisted emulsification microextraction (LL-USAEME) followed by inductively coupled plasma-optical emission spectrometry (ICP-OES) has been developed for simultaneous extraction, preconcentration and determination of manganese, cadmium, cobalt and nickel in water samples. In the proposed approach, tetrachloroethylene was selected as extraction solvent. The effect of important experimental factors such as volume of extraction solvent, pH, sonication time, salt concentration, and temperature was investigated by using a fractional factorial design (2^5?1) to identify important factors and their interactions. In the next step, a Box-Behnken design (BBD) was applied for optimisation of significant factors. The obtained optimal conditions were: 30?µL for extraction solvent, 12 for pH, 5?min for sonication time, and 5% w/v for salt concentration. The limits of detections (LODs) for Cd(II), Co(II), Mn(II) and Ni(II) were 0.20, 0.13, 0.21 and 0.28?µg?L^?1, respectively. Relative standard deviations (RSD, C?=?200.0?µg?L^?1, n?=?9) were between 3.4–7.5% and the calibration graphs were linear in the range of 0.25 to 1000.0?µg?L^?1 for Mn, 0.5–1000.0?µg?L^?1 for Co and Ni and 1.0–250.0?µg?L^?1 for Cd. The determination coefficients (R ²) of the calibration curves for the analytes were in the range of 0.993 to 0.999. The proposed method was validated by using two certified reference materials, and also the method was applied successfully for the determination of heavy metals in different real water samples.     

Solid phase extraction of Cd(II) and Pb(II) using a magnetic metal-organic framework, and their determination by FAAS

We describe a novel magnetic metal-organic framework (MOF) for the preconcentration of Cd(II) and Pb(II) ions. The MOF was prepared from the Fe₃O₄-pyridine conjugate and the copper(II) complex of trimesic acid. The MOF was characterized by IR spectroscopy, elemental analysis, SEM and XRD. A Box-Behnken design through response surface methodology and experimental design was used to identify the optimal parameters for preconcentration. Extraction time, amount of magnetic MOF and pH value were found to be critical factors for uptake, while type, volume, concentration of eluent, and elution time are critical in the elution step. The ions were then determined by FAAS. The limits of detection are 0.2 and 1.1 μg?L^?1 for Cd(II), and Pb(II) ions, respectively, relative standard deviations are <4.5% (for five replicates at 50 μg?L^?1 of Cd(II) and Pb(II) ions), and the enrichment capacity of the MOF is at around 190 mg?g^?1 for both ions which is higher than the conventional Fe3O4-pyridine material. The magnetic MOF was successfully applied to the rapid extraction of trace quantities of Cd(II) and Pb(II) ions in fish, sediment, and water samples.

Emulsification based dispersive liquid microextraction prior to flame atomic absorption spectrometry for the sensitive determination of Cd(II) in water samples

We report on the application of emulsification-based dispersive liquid microextraction (EB-DLME) to the preconcentration of Cd(II). This procedure not only possesses all the advantages of routine DLLME, but also results in a more stable cloudy state which is particularly useful when coupling it to FAAS. In EB-DLME, appropriate amounts of the extraction solvent (a solution of dithizone in chloroform) and an aqueous solution of sodium dodecyl sulfate (SDS; acting as a disperser) are injected into the samples. A stable cloudy microemulsion is formed and Cd(II) ion is extracted by chelation. After phase separation, the sedimented phase is subjected to FAAS. Under optimized conditions, the calibration curve for Cd(II) is linear in the range from 0.1 to 25 μg L^?1, the limit of detection (at S/N?=?3) is 30 pg L^?1, the relative standard deviations for seven replicate analyses (at 0.56 μg L^?1 of Cd(II)) is 4.6 %, and the enrichment factor is 151. EB-DLME in our opinion is a simple, efficient and rapid method for the preconcentration of Cd(II) (and most likely of many other ions) prior to FAAS determination.

Pulverized Banana Peel as an Economical Sorbent for the Preconcentration of Metals

A procedure for the determination of trace levels of Cd, Co, Cr, Fe, Mn, Ni, and Pb by flame atomic absorption spectrometry using a column preconcentration system is described in which the metals were adsorbed on pulverized banana peel, an economically and environmentally acceptable sorbent. In the optimization procedure, five variables (sample pH, mass of biosorbent, type of eluent, sample flow rate, and volume) were optimized and the capacity of the biosorbent was established. Under the optimized conditions, the detection limits of the method were 2.4, 27.0, 49.4, 31.1, 6.7, 29.6, and 46.2 µg L^?1 for Cd, Co, Cr, Fe, Mn, Ni, and Pb, respectively. The precision, expressed as relative standard deviation, was less than 4% based on twelve measurements. The recoveries were 81.1% (Cd), 91.4% (Co), 87.2% (Cr), 90.1% (Fe), 88.0% (Mn), 94.1% (Ni), and 93.2% (Pb) under the optimum conditions (pH; 9, sample flow rate; 3 mL min^?1, mass of biosorbent; 200 mg; eluent; 1 mol L^?1 nitric acid, preconcentration factor; 10). The sorption capacity of pulverized banana peel was 15.12, 28.85, 32.70, 30.44, 30.94, 28.97, and 8.21 µmol per gram of adsorbent for Cd, Co, Cr, Fe, Mn, Ni, and Pb, respectively.     

Anodic Stripping Voltammetry Determination of Pb(II) and Cd(II) at a Bismuth/Poly(aniline) Film Electrode

Abstract

A novel voltammetric method—anodic—using a bismuth/poly(aniline) film electrode has been developed for simultaneous measurement of Pb(II) and Cd(II) at low µg L^?1 concentration levels by stripping voltammetry. The results confirmed that the bismuth/poly(aniline) film electrode offered high‐quality stripping performance compared with the bismuth film electrode. Well‐defined sharp stripping peaks were observed for Pb(II) and Cd(II), along with an extremely low baseline. The detection limits of Pb(II) and Cd(II) are 1.03 µg L^?1 and 1.48 µg L^?1, respectively. The bismuth/poly (aniline) electrode has been applied to the determination of Pb(II) in tap water samples with satisfactory results.     

Activated carbon cloth filled pipette tip for solid phase extraction of nickel(II), lead(II), cadmium(II), copper(II) and cobalt(II) as 1,3,4-thiadiazole-2,5-dithiol chelates for ultra-trace detection by FAAS

A solid phase extraction method is established for preconcentration of nickel, lead, cadmium, copper and cobalt using pipette tip solid phase extraction. The presented process was dependent on chelation of analytes with 1,3,4-thiadiazole-2,5-dithiol, then allowing the solution to flow through an activated carbon cloth packed pipette tip. The adsorbed metal chelates on the surface of activated carbon cloth were eluted by 5 mL of 3 M HNO₃. The concentrations of nickel, lead, cadmium, copper and cobalt were detected using a flame atomic absorption spectrometer (FAAS). The pipette tip solid phase extraction exhibit a preconcentration factor of 120. The limit of detection values were 2.7, 1.7, 1.3, 2.0 and 2.9 µg L^?1 for Ni(II), Pb(II), Cd(II), Cu(II) and Co(II), respectively. Validation of the method was checked by the analysis of TMDA-53.3 and TMDA-64.2 certified reference materials. The method was successfully applied for water and fertiliser samples.