Ultra trace analysis of 17 organochlorine pesticides in water samples from the Arctic based on the combination of solid-phase extraction and headspace solid-phase microextraction–gas chromatography-electron-capture detector

Solid-phase extraction (SPE) was combined with headspace solid-phase microextraction (HS-SPME) for the highly effective enrichment of 17 ultra trace organochlorine pesticides in water samples. The target compounds were successfully transferred from water samples to a gas chromatography capillary column by means of four consecutive steps, namely SPE, solvent conversion, HS-SPME, and thermal desorption of the SPME fiber. Parameters, including elution volume and breakthrough volume in the SPE step, temperature in the solvent conversion step, and fiber type, ionic strength, extraction temperature, extraction time, and pH in the SPME step were optimized to improve the performance of the method through either single factor comparative experiment or the orthogonal experimental design approach. After optimization, the method gave high sensitivity with a method detection limit ranging from 0.0018 to 0.027 ng L⁻¹, good repeatability with a relative standard deviation less than 20% (n = 4) and acceptable recovery with a value mostly exceeding 60%. External standard calibration was employed for the quantification, and a wide linear range (from 0.0010 to 60 ng mL⁻¹) with R² values ranging from 0.9988 to 0.9999 were observed. In the end, the method was successfully applied to the Arctic samples, and the results showed that, among all the organochlorine pesticides, hexachlorocyclohexanes (HCHs) were the most predominant in the Arctic surface water body with sum of their concentrations ranging from 0.262 to 3.156 ng L⁻¹.     

In situ growth and phenyl functionalization of titania nanoparticles coating for solid-phase microextraction of ultraviolet filters in environmental water samples followed by high performance liquid chromatography–UV detection

Based on TiO₂-nanoparticles coating fabricated by a one-step anodization method on titanium wire substrate, a novel phenyl functionalized solid-phase microextraction (SPME) fiber coating was prepared by simple and rapid in situ chemical assembling technique between the fiber surface titanol groups and trichlorophenylsilane reaction. The as-fabricated fiber exhibited good extraction capability for some UV filters and was employed to determine the ultraviolet (UV) filters in combination with high performance liquid chromatography–UV detection (HPLC–UV). The main parameters affecting extraction performance were investigated and optimized. Under the optimized conditions, the developed method was applied to detect several UV filters at trace concentration levels with only 8 mL of sample volume. They were determined in the range from 0.005 to 25 μg L⁻¹ with detection limits (S/N = 3) from 0.1 to 50 ng L⁻¹. The relative standard deviations (RSDs) for single fiber repeatability varied from 4.6 to 6.5% (n = 5) and fiber-to-fiber reproducibility (n = 5) ranged from 5.5 to 9.1%. The linear ranges spanned two-four magnitudes with correlation coefficients above 0.9990. Five real water samples including four Yellow River water samples and one rain water sample were determined sensitively with good recoveries ranging from 86.2 to 105.5%. The functionalized fiber coating performed good reproducible manner, high mechanical strength, good stability and long service life. Moreover, this study proposed an efficient sample pretreatment method for the determination of UV filters from environmental water samples.     

Improvement of UV spectrophotometry methodology for the determination of total polycyclic aromatic compounds in contaminated soils

Solid phase extraction (SPE) and UV spectrophotometry is used for the determination of polycyclic aromatic hydrocarbons in soils. A combination of aminopropyl and octadecyl bonded silica in a double SPE cartridge system has been optimized and validated using a certified reference material. The quantification is carried out after a principal component regression. The calibration has been done on a set of 40 samples of contaminated soils and has been optimized by using cross-validation. The 3σ detection limit was found to be 4.5 mg kg⁻¹.     

Using sweeping-micellar electrokinetic chromatography to determine voriconazole in patient plasma

Invasive fungal infection is a life-threatening condition; its occurrence has increased significantly over the past 20 years. We have developed a sensitive and efficient sweeping-micellar electrokinetic chromatography (sweeping-MEKC) method to quantify voriconazole, a potent triazole antifungal drug, in patient plasma. Solid phase extraction (SPE) conditions were first optimized to minimize plasma interference while maintaining a high recovery; the sweeping-MEKC conditions were then systematically optimized to obtain a high sweeping efficiency with good selectivity. Under the optimal analytical conditions, voriconazole was baseline-separated from endogenous materials within 10.5 min with a limit of detection of 0.075 μg mL⁻¹. The background electrolyte comprised 40 mM phosphoric acid, 110 mM sodium dodecyl sulfate, and 20% acetonitrile. In terms of method repeatability, the relative standard deviations (RSDs) of the migration time and the peak area (intra-day; n = 6) were both less than 5.5%; in terms of intermediate precision, and the RSDs of the peak area and the migration time (inter-day; n = 3) were both less than 6.3%. We successfully applied this developed method to the quantitative determination of plasma voriconazole levels in 16 patients; the results correlated well with those obtained through analyses using high-performance liquid chromatography. This sweeping-MEKC method is accurate and efficient and appears to be applicable to therapeutic drug monitoring and clinical research.     

Determination of haloethers in water with dynamic hollow fiber liquid-phase microextraction using GC-FID and GC-ECD

Dynamic hollow fiber liquid-phase microextraction (HF-LPME) coupled with gas chromatography with flame ionization detection (GC-FID) and GC-electron capture detecion (GC-ECD) was used for quantification of toxic haloethers in lake water. The analytes were extracted from 5 ml of aqueous sample using 4 μl of organic solvent through a porous polypropylene hollow fiber. The effects on extraction performance of solvent selection, agitation rate, extraction time, extraction temperature, concentration of salt added and volumes of solvent for extraction and injection were optimized. The proposed method provided a good average enrichment factor of up to 231-fold, reasonable reproducibility ranging from 9 to 12% (n = 3), and good linearity (R² ≧ 0.9973) for spiked water samples. Method detection limits (MDLs) ranged from 0.55 to 4.30 μg/l for FID and 0.11-0.34 μg/l for ECD (n = 7).     

Method development for the determination of teicoplanin in patient serum by solid phase extraction and micellar electrokinetic chromatography

In-hospital deaths caused by the infection of methicillin-resistant Staphylococcus aureus (MRSA) are on the increase worldwide. Teicoplanin is a potent glycopeptide antibiotic against MRSA. A rapid and cost-saving micellar electrokinetic chromatography (MEKC) method combined with solid phase extraction (SPE) was developed and then validated to quantify teicoplanin in patient serum in this work. The method includes the following steps: (1) pretreatment of the serum samples with 10 M urea to denature proteins, (2) application of SPE by using an OASIS HLB cartridge to clean up and concentrate the serum samples, and (3) use of MEKC for sample analysis. Under the optimized conditions, the SPE recovery of teicoplanin is higher than 90%. The six major components of teicoplanin could be baseline-separated from one another and endogenous materials in 12 min with a background electrolyte composed of 20 mM sodium tetraborate buffer pH 8.8, 40 mM sodium dodecyl sulfate, and 11% (v/v) ACN. The relative standard deviation (R.S.D.) of the peak area ratios for method repeatability (n = 6) and intermediate precision (inter-day, n = 3) were found to be lower than 4.18% and 5.30%, respectively. The calibration curves were linear between the chromatographic response and total teicoplanin concentration over the range of 5 μg/mL to 55 μg/mL. Limit of detection (LOD) for each of the six components was found to be lower than 0.06 μg/mL. Pearson’s correlation revealed that a good correlation (r = 0.98) was obtained between the SPE-MEKC method and the fluorescence polarization immunoassay (FPIA) method. The developed method can be used to quantitatively determine serum teicoplanin concentration in patients for dose monitoring and clinical research.     

HPLC-UV and HPLC-MSn multiresidue determination of amidosulfuron, azimsulfuron, nicosulfuron, rimsulfuron, thifensulfuron methyl, tribenuron methyl and azoxystrobin in surface waters

The paper presents a new HPLC method, with UV and MSⁿ detection, for the determination of seven pesticides, including the sulfonylurea herbicides amidosulfuron, azimsulfuron, nicosulfuron, rimsulfuron, thifensulfuron methyl, tribenuron methyl, and the fungicide azoxystrobin characterised by a methoxyacrilate structure. The methodology consists of a preconcentration/SPE (solid phase extraction) step and HPLC-UV (240 nm detection wavelength)-MSⁿ analysis. Under the optimised conditions and after a 1000/1 preconcentration factor, the limits of detection were lower than 14.5 ng L⁻¹ for UV detection and lower than 8.1 ng L⁻¹ for MS detection. The limits of quantification were lower than 48.3 ng L⁻¹ in UV detection and than 26.9 ng L⁻¹ in MSⁿ detection. The analysis of two samples, spiked with a mixture of the pesticides at threshold level concentrations, gave more than 60% recovery.     

Determination of pesticides in surface and ground waters by liquid chromatography-electrospray-tandem mass spectrometry

The sensitive multiresidual analytical method for simultaneous analysis of 14 most commonly used agricultural pesticides in Serbia was developed and optimized. The selected insecticides, fungicides and herbicides belong to seven chemical classes (organophosphates, neonicotinoids, carbamates, diacylhydrazines, benzimidazoles, triazines and phenylureas). The method was based on solid-phase extraction followed by liquid chromatography-tandem mass spectrometry. The following parameters that may affect the SPE procedure efficiency were optimized: the sorbent type in combination with different elution solvents, the sample pH and the sample volume. For each pesticide, MSⁿ analysis was performed and distinctive ions and transitions were selected for identification and quantification, as well as for confirmation purposes. External matrix-matched calibration method was used to eliminate variable matrix effect and ensure precise quantification. Good recoveries (72-129%), and low limits of detection (0.4-5.5 ng L⁻¹) and quantification (1.1-18.2 ng L⁻¹) were achieved for all selected pesticides. The developed and optimized method was successfully applied in the analysis of several river waters, as well as ground waters in Serbia, influenced by agriculture. The most frequently detected pesticide was carbendazim. Dimethoate, carbofuran and propazine were also found in the investigated samples.     

A chitosan–polypyrrole magnetic nanocomposite as μ-sorbent for isolation of naproxen

An extracting medium based on chitosan–polypyrrole (CS–PPy) magnetic nanocomposite was synthesized by chemical polymerization of pyrrole at the presence of chitosan magnetic nanoparticles (CS-MNPs) for micro-solid phase extraction. In this work, magnetic nanoparticles, the modified CS-MNPs and different types of CS–PPy magnetic nanocomposites were synthesized. Extraction efficiency of the CS–PPy magnetic nanocomposite was compared with the CS-MNPs and Fe₃O₄ nanoparticles for the determination of naproxen in aqueous samples, via quantification by spectrofluorimetry. The scanning electron microscopy images obtained from all the prepared nanocomposites revealed that the CS–PPy magnetic nanocomposite possess more porous structure. Among different synthesized magnetic nanocomposites, CS–PPy magnetic nanocomposite showed a prominent efficiency. Influencing parameters on the morphology of CS–PPy magnetic nanocomposite such as weight ratio of components was also assayed. In addition, effects of different parameters influencing the extraction efficiency of naproxen including desorption solvent, desorption time, amount of sorbent, ionic strength, sample pH and extraction time were investigated and optimized. Under the optimum condition, a linear calibration curve in the range of 0.04–10 μg mL⁻¹ (R² = 0.9996) was obtained. The limits of detection (3S_b) and limits of quantification (10S_b) of the method were 0.015 and 0.04 μg mL⁻¹ (n = 3), respectively. The relative standard deviation for water sample spiked with 0.1 μg mL⁻¹ of naproxen was 3% (n = 5) and the absolute recovery was 92%. The applicability of method was extended to the determination of naproxen in tap water, human urine and plasma samples. The relative recovery percentages for these samples were in the range of 56–99%.     

On-line trace enrichment of phenolic compounds from water using a pyrrole-based polymer as the solid-phase extraction sorbent coupled with high-performance liquid chromatography

A pyrrole-based conductive polymer was prepared and applied as new sorbent for on-line solid-phase extraction (SPE) of phenol and chlorophenols from water samples. Polypyrrole (PPy) was synthesized by chemical oxidation of the monomer in non-aqueous solution. The efficiency of this polymer for extraction of phenol and chlorophenols was evaluated using 35 mg of PPy as the sorbent in an on-line SPE system coupled to reversed-phase liquid chromatography with UV detection. The mobile phase were mixture of phosphate buffer-acetonitrile and compounds were eluted by the mobile phase using a six-port switching valve. High volumes of water, up to 160 ml, could be preconcentrated without the loss of phenols, except for the more polar ones. The R.S.D. for a river water sample spiked with phenol and chlorophenols at sub-ppb level was lower than 7% (n=5) and detection limits of 15-100 and 35-150 ng l⁻¹ for tap and river water were obtained, respectively.     

Application of dispersive liquid-liquid microextraction and spectrophotometric detection to the rapid determination of rhodamine 6G in industrial effluents

A rapid and effective preconcentration method for extraction of rhodamine 6G was developed by using a dispersive liquid-liquid microextraction (DLLME) prior to UV-vis spectrophotometry. In this extraction method, a suitable mixture of acetone (disperser solvent) and chloroform (extractant solvent) was injected rapidly into a conical test tube containing aqueous solution of rhodamine 6G. Therefore, a cloudy solution was formed. After centrifugation of the cloudy solution, sedimented phase was evaporated, reconstituted with methanol and measured by UV-vis spectrophotometry. Different operating variables such as type and volume of extractant solvent, type and volume of disperser solvent, pH of the sample solution, salt concentration and extraction time were investigated. The optimized conditions (extractant solvent: 300 μL of chloroform, disperser solvent: 3 mL of acetone, pH: 8 and without salt addition) resulted in a linear calibration graph in the range of 5-900 ng mL⁻¹ of rhodamine 6G in initial solution with R² = 0.9988 (n = 5). The Limits of detection and quantification were 2.39 and 7.97 ng mL⁻¹, respectively. The relative standard deviation for 50 and 250 ng mL⁻¹ of rhodamine 6G in water were 2.88% and 1.47% (n = 5), respectively. Finally, the DLLME method was applied for determination of rhodamine 6G in different industrial waste waters.     

Evaluation of the solid-phase microextraction fiber coated with single walled carbon nanotubes for the determination of benzene,toluene, ethylbenzene,xylenes in aqueous samples

A solid-phase microextraction (SPME) fiber coated with single walled carbon nanotubes (SWCNTs) was prepared by electrophoretic deposition and treated at 500 °C in H₂ stream. In order to evaluate the characteristics of the obtained fiber, it was applied in the headspace solid-phase microextraction (HS-SPME) of benzene, toluene, ethylbenzene and xylenes (BTEX) from water sample and quantification by gas chromatography with flame ionization detection (GC-FID). The results indicated that the thermal treatment with H₂ enhanced the extraction of the SWCNTs fiber for BTEX significantly. Thermal stability and durability of the fiber were also investigated, showing excellent stability up to 350 °C and life time over 120 times. In the comparison with the commercial CAR–PDMS fiber, the SWCNTs fiber showed similar and higher extraction efficiencies for BTEX. Under the optimized conditions, the linearity, LODs (S/N = 3) and LOQs (S/N = 10) of the method based on the SWCNTs fiber were 0.5–50.0, 0.005–0.026 and 0.017–0.088 μg/L, respectively. Repeatability for one fiber (n = 3) was in the range of 1.5–5.6% and fiber-to-fiber reproducibility (n = 3) was in the range of 4.2–8.3%. The proposed method was successfully applied in the analysis of BTEX compounds in seawater, tap water and wastewater from a paint plant.     

Improved methods for urinary atrazine mercapturate analysis--assessment of an enzyme-linked immunosorbent assay (ELISA) and a novel liquid chromatography-mass spectrometry (LC-MS) method utilizing online solid phase extraction (SPE)

Elimination of interfering substances in urine by solid phase extraction (SPE) prior to analysis resulted in 10-fold improvement in the sensitivity of atrazine mercapturate (AM) enzyme-linked immunosorbent assay (ELISA) compared to previous reports. Of the two tested SPE systems, Oasis^® HLB and MCX, the mixed-mode MCX gave good recoveries (82%) of AM in spiked samples measured by ELISA, whereas the reverse-phase HLB phase was not compatible with the immunochemical method. At relatively high concentrations of urinary AM (>20 ng mL⁻¹), sample dilution was effective enough for the elimination of interfering substances. The new liquid chromatography-mass spectrometry (LC-MS) method developed for AM utilizes online-SPE with Oasis^® HLB, column switching and a stable-isotope internal standard. The limit of quantification (0.05 ng mL⁻¹) indicates improved sensitivity compared with most previously published LC-MS methods for AM. Validation of all three methods, LC-MS, ELISA + SPE and ELISA + dilution with spiked urine samples showed good correlation between the known and measured concentrations with R² values of 0.996, 0.957 and 0.961, respectively. When a set (n = 70 plus 12 blind duplicates) of urine samples from farmers exposed to atrazine was analyzed, there was a good agreement (R² = 0.917) between the log normalized data obtained by ELISA + SPE and LC-MS. High correlation among the data obtained by the two tested methods and the LC-MS method by the Center of Disease Control and Prevention (CDC), together with low variability among the blind duplicates, suggests that both methods reported here would be suitable for the analysis of urinary AM as a biomarker for human exposure of atrazine.     

Determination of andrographolide and dehydroandrographolide in rabbit plasma by on-line solid phase extraction of high-performance liquid chromatography

The high-performance liquid chromatography (HPLC) coupled with on-line solid phase extraction (SPE) and ultraviolet (UV) detection was developed for determining andrographolide and dehydroandrographolide in rabbit plasma. Plasma samples (100 μL) were injected directly into a C18 SPE column and the biological matrix was washed out for 6 min using 15% aqueous methanol. By rotation of the switching valve, andrographolide and dehydroandrographolide were eluted in the back-flush mode and transferred to the analytical column by the chromatographic mobile phase consisted of methanol:acetonitrile (ACN):water (50:10:40; v/v). The UV detection was performed at 225 nm. The calibration curves showed excellent linear relationship (R ≥ 0.9993) over the concentration range of 0.05-5.0 μg mL⁻¹. The within- and between-day precisions (R.S.D.) of two analytes were in the range of 1.2-6.5% and the accuracies were between 92.0% and 102.1%. Their recoveries were all greater than 94%. The limits of detection were 0.019 μg mL⁻¹ for andrographolide and 0.022 μg mL⁻¹ for dehydroandrographolide. This method was successfully applied to the plasma concentration-time curve study after oral administration of Andrographis paniculata Nees extract in rabbit.     

Combination of solid phase extraction and in vial solid phase derivatization using a strong anion exchange disk for the determination of nerve agent markers

Alkylphosphonic acids (APAs) are degradation products and chemical markers of organophosphorous (OP) nerve agents (chemical warfare agents). Anion exchange disk-based solid phase extraction (SPE) has been combined with in vial solid phase derivatization (SPD) and GC–MS analysis for the determination of APAs in aqueous samples. The optimization of critical method parameters, such as the SPD reaction, was achieved using statistical experimental design and multivariate data analysis. The optimized method achieved quantitative recoveries in the range from 83% to 101% (n = 13, RSD from 4% to 10%). The method was sensitive, with LODs in SIM mode of 0.14 ppb, and demonstrated excellent linearity with an average R² ≥ 0.99 over the concentration range of 0.07–1.4 ppm in full scan mode and from 0.14 ppb to 14 ppb in SIM mode. For forensic applications, aqueous samples containing APAs at concentrations exceeding 14 ppb were concentrated and target analytes were successfully identified by spectral library and retention index matching. Method robustness was evaluated using aqueous samples from the official OPCW Proficiency Test (round 19) and all APAs present in the sample were conclusively identified. The SPE disk retained the underivatized APAs in a stable condition for extended periods of time. No significant losses of APAs from the disk were observed over a 36-day period. Overall, the method is well suited to the qualitative and quantitative analysis of degradation markers of OP nerve agents in aqueous matrices with simplicity, a low risk of cross-contamination and trace level sensitivity.     

Determination of 16 polycyclic aromatic hydrocarbons in environmental water samples by solid-phase extraction using multi-walled carbon nanotubes as adsorbent coupled with gas chromatography–mass spectrometry

A solid-phase extraction (SPE) using multi-walled carbon nanotubes (MWCNTs) as adsorbent coupled with gas chromatography–mass spectrometry (GC–MS) method was developed for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. Several condition parameters, such as extraction adsorbents, elution solvents and volumes, and sample loading flow rate and volume were optimized to obtain high SPE recoveries and extraction efficiency. 150 mg MWCNTs as sorbent presented high extraction efficiency of 16 PAHs due to the large specific surface area and high adsorption capacity of MWCNTs compared with the commercial C18 column (250 mg/2 mL). The calibration curves of 16 PAHs extracted were linear in the range of 20–5000 ng L⁻¹, with the correlation coefficients (r²) between 0.9848 and 0.9991. The method attained good precisions (relative standard deviation, RSD) from 1.2% to 12.1% for standard PAHs aqueous solutions; method recoveries ranged in 76.0–125.5%, 74.5–127.0%, and 70.0–122.0% for real spiked samples from river water, tap water and seawater, respectively. Limits of detection (LODs, S/N = 3) of the method were determined from 2.0 to 8.5 ng L⁻¹. The optimized method was successfully applied to the determination of 16 PAHs in real environmental water samples.     

Direct quantification of creatinine in human urine by using isotope dilution extractive electrospray ionization tandem mass spectrometry

Urinary creatinine (CRE) is an important biomarker of renal function. Fast and accurate quantification of CRE in human urine is required by clinical research. By using isotope dilution extractive electrospray ionization tandem mass spectrometry (EESI–MS/MS) a high throughput method for direct and accurate quantification of urinary CRE was developed in this study. Under optimized conditions, the method detection limit was lower than 50 μg L⁻¹. Over the concentration range investigated (0.05–10 mg L⁻¹), the calibration curve was obtained with satisfactory linearity (R² = 0.9861), and the relative standard deviation (RSD) values for CRE and isotope-labeled CRE (CRE-d3) were 7.1–11.8% (n = 6) and 4.1–11.3% (n = 6), respectively. The isotope dilution EESI–MS/MS method was validated by analyzing six human urine samples, and the results were comparable with the conventional spectrophotometric method (based on the Jaffe reaction). Recoveries for individual urine samples were 85–111% and less than 0.3 min was taken for each measurement, indicating that the present isotope dilution EESI–MS/MS method is a promising strategy for the fast and accurate quantification of urinary CRE in clinical laboratories.     

Chitosan modified ordered mesoporous silica as micro-column packing materials for on-line flow injection-inductively coupled plasma optical emission spectrometry determination of trace heavy metals in environmental water samples

A novel adsorbent of chitosan chemically modified ordered mesoporous silica was synthesized and employed as a solid phase extraction (SPE) material for flow injection (FI) micro-column preconcentration on-line coupled with inductively coupled plasma optical emission spectrometry (ICP-OES) determination of trace heavy metals V, Cu, Pb, Cd and Hg in environmental water samples. The factors affecting separation and preconcentration of target heavy metals such as pH, sample flow rate and volume, eluent concentration and volume, interfering ions were investigated. Under the optimized experimental conditions, an enrichment factor of 20 and sampling frequency of 10 h⁻¹ were obtained. The detection limits of the method for V, Cu, Pb, Cd and Hg were 0.33, 0.30, 0.96, 0.05 and 0.93 ng mL⁻¹, and the relative standard deviations (RSDs) were 2.8%, 6.7%, 1.8%, 4.0% and 5.3% (n = 7, C = 10 ng mL⁻¹), respectively. The adsorption capacities of chitosan modified ordered mesoporous silica for V, Cu, Pb, Cd, and Hg were found to be 16.3, 21.7, 22.9, 12.2 and 13.5 mg g⁻¹, respectively. In order to validate the developed method, a certified reference material of GSBZ50009-88 environmental water sample was analyzed and the determined values were in good agreement with the certified values. The proposed method has also been applied to the determination of trace heavy metals in natural water samples with satisfactory results.     

A simple and fast method for chlorsulfuron and metsulfuron methyl determination in water samples using multiwalled carbon nanotubes (MWCNTs) and capillary electrophoresis

A new method to determine metsulfuron methyl (MSM) and chlorsulfuron (CS) in different water samples was developed. It consists in a solid phase extraction (SPE) procedure using multiwalled carbon nanotubes (MWCNTs) as sorbent material in combination with capillary zone electrophoretic determination. To carry out the pre-concentration step, a simple flow injection system was developed and optimized. Thus, 250 μL of aqueous solution containing methanol 50% (v/v) and acetonitrile 2% (v/v) as eluent, 10 mL of sample and a flow rate of 1.15 mL min⁻¹ were selected. The CE variables also were optimized. A rapid determination and good resolution of two herbicides were obtained within 9 min using a simple electrophoretic buffer (50 mmol L⁻¹ sodium tetraborate with 3% of methanol, pH = 9.0). Under the optimum conditions, the calibration curves were linear between 0.5 and 6 μg L⁻¹ for MSM and CS with R² = 0.995 and 0.997, respectively. The repeatability of the proposed method, expressed as relative standard deviation (RSD), varied between 4.1% and 5.4% (n = 10) and the detection limits for MSM and CS were 0.40 and 0.36 μg L⁻¹, respectively. Good results were achieved when the proposed method was applied to spiked real water samples. The recoveries percentages of the two analytes were over the range 86-108%.