Sensitive sequential injection determination of naproxen based on interaction with beta-cyclodextrin

A sensitive sequential injection analysis (SIA) methodology for the fluorimetric determination of naproxen is proposed. The developed automatic analytical procedure is based on the complexation of naproxen with β-cyclodextrin (β-CD) yielding an enhanced fluorimetric signal (λ_ex = 280 nm, λ_em = 356 nm).Linear calibration plots were obtained for naproxen concentrations up to 1 × 10⁻⁵ mol l⁻¹. The developed methodology exhibited a good precision, with a R.S.D. < 2.1% (n = 15). The detection limit of the determination was 1.9 × 10⁻⁷ mol l⁻¹ with a sampling rate of about 70 h⁻¹. The automatic method was applied to the determination of naproxen in pharmaceutical formulations. The obtained results were compared with those furnished by the reference procedure and the relative deviations were lower than 3.6%. No interference was found from the excipients usually used in solid pharmaceutical formulations.     

Fluorimetric determination of aminocaproic acid in pharmaceutical formulations using a sequential injection analysis system

A sequential injection analysis (SIA) methodology for the fluorimetric determination of aminocaproic acid in pharmaceutical formulations is proposed. The developed analytical procedure is based on the derivatisation reaction of the aminocaproic primary amine with o-phthalaldehyde (OPA) and N-acetylcysteine (NAC) and fluorimetric detection of the formed product (λ_ex = 350 nm; λ_em = 450 nm). The implementation of a SIA flow system allowed for the development of a simple, fast and versatile automated methodology, which exhibits evident advantages regarding the US Pharmacopoeia 24 (USP 24) reference procedure. By combining the SIA time-based sample insertion with a subsequent zone sampling approach, which permitted to select for detection of a well-defined sample zone, it was possible to implement an on-line dilution strategy that enabled the expansion of the analytical working range of the methodology, and thus its application in dissolution studies, without manifold re-configuration.Linear calibration plots were obtained for aminocaproic acid concentrations up to 6 × 10⁻⁵ mol l⁻¹. The developed methodology exhibit a good precision, with a R.S.D. < 2.0% (n = 15) and the detection limit was 2.5 × 10⁻⁷ mol l⁻¹. The obtained results complied with those furnished by the reference procedure with a relative deviation lower than 1.2%. No interference was found.     

Direct and rapid determination of sulphate in environmental samples with diffuse reflectance Fourier transform infrared spectroscopy using KBr substrate

The feasibility of employing diffuse reflectance Fourier transform infrared spectroscopy (DRS-FTIR) as a sensitive tool in the submicrogram level determination of sulphate (SO₄²⁻) was checked in this work. This paper presents the development of a new, rapid and precise analytical method for ppb levels of sulphate (SO₄²⁻) in environmental samples like coarse and fine aerosol particles, dry deposits and soil. The determination of submicrogram levels of sulphate is based on the selection of a quantitative analytical peak at 617 cm⁻¹ among the three observed vibrational peaks and preparing calibration curve using different known concentrations of sulphate by diffuse reflectance-Fourier transform infra red spectrometric (DRS-FTIR) technique. Pre-weighed and ground IR grade KBr was used as substrate over which remarkably wide range of known concentration of sulphate was sprayed and dried. The dried sample was analysed by DRS-FTIR. Three calibration curves for three different concentration ranges of sulphate were prepared for samples containing low and relatively higher sulphate contents. The relative standard deviation (n = 8) for the sulphate concentration ranges, 2.5-35.5, 25.5-165, 55-1000 μg/0.5 g KBr, as used to prepare calibration curves, were 2.4%, 2.1% and 1.5%, respectively. The relative standard deviation for the sulphate concentration in real samples were found to be in the range, 3.11-5.76% (n = 16), 4.05-7.75% (n = 16) and 1.48-3.52% (n = 10) for aerosol, dry deposits and soil, respectively. The LOD of the method is 0.20 μg/g SO₄²⁻. The F- and t-tests were performed to check the analytical quality assurance test. The noteworthy feature of the reported method is the non-interference of any of the associated anions and cations. The results were compared with that of ion-chromatographic method with high degree of acceptability. The method can be applied in wide concentration ranges. A method for sulphate determination was introduced that did not require pretreatment of samples. This method employed the direct determination of the sulphate. The method is reagent less, nondestructive, very fast, repeatable, and accurate and has high sample throughput value.     

Spectrofluorimetric determination of aluminum in drinking waters by sequential injection analysis

A selective procedure for the determination of Al³⁺ in drinking and natural waters is proposed. The analytical procedure is based both on the complex formation between Al³⁺ and 8-hydroxyquinoline-5-sulfonic acid (HQS) and on a fluorimetric detection of the complex. The reaction was carried out in presence of thioglycolic acid as a masking agent. This procedure has been adapted to a sequential injection analysis (SIA) system. Operative conditions both for batch and SIA procedures were investigated including reagent concentration, volumes, pH and wavelengths used for the fluorimetric detection. Batch procedure allows determination of Al³⁺ at ppb level (LOQ: 2.8 μg l⁻¹) within a working range of 2.2-300 μg l⁻¹. The SIA procedure was successfully employed for the determination of Al³⁺ in several commercial drinking and tap waters.     

A flow sampling strategy for the analysis of oil samples without pre-treatment in a sequential injection analysis system

The present work describes a sequential injection analysis (SIA) system adapted to direct analysis of oil samples. In this way, the flow system was designed by incorporation, in the SIA system, of an injection valve that was responsible for the sample insertion. With the developed sampling strategy the sample pre-treatment outside the flow system is avoided and also the problems associated with viscous samples in flow systems.The developed SIA system was applied to the determination of iron (Fe(III)) in edible oil samples and was based on the formation of a red complex (λ = 510 nm) between Fe(III) and thiocyanate in organic medium. A mixture of methanol:chloroform (85:15) was used as carrier solution and possible refractive index associated with the spectrophotometric detection was avoided by introduction of a mixing chamber in the flow system. The presented methodology produced 4.2 ml of effluent and consumed 150 μl of sample and 0.95 mg of thiocyanate per determination.Linear calibration plots were obtained for Fe(III) concentrations up to 25 mg l⁻¹ and the detection limit of the determination was 0.31 mg l⁻¹. The developed methodology exhibited a good precision, with an R.S.D. < 3.5% (n = 15) and a determination frequency of 20 determinations h⁻¹. The results of the analysis were evaluated by recovery studies (96.5-104.5%) and by the analysis of two AOCS reference samples.     

Fast spectrophotometric determination of fluoride in ground waters by flow injection using partial least-squares calibration

The presence of sulphate constitutes a serious interference in the usual zirconium lake-based spectrophotometric method for the determination of fluoride in water. In this report, full spectral data have been recorded for the zirconium lake of 2-(parasulfophenylazo)-1,8-dihydroxy-3,6-naphthalene-disulfonate (SPADNS) in the simultaneous presence of fluoride and sulphate, as obtained with a flow injection system with a diode-array detector. The information has been processed with partial least-squares (PLS) multivariate calibration. Adequate modeling using a sixteen-sample calibration set allows fluoride to be determined in ground waters by the automated flow injection method, even in the presence of sulphate in concentrations up to 1000 mg l⁻¹. In the calibration range 0-1.50 mg l⁻¹ for fluoride, the limit of detection is 0.1 mg l⁻¹. The fluoride contents in real samples, as determined with the present method, were satisfactorily compared with those provided by ion selective potentiometry.     

A reagent-free method based on a photo-induced fluorimetry in a sequential injection system

According to the current demands of environmentally friendly analytical chemistry and with a view to achieving lower reagent consumption with improved analytical performance, an automatic methodology composed of a photoreactor and fluorimetric detection (λ_exc = 287 nm, λ_em = 378 nm) was developed. To this end, a sequential injection analysis (SIA) system was developed for indomethacin determination using ultra-violet (UV) light which promotes an increase in the fluorescence of indomethacin. This increase in sensitivity makes it possible to apply this methodology to a dissolution test and to determine indomethacin in pharmaceutical formulations.The calibration graph for indomethacin was linear between 4.10 × 10⁻⁶ and 9.00 × 10⁻⁵ mol L⁻¹and the detection limit was 1.23 × 10⁻⁶ mol L⁻¹. The method was proven to be reproducible with a R.S.D. < 5% and sampling rate of approximately 20 per hour. The potential effect of several compounds commonly used as excipients on analytical signals was studied and no interfering effect was observed. Statistical evaluation at the 95% confidence level showed good agreement between the results obtained for the pharmaceutical samples with both the SIA system and comparison batch procedures.     

Post-column terbium complexation and sensitized fluorescence detection for the determination of norepinephrine, epinephrine and dopamine using high-performance liquid chromatography

Terbium sensitized fluorescence was used as a post-column detection system to develop a simple, sensitive and rapid high-performance liquid chromatographic method for the simultaneous determination of catecholamines norepinephrine (NE), epinephrine (E) and dopamine (DA).Catecholamines were separated by an ion-pair reversed-phase chromatography on a BDS-Hypersil analytical column with a mobile phase of methanol and 50 mmol l⁻¹ acetate buffer (pH 4.7) containing 1.1 mmol l⁻¹ SOS and 0.11 mmol l⁻¹ EDTA (15+85 v/v).Catecholamines and the internal standard (3,4-dihydroxybenzylamine, DHBA) were post-column derivatized by the addition to the eluent of an alkaline solution containing a stoichiometric mixture of terbium(III) chloride and EDTA. Fluorescence detection (λ_ex=300 nm, λ_em=545 nm) is based on the sensitization of terbium ion fluorescence after complexation with catecholamines.The chemical compatibility between the eluent and the post-column reagent was studied and the analytical characteristics of the method were established. Detection limits found were 1.0×10⁻⁸, 4.0×10⁻⁸ and 7.0×10⁻⁸ mol l⁻¹ for NE, E and DA, respectively. The method has been successfully applied to the determination of catecholamines in urine samples after solid-phase extraction (SPE) pre-treatment. Recoveries from urine spiked with NE (4.0×10⁻⁷, 2.0×10⁻⁶ and 4.0×10⁻⁶ mol l⁻¹), E (8.2×10⁻⁸, 4.1×10⁻⁷ and 8.2×10⁻⁷ mol l⁻¹) and DA (1.0×10⁻⁶, 5.0×10⁻⁶ and 1.0×10⁻⁵ mol l⁻¹) varied from 98 to 100% (mean=99.3%), from 106 to 107% (mean=106.3%) and from 98 to 101% (mean=99.3%), respectively. The between-run precision (relative standard deviation, R.S.D.) for the method for three urine samples at different concentration levels of each catecholamine varied from 3.6 to 7.0%.     

Spectrophotometric catalytic determination of Fe(III) in estuarine waters using a flow-batch system

A flow-batch system was developed for the determination of Fe(III) in estuarine waters with high variability in salinity. The method is based on the catalytic effect of iron(III) on the oxidation rate of N,N-dimethyl-p-phenylenediammonium dichloride (DmPD) by hydrogen peroxide and the formed product is spectrophotometrically monitored at 554 nm. A controlled addition of sodium chloride to every assayed sample is accomplished for in-line individual salinity matching.The proposed system processes about 30 samples h⁻¹ and yields reproducible results. Relative standard deviations were estimated as <1.5% after 10 injections of typical samples (10.0-50.0 μg l⁻¹ Fe; ca. 0.5 mol l⁻¹ Cl). Synthetic samples (15.0 μg l⁻¹ Fe; 0.25-1.0 mol l⁻¹ NaCl) were efficiently processed, and no significant differences in results were found at a probability level of 99.7%. The method works for the full range of salinities. Only 120 μg DmPD are consumed per determination. The analytical curve is linear up to about 60 μg l⁻¹ Fe (r>0.999; n=5) and the detection limit is 5 μg l⁻¹ Fe. Results are in agreement with graphite furnace atomic absorption spectrometry.     

Flow injection spectrophotometric method for chloride determination in natural waters using Hg(SCN)(2) immobilized in epoxy resin

A flow injection (FI) spectrophotometric method was proposed for the determination of chloride ion in natural waters. The determination of chloride was carried out by reaction with Hg(SCN)₂ immobilized in an epoxy resin bead in a solid-phase reactor (SPR) and the thiocyanate ions released were determined spectrophotometrically at 480 nm after complexing reaction with Fe(III). The analytical curve for chloride was linear in the concentration range from 5.6 × 10⁻⁵ to 2.2 × 10⁻⁴ mol l⁻¹ with a detection limit of 1.4 × 10⁻⁵ mol l⁻¹. The relative standard deviation (R.S.D.) was 2.2% for a solution containing 2.2 × 10⁻⁴ mol l⁻¹ (n = 10). The simple manifold allows a routine analytical frequency of 100 determinations per hour. The main advantage of the developed method is the 400% reduction of the Hg waste solution generated when compared to conventional methods for chloride determination based on the same spectrophotometric reaction.     

Sequential injection methodology for carbon speciation in bathing waters

A sequential injection method (SIA) for carbon speciation in inland bathing waters was developed comprising, in a single manifold, the determination of dissolved inorganic carbon (DIC), free dissolved carbon dioxide (CO₂), total carbon (TC), dissolved organic carbon and alkalinity. The determination of DIC, CO₂ and TC was based on colour change of bromothymol blue (660 nm) after CO₂ diffusion through a hydrophobic membrane placed in a gas diffusion unit (GDU). For the DIC determination, an in-line acidification prior to the GDU was performed and, for the TC determination, an in-line UV photo-oxidation of the sample prior to GDU ensured the conversion of all carbon forms into CO₂. Dissolved organic carbon (DOC) was determined by subtracting the obtained DIC value from the TC obtained value. The determination of alkalinity was based on the spectrophotometric measurement of bromocresol green colour change (611 nm) after reaction with acetic acid. The developed SIA method enabled the determination of DIC (0.24–3.5 mg C L⁻¹), CO₂ (1.0–10 mg C L⁻¹), TC (0.50–4.0 mg C L⁻¹) and alkalinity (1.2–4.7 mg C L⁻¹ and 4.7–19 mg C L⁻¹) with limits of detection of: 9.5 μg C L⁻¹, 20 μg C L⁻¹, 0.21 mg C L⁻¹, 0.32 mg C L⁻¹, respectively. The SIA system was effectively applied to inland bathing waters and the results showed good agreement with reference procedures.     

Flow system to gas capture from a nebulized solution

The use of aerosol produced in a nebulization chamber is proposed as an alternative to gas sample capture in flow systems. This paper describes the coupling of a sampling interface with a flow system, for in situ gas monitoring. Aspects related with the behavior of aerosol formation and gas solubilization in liquid drops are discussed. The method is applied to the determination of residual lime in acidic soils. Aliquots of 5.0 ml of 1.0 mol l⁻¹ HCl were mixed with soil samples (1 g). The CO₂ released from these samples was captured by a nebulized aerosol and determined conductivity. The analytical curve from 1.0×10⁻² to 5.0×10⁻² mol kg⁻¹ CaCO₃ was ploted applying the matrix matching approach. This proposition, allowed an increase in the sensibility with detection limit of 6.0×10⁻³ mol kg⁻¹. The precision was good (R.S.D. <3%) for an analytical frequency of 22 determinations per hour. A fair agreement, at 95% confidence level, was found between the results from the proposed method and certified values of the investigated samples.     

Highly sensitive catalytic determination of molybdenum

A novel, highly sensitive, selective, and simple kinetic method was developed for the determination of Mo(VI) based on its catalytic effect on the oxidation of 1-amino-2-naphthol-4-sulfonic acid (ANSA) with H₂O₂. The reaction was followed spectrophotometrically by tracing the oxidized product at 465 nm after 30 min of mixing the reagents. The optimum reaction conditions were: 10 mmol l⁻¹ ANSA, 50 mmol l⁻¹ H₂O₂, 100 mmol l⁻¹ acetate buffer of pH 5.0 ± 0.05 and at 40 °C. Addition of 200 μg ml⁻¹ diethylenetriaminepentaacetic acid (DTPA) conferred high selectivity for the proposed method. Following the recommended procedure, Mo(VI) could be determined with a linear calibration graph up to 2.5 ng ml⁻¹ and a detection limit, based on the 3S_b-criterion, of 0.027 ng ml⁻¹. The unique sensitivity and selectivity of the implemented method allowed its direct application to the determination of Mo(VI) in natural and industrial waste water. The method was validated by comparison with the standard ETAAS method. Moreover, published catalytic-spectrophotometric methods for the determination of molybdenum were reviewed.     

Sensitized extraction spectrophotometric determination of Hg(II) with dithizone after its flotation as ion-associate using iodide and ferroin

This paper describes a simple and highly selective method for the separation, preconcentration and spectrophotometric determination of extremely low concentration of mercury. The method is based on the flotation of an ion-associate of HgI₄²⁻ and ferroin between aqueous and n-heptane interface at pH 5. The ion-associate was then separated and treated with ammonia and dithizone solutions to extract only the mercury chelate with CH₂Cl₂. The measurement is feasible when the volume of the water sample containing Hg(II) was varied over 50-800 ml. Beer's law was obeyed over the concentration range of 8 × 10⁻⁹ to 1.6 × 10⁻⁷ mol l⁻¹ with an apparent molar absorptivity of 6.53 × 10⁶ l mol⁻¹ cm⁻¹ for a 500 ml aliquot of the water sample. The detection limit (n = 7) was 5.0 × 10⁻¹⁰ mol l⁻¹ and the R.S.D. (n = 5) for 8.0 × 10⁻⁷ mol l⁻¹ of Hg(II) was 3.7%. A notable advantage of the method is that the determination of Hg(II) is free from the interference of almost all cations and anions found in the environmental and waste water samples. The determination of Hg(II) in tap, synthetic sea water and human hair samples was carried out by the present method and cold vapor atomic absorption spectrometry (CV-AAS). The results were satisfactorily comparable so that the applicability of the proposed method was confirmed to the real samples.     

Voltammetric behaviour of the synthetic pyrethroid lambda-cyhalothrin and its determination in soil and well water

The pyrethroid lambda-cyhalothrin is a common insecticide which is widespread in the environment. A study of the electrochemical reduction of the pesticide on a hanging mercury drop electrode (HMDE) was performed as basis for the development of a sensitive analytical method for determination of lambda-cyhalothrin in natural samples. Two electrochemical techniques—cyclic voltammetry (CV) and differential pulse voltammetry (DPV)—were applied. The study was performed in the pH range 2-13 using Britton-Robinson (B-R) buffer to control the pH of the measuring solutions and tetrabutylammonium chloride (TBAC) salt as supporting electrolyte. In DPV, a single reduction peak was observed at both pH<4.0 and pH>10.5 while two cathodic peaks were produced in the pH range 4.0-10.5. The results showed that the reduction of lambda-cyhalothrin in the measuring solution is irreversible. The limiting current was found to be diffusion-controlled and free of adsorption of the electroactive species to HMDE over the whole pH range tested. For the analytical DPV method running at pH 2 the relationship between peak current and lambda-cyhalothrin concentration was linear up to 500 μg l⁻¹ (1.1×10⁻⁶ mol l⁻¹) with a detection limit of 2.5 μg l⁻¹. The repeatability in terms of relative standard deviation (n=10) was in the order of 3.5% at concentration levels of 5 and 10 μg l⁻¹. A DPV method for determining lambda-cyhalothrin in the agrochemical formulation Karate, spiked soil and well water was developed. The recovery was about 94% in well water and 92% in soil samples at concentration range of 0.05-0.5 μg l⁻¹ and 0.05-0.5 μg g⁻¹, respectively.     

Voltammetry determination of trace manganese with pretreatment glassy carbon electrode by linear sweep voltammetry

This paper described the determination of trace manganese using linear sweep voltammetry at a pretreatment glassy carbon electrode. The glassy carbon electrode pretreated by electrochemical method in the 0.1 mol l⁻¹ NaOH solution greatly improved the electrode responsibility in the determination of manganese(II). The barrier to the detection of low manganese concentration was overcome by means of autocatalytic effect of manganese oxide deposited on the electrode in advance. Under the optimum experiments condition (0.04 mol l⁻¹ NH₃-NH₄Cl buffer solution, pH 9.0), the linear range was 4×10⁻⁸ to 1×l0⁻⁶ mol l⁻¹ Mn(II) for linear sweep voltammetry and 1×10⁻⁹ to 4×10⁻⁸ mol l⁻¹ Mn(II) for convolution voltammetry. The relative standard deviation for 2×10⁻⁸ mol l⁻¹ Mn(II) is 3.4%. The proposed method is simple, rapid, sensitive and selective. It had been applied to the determination of trace manganese in samples with satisfactory results.     

Analytical strategy photodegradation/chemiluminescence/continuous-flow multicommutation methodology for the determination of the herbicide Propanil

The present paper is dealing with an analytical strategy based on coupling photodegradation, chemiluminescence and multicommutation continuous-flow methodology for the determination of the pesticide Propanil, a common herbicide. The pesticide solution is inserted as small segments sequentially alternated with segments of the solution for adjusting the suitable medium for the photodegradation. Both flow-rates (sample and medium) are adjusted to required time for photodegradation, 2.0 min; and then, the resulting solution is also sequentially inserted as segments alternated with segments of the oxidizing solutions system, 1.00 × 10⁻⁴ mol l⁻¹ potassium permanganate in 2.00 mol l⁻¹ sulphuric acid medium. The calibration range, from 10 μg l⁻¹ to 25 mg l⁻¹, resulted in a linear behaviour over the range 10 μg l⁻¹-5 mg l⁻¹ and fitting the linear equation: I = 780.30C + 95.28; correlation coefficient 0.9999. The limit of detection was 8 μg l⁻¹ and the sample throughput 20 h⁻¹. After testing the influence of a large series of potential interferents the method is applied to water samples obtained from different places and to one formulation. The method is valid for the determination of other pesticides from the same chemical family, namely: alachlor, flumetsulam, furalaxyl and ofurace. Calibration graphs, limits of detection, repeatability and determination in water samples are obtained for each reported pesticide.     

Thermal modified Kaolinite as useful material for separation and preconcentration of trace amounts of manganese ions

This work assesses for the first time the potential of natural Kaolinite as adsorptive material for preconcentration of metal traces. Manganese is quantitatively retained by 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) on thermal modified Kaolinite by column method in pH range of 8.5-10.0 at flow rate of 2 ml min⁻¹. Manganese was removed from column with 5.0 ml of H₂SO₄ 4 mol l⁻¹ and determined by flame atomic absorption spectrometric at 279.5 nm. In this case, 0.l μg of manganese can be concentrated from 800 ml of aqueous sample (where concentration is as low as 0.125 μg l⁻¹). Detection limit is 4.3 μg l⁻¹ (3 δ_bl m⁻¹) and analytical curve is linear in the 0.02-10 mg l⁻¹ in final solution with correlation coefficient 0.9997 and relative standard deviation for eight replicate determination of 5 μg of manganese in final solution is 0.71%. The interference of a large number of anions and cations has been studied in detail to optimize the conditions and method was successfully applied for determination of manganese in complex materials.     

Development of a sequential injection system for trace mercury determination by cold vapour atomic absorption spectrometry utilizing an integrated gas-liquid separator/reactor

A simple and robust time-based on-line sequential injection system for trace mercury determination via cold vapour atomic absorption spectrometry (CVAAS), employing a new integrated gas-liquid separator (GLS), which in parallel operates as reactor, was developed. Sample and reductant are sequentially loaded into the GLS while an argon flow delivers the released mercury vapour through the atomic absorption cell. The proposed method is characterized by the ability of successfully managing variable sample volume up to 30 ml in order to achieve high sensitivity. For 20 ml sample volume, the sampling frequency is 25 h⁻¹. The calibration curve is linear over the concentration range 0.05-5.0 μg l⁻¹ of Hg(II), the detection limit is c_L = 0.02 μg l⁻¹, and the relative standard deviation is s_r = 2.6% at 1.0 μg l⁻¹ Hg(II) level. The performance of the proposed method was evaluated by analyzing certified reference material and applied to the analysis of natural waters and biological samples.     

High performance liquid chromatography determination of chlorophenols in water samples after preconcentration by continuous flow liquid membrane extraction on-line coupled with a precolumn

A continuous flow liquid membrane extraction (CFLME)-C₁₈ precolumn-liquid chromatography system was developed for preconcentration and determination of chlorinated phenols (CPs). After preconcentration by CFLME, which is based on the combination of continuous flow liquid-liquid extraction and supported liquid membrane, CPs were enriched in 960 μl of 0.5 mol l⁻¹ NaOH used as acceptor. This acceptor was on-line neutralized and transported onto the C₁₈ precolumn where analytes were absorbed and focused. Then the focused analytes were injected onto the C₁₈ analytical column for separation and detected at 215 nm with a diode array detector. CFLME related parameters such as flow rates, pH of donor and acceptor concentration were optimized. The proposed method presents detection limits of 0.02-0.09 μg l⁻¹ (S/N=3) when 100 ml samples were enriched. The proposed method was successfully applied to determine CPs in tap water and river water samples with spiked recoveries in the range of 70-121%.