聚偏氟乙烯中空纤维亲和膜分离γ-球蛋白的研究(Ⅰ)——聚偏氟乙烯中空纤维亲和膜的制备及其吸附性能

对聚偏氟乙烯(PVDF)中空纤维膜进行表面亲水化处理,再经活化、偶联制得了带有苯丙氨酸(Phe)的PVDF中空纤维亲和膜.制备过程中以光电子能谱(XPS)及红外光谱分析膜表面基团的变化,经亲水化处理及活化偶联后,膜表面的O和N含量分别从5.6％和0.6％增加到16.5％和3.0％,而F含量由38.3％降低为23.0％,将该亲和膜用于室温下血浆中γ-球蛋白的分离实验,在pH=7.4,离子强度I=0.18的缓冲液体系及进料质量浓度为1.0mg/mL条件下,该亲和膜对γ-球蛋白的吸附量可达到5.85mg/g膜;与市售γ-球蛋白相比,血浆中提取纯度可达83.9％。     

Synthesis of polypiperazine-amide thin-film membrane on PPESK hollow fiber UF membrane

A new interfacial polymerization (IP) procedure is developed in order to synthesize polypiperazine-amide thin-film membrane on the inner surface of poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber ultrafiltration (UF) membrane.A hollow fiber composite membrane with good performance was prepared and studied by FT-IR and scanning electron microscopy.     

Porous membranes modified by hyperbranched polymers: I. Preparation and characterization of PVDF membrane using hyperbranched polyglycerol as additive

Porous membranes were prepared via phase inversion process from casting solution composed of poly(vinylidene fluoride) (PVDF), N,N-dimethylacetamide (DMAc), and hyperbranched polyglycerol (HPG). The membranes were characterized in terms of surface and bulk chemical compositions, morphology, water contact angle, porosity, and water flux. The effects of HPG content on membrane structures and properties were investigated. The effect of HPG addition on the hydrophilicity was discussed as well when the compositions of coagulation bath were changed. To better understand the special effects of HPG on the structures and properties of the membranes, PVDF membranes prepared using HPG as the additive were compared with those prepared using polyethylene glycol (PEG) as the additive.     

Evolution of the precipitation kinetics,morphologies, permeation performances,and crystallization behaviors of polyvinylidenefluoride (PVDF) hollow fiber membrane by adding different molecular weight polyvinylpyrrolidone (PVP)

Polyvinylidenefluoride (PVDF) hollow fiber membranes were fabricated by wet spinning (wet/wet) and dry‐jet wet spinning (dry/wet; 3 cm air gap) processes with four types of polyvinylpyrrolidone (PVP) of different molecular weight as additives. Evolution of the precipitation kinetics, morphologies, permeation performances, and crystallization behaviors of the as‐spun PVDF membranes were investigated. The PVDF membranes were well characterized by numerous state‐of‐the‐art analytical techniques: scanning electron microscopy (SEM), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and attenuated total reflectance fourier Transform Infrared (FTIR‐ATR) and elucidated accompanying with its precipitation kinetics obtained by light transmittance measurements. The precipitation kinetics results confirm that four PVDF/PVP/NMP dopes experience instantaneous demixing mechanism and the precipitation rate decreases as PVP molecular weight increases. Little peaks are found in the precipitation curves of the PVDF dopes containing PVP of low molecular weight. The SEM images indicate that the middle sponge‐like layer sandwiched by double finger‐like layers becomes thinner for the special precipitation behaviors. Visible large pores exist in the internal surfaces of the PVDF membranes spun by both wet/wet and dry/wet spinning processes. The increase in PVP molecular weight restricts the formation of large pores in the internal surfaces of the PVDF membranes for the increase in dope viscosity. The pure water permeability (PWP) of the as‐spun PVDF membranes increases initially and then decreases as PVP molecular weight increases. The largest PWP flux of 316.7 L m^?2 h^?1 bar^?1 is obtained for the PVDF membrane containing PVP K25 by wet/wet spinning process. The rejections for bovine serum albumin (BSA) by the as‐spun PVDF membranes range from 35.4 to 82.9%. It illustrates that typical PVDF ultrafiltration membranes were obtained in this research. The melting temperature(T_m) of the PVDF hollow fiber membranes decreases with the increase in the PVP molecular weight as a whole. IR spectra and XRD patterns verify the exclusive formation of β crystalline phase structure in the as‐spun PVDF membranes. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of the preparation conditions on the formation of asymmetric poly(vinylidene fluoride) hollow fibre membranes with a dense skin

Integrally skinned asymmetric poly(vinylidene fluoride) hollow fibre membranes were prepared and characterized. The effects of phase inversion methods (dry-wet or wet) and spinning conditions, such as the type of solvent (NMP, DMAc), the concentration of polymer in dope solution, temperature of the external coagulation bath and the composition of the inner coagulant on the morphology and on the formation of a dense skin layer were investigated. The structure of the membranes was analyzed by scanning electron microscopy and the gas permeation properties with six different gases (He, H₂, N₂, O₂, CH₄ and CO₂) were measured at 25 °C to confirm the integrity of the selective skin layer. Under the proper conditions highly selective and permeable PVDF hollow fibre membranes were thus obtained by dry-wet spinning of a 30 wt.% PVDF solution in DMAc, using hot water (50 °C) as the external coagulant and a bore fluid of pure water as the internal coagulant. The best membrane had a selective outer skin with an effective thickness of approximately 0.2 μm. The ideal selectivity of the hollow fibres approached or even exceeded the intrinsic ideal selectivity of a dense PVDF film, for instance the selectivity for He over N₂ was 86.2 for the hollow fibre, whereas it was 83.5 for a dense PVDF reference film. DSC and FT-IR/ATR analysis indicated a higher fraction of the β-crystal phase in the selective skin and a high overall crystallinity than in the melt-processed film. The latter explains the relatively high selectivity and low permeability of the membranes. Intrinsic polymer properties make the membranes also suitable for vapour transport than for gas separation.     

Modification of porous poly(vinylidene fluoride) membrane using amphiphilic polymers with different structures in phase inversion process

Three kinds of amphiphilic polymers, including the tri-block copolymer of (polyethylene oxide)–(polypropylene oxide)–(polyethylene oxide) (I, EPTBP), the comb-like copolymer of polysiloxane with polyethylene oxide and polypropylene oxide side chains (II, ACPS) and the hyperbranched star copolymer of polyester-g-methoxyl polyethylene glycol (III, HPE-g-MPEG), were blended with PVDF to fabricate porous membranes via a phase inversion process, respectively, and the effects of the different structures of the amphiphilic polymers on the properties of the blend membranes were compared. The membranes were characterized by scanning electron microscopy (SEM), elemental analysis, X-ray photoelectron spectroscopy (XPS) analysis, mercury porosimetry, water contact angle measurements, etc. The anti-fouling properties of the prepared membranes were evaluated by static and dynamic bovine serum albumin (BSA) adsorptions. Specially, the stabilities of these amphiphilic polymers in the final membranes were estimated by continuous leaching tests. At the same time, the properties of the membranes using the amphiphilic polymers as modifiers were compared with those of the membrane using poly(ethylene glycol) (PEG) as modifier.     

Ultrasensitive determination of cadmium in seawater by hollow fiber supported liquid membrane extraction coupled with graphite furnace atomic absorption spectrometry

A new procedure, based on hollow fiber supported liquid membrane preconcentration coupled with graphite furnace atomic absorption spectrometry (GFAAS) detection, was developed for the determination of trace Cd in seawater samples. With 1-octanol that contained a mixture of dithizone (carrier) and oleic acid immobilized in the pores of the polypropylene hollow fiber as a liquid membrane, Cd was selectively extracted from water samples into 0.05 M HNO₃ that filled the lumen of the hollow fiber as a stripping solution. The main extraction related parameters were optimized, and the effects of salinity and some coexisting interferants were also evaluated. Under the optimum extraction conditions, an enrichment factor of 387 was obtained for a 100-mL sample solution. In combination with graphite furnace atomic absorption spectrometry, a very low detection limit (0.8 ng L^− 1) and a relative standard deviation (2.5% at 50 ng L^− 1 level) were achieved. Five seawater samples were analyzed by the proposed method without dilution, with detected Cd concentration in the range of 56.4–264.8 ng L^− 1 and the relative spiked recoveries over 89%. For comparison, these samples were also analyzed by the Inductively Coupled Plasma Mass Spectrometry (ICP-MS) method after a 10-fold dilution for matrix effect elimination. Statistical analysis with a one-way ANOVA shows no significant differences (at 0.05 level) between the results obtained by the proposed and ICP-MS methods. Additionally, analysis of certified reference materials (GBW (E) 080040) shows good agreement with the certified value. These results indicate that this present method is very sensitive and reliable, and can effectively eliminate complex matrix interferences in seawater samples.     

Versatility of hydrophilic and antifouling PVDF ultrafiltration membranes tailored with polyhexanide coated copper oxide nanoparticles

Hydrophilic poly(vinylidene fluoride) (PVDF) nanocomposite ultrafiltration (UF) membranes with excellent antifouling and antibiofouling characteristics are fabricated by employing polyhexanide coated copper oxide nanoparticles (P–CuO NPs). The presence of P–CuO NPs is played a significant role in altering the PVDF membrane matrix and probed by XRD, FTIR, FESEM and contact angle analysis. The PVDF/P–CuO nanocomposite membranes exhibited an outstanding antifouling performance indicated by the superior pure water flux, effective foulant separation and maximum flux recovery ratio during UF experiments as a result of the formation of the hydrophilic and more porous membrane due to the uniform distribution of P–CuO NPs. Particularly, the PVDF/P–CuO-3 membrane showed higher PWF of 152.5 ± 2.4 lm⁻²h⁻¹ and porosity of 64.5% whereas the lower contact angle of 52.5°. Further, it showed the higher rejection of 99.5 and 98.4% and the flux recovery ratio of 99.5 and 98.5% respectively for BSA and HA foulants, demonstrated its increased water permeation, foulant separation and antifouling behavior. Further, the decent antibacterial activity is showed by the PVDF/P–CuO nanocomposite membranes with the formation of halo-zone around the membrane when exposed to the bacterial medium demonstrated that, by this process an antibacterial water treatment membrane can be developed by simple phase inversion technique with good membrane stability.     

Effect of polyaniline (PANI) on Poly(vinylidene fluoride-co-hexaflouro propylene) (PVDF-co-HFP) polymer electrolyte membrane prepared by breath figure method

Poly(vinylidene fluoride-co-hexaflouro propylene) is a well-known material for polymer electrolyte membranes (PEMs) due to its low cost, high mechanical integrity and excellent chemical resistance; however, its pure form has limited characteristics that require further modification to achieve optimum results. Therefore, the different dosages of polyaniline (PANI) (10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt%) were incorporated into PVDF-HFP blend to fabricate PVDF-HFP/PANI polymer electrolyte membrane by using breath-figure method. The FTIR peaks of PVDF-HFP and PVDF-HFP/PANI membrane confirms the successful incorporation of PANI into PVDF-HFP blend, while TGA, DSC and XRD analysis shows the PANI effect on stability and ionic conductivity of PVDF-HFP membrane. The PVDF-HFP/PANI membrane with 30 wt% PANI found superior with the highest porosity of 83%, electrolyte uptake of 270% and ionic conductivity of 1.96 mS cm⁻¹; however, the other concentrations of PANI were also effective and enhanced the performance of PVDF-HFP membrane. This shows the improved performances of PVDF-HFP membrane were attributed to successful incorporation of PANI and the proposed membrane can be a suitable alternative PEM or a separator for energy devices.     

PVDF membrane formation by diffusion‐induced phase separation‐morphology prediction based on phase behavior and mass transfer modeling

The equilibrium phase behavior of water (nonsolvent)‐DMF (solvent)‐PVDF system at 25°C was investigated via both theoretical and experimental approaches. Using binary interaction parameters, χ_ij, obtained previously, the theoretical phase boundaries were computed and were found to match closely the measured binodal and crystallization‐induced gelation data. Membranes were prepared using the isothermal immersion‐precipitation processes in various dope and bath conditions. The formed membranes demonstrated a broad spectrum of morphologies: At one extreme, asymmetric structure was obtained featuring a continuous tight skin and a sublayer composed of parallel macrovoids and cellular pores; at the other limit, skinless microporous membrane was produced with spherical particles packed into a bi‐continuous structure. The crystalline characters of PVDF gels and membranes were examined by small angle light scattering, scanning electron microscopy, and differential scanning calorimetry techniques. In addition, diffusion trajectories and concentration profiles in the membrane solution before precipitation were calculated for the immersion process. These results predicted reasonably the various morphologies observed in the membranes. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2079–2092, 1999     

TMAH改性PVDF一步接枝PSBMA质子交换膜的制备与性能

使用四甲基氢氧化铵(TMAH)液相改性聚偏氟乙烯(PVDF),以过氧化苯甲酰(BPO)为引发剂,一步将磺酸基甲基丙烯酸甲酯(SBMA)接枝到改性的PVDF上,制备了聚偏氟乙烯接枝聚磺酸基甲基丙烯酸甲酯(PVDFg-PSBMA)质子交换膜.利用傅里叶变换红外(FTIR)光谱和扫描电镜-X射线能谱(SEM-EDX)分析了膜的结构、形貌及硫元素分布情况.同时研究了不同质量分数的TMAH甲醇溶液对PVDF-g-PSBMA膜电导率和甲醇渗透率的影响.结果表明, TMAH使PVDF脱去HF产生碳碳双键且SBMA成功接枝到改性的PVDF骨架上,硫元素在膜内外分布均匀; PVDF-g-PSBMA膜的电导率和甲醇渗透率随TMAH在甲醇中质量分数的增多而增大, TMAH质量分数为20%的膜的质子电导率在20 ℃下达到0.0892 S·cm^-1,常温下的甲醇渗透率为4.04 × 10^-7cm²·s^-1;热重分析(TGA)表明,膜的热稳定性良好,耐热温度高达270 ℃.该膜作为电解质材料的直接甲醇燃料电池(DMFC)的最大功率密度达到17.06 mW·cm^-2.     

Removal of 2,4-dichlorophenol from wasterwater by vacuum membrane distillation using hydrophobic PPESK hollow hiber membrane

2,4-Dichlorophenol was removed from wasterwater using a new hydrophobic poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber membrane by vacuum membrane distillation(VMD).     

Crystallization behavior and hydrophilicity of poly(vinylidene fluoride) (PVDF)/poly(methylmethacrylate) (PMMA)/poly(styrene-<Emphasis Type="Italic">co</Emphasis>-acrylonitrile) (SAN) ternary blends

Compatibilization of the partially miscible poly(vinylidene fluoride) (PVDF)/poly(styrene-co-acrylonitrile) (SAN) pair by a third homopolymer, i.e., poly(methyl methacrylate) (PMMA), was investigated in relation to cross section morphology, crystallization behaviors and hydrophilicity of the polyblends. Scanning electron microscopy showed a more regular and homogeneous morphology when more than 15 wt.% PMMA was incorporated. The samples presented only α phase regardless of PMMA content in the blend. As the PMMA content increased in the blends, the interactions between each component were enhanced, and the crystallization of PVDF was limited, leading to a decreasing of the crystallinity and the crystallite thickness. Besides, the hydrophilicity of PVDF was further improved by PMMA addition. The sample containing 15 wt.% PMMA showed a more hydrophilic property due to the more polar part of surface tension induced by PMMA addition. Observed from the cross section of the blends, the miscibility of partially miscible PVDF/SAN blends were efficiently improved by PMMA incorporation.     

Poly(vinylidene fluoride) membrane based thin film microextraction for enrichment of benzoylurea insecticides from water samples followed by their determination with HPLC

Thin-film microextraction(TFME),a new geometry for solid-phase microextraction,has become an attractive sample-preparation technique.Compared to other microextraction approaches,the sensitivity of this technique was enhanced without sacrificing the sampling time due to the high surface area-tovolume ratio together with the increase of extraction-phase volume.In this paper,a new TFME method based on poly(vinylidene fluoride) membrane was developed for the extraction of benzoylurea insecticides(diflubenzuron,triflumuron,hexaflumuron and teflubenzuron) from water samples followed by their determination with high performance liquid chromatography-diode array detection.Under the optimal conditions,good linearity was observed over the concentration range of 0.5-100.0 ng/mL with correlation coefficient greater than 0.9994.The limits of detection(S/N = 3) of the method for the target analytes were 0.1 ng/mL.Mean recoveries ranged from 87.7% to 103.9% with relative standard deviations lower than 6.5%.The results indicated that the developed TFME method is simple,efficient,and cost effective.     

Effect of surface morphology on membrane fouling by humic acid with the use of cellulose acetate butyrate hollow fiber membranes

A serious problem faced during the application of membrane filtration in water treatment is membrane fouling by natural organic matter (NOM). The hydrophilicity, zeta potential and morphology of membrane surface mainly influence membrane fouling. The aim of the present study is to reveal the correlation between membrane surface morphology and membrane fouling by use of humic acid solution and to investigate the efficiency of backwashing by water, which is applied to restore membrane flux. Cellulose acetate butyrate (CAB) hollow fiber membranes were used in the present study. To obtain the membranes with various surface structures, membranes were prepared via both thermally induced phase separation (TIPS) and nonsolvent-induced phase separation (NIPS) by changing the preparation conditions such as polymer concentration, air gap distance and coagulation bath composition. Since the membrane material is the same, the effects of hydrophilicity and zeta potential on membrane fouling can be ignored. More significant flux decline was observed in the membrane with lower humic acid rejection. For the membranes with similar water permeability, the lower the porosity at the outer surface, the more serious the membrane fouling. Furthermore, the effect of the membrane morphology on backwashing performance was discussed.     

Selective separation of trace nickel(II) and gold(I) ions via hollow fiber supported liquid membrane enhanced by synergistic extractants D2EHPA/TBP

This work presents the selective and simultaneous separation of nickel (Ni²⁺) and gold ([Au(CN)₂]⁻) ions, in trace amounts, from alkaline solution via hollow fiber supported liquid membrane (HFSLM) technique. HFSLM is challengingly carried out in real rinse wastewater generated by the ENIG plating process. The influence of various chemical parameters, including the type of extractant and their concentrations, molar ratios of mixed extractant as well as type of strippant, are also studied. The organophosphorus extractant mixtures of D2EHPA and TBP provide a synergistic effect for target Ni²⁺ ions but has an antagonistic effect as regards the extraction of non-target [Au(CN)₂]⁻ ions. Compared to other inorganic acids, HCl is seen to be the most suitable strippant for the selective stripping. Results demonstrate that percentages of extraction and stripping of Ni²⁺ ions achieved 85.7 and 83.2%, respectively. In contrast, percentages of extraction and stripping of non-target [Au(CN)₂]⁻ ions attained 15.6 and 1.94%.     

Hollow fiber supported liquid membrane extraction coupled with thermospray flame furnace atomic absorption spectrometry for the speciation of Sb(III) and Sb(V) in environmental and biological samples

A new method of hollow fiber supported liquid membrane extraction (HF-SLME) coupled with thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS) for the speciation of Sb(III) and Sb(V) in environmental and biological samples has been developed. The method is based on the complex of Sb(III) with sodium diethyldithiocarbamate (DDTC). The formed hydrophobic complex is subsequently extracted into the lumen of hollow fiber, whereas Sb(V) is remained in aqueous solutions. The extraction organic phase was injected into TS-FF-AAS for the determination of Sb(III). Total Sb concentration was determined after reduction of Sb(V) to Sb(III) in the presence of l-cysteine and the extraction procedure mentioned above. Sb(V) was calculated by subtracting of Sb(III) from the total Sb. DDTC was used as complexing reagent. 1-Octanol was immobilized in the pores of the polypropylene hollow fiber as liquid membrane and also used as the acceptor solution. Some parameters that influenced extraction and determination were evaluated in detail, such as concentration of sodium diethyldithiocarbamate (DDTC), type of organic solvent, pH of samples, stirring rates, extraction time, as well as interferences. Under optimized conditions, a detection limit of 0.8 ng mL⁻¹ and an enrichment factor of 160 were achieved. The relative standard deviation (RSD) was 6.2% for Sb(III) (50 ng mL⁻¹, n = 5). The proposed method was successfully applied to the speciation of Sb(III) and Sb(V) in environmental and biological samples with satisfactory results.     

Simple hollow fiber renewal liquid membrane extraction method for pre-concentration of Cd(II) in environmental samples and detection by Flame Atomic Absorption Spectrometry

A hollow fiber renewal liquid membrane (HFRLM) extraction method to determine cadmium (II) in water samples using Flame Atomic Absorption Spectrometry (FAAS) was developed. Ammonium O,O-diethyl dithiophosphate (DDTP) was used to complex cadmium (II) in an acid medium to obtain a neutral hydrophobic complex (ML₂). The organic solvent introduced to the sample extracts this complex from the aqueous solution and carries it over the poly(dimethylsiloxane) (PDMS) membrane, that had their walls previously filled with the same organic solvent. The organic solvent is solubilized inside the PDMS membrane, leading to a homogeneous phase. The complex strips the lumen of the membrane where, at higher pH, the complex Cd-DDTP is broken down and cadmium (II) is released into the stripping phase. EDTA was used to complex the cadmium (II), helping to trap the analyte in the stripping phase. A multivariate procedure was used to optimize the studied variables. The optimized variables were: sample (donor phase) pH 3.25, DDTP concentration 0.05% (m/v), stripping (acceptor phase) pH 8.75, EDTA concentration 1.5 × 10⁻² mol L⁻¹, extraction temperature 40 °C, extraction time 40 min, a solvent mixture N-butyl acetate and hexane (60/40%, v/v) with a volume of 100 μL, and addition of ammonium sulfate to saturate the sample. The sample volume used was 20 mL and the stripping volume was 165 μL. The analyte enrichment factor was 120, limit of detection (LOD) 1.3 μg L⁻¹, relative standard deviation (RSD) 5.5% and the working linear range 2-30 μg L⁻¹.     

A non‐gassing electroosmotic pump with sandwich of poly(2‐ethyl aniline)‐Prussian blue nanocomposite and PVDF membrane

Low voltage, non‐gassing electroosmotic pump (EOP) was assembled with poly(2‐ethyl aniline) (EPANI)‐Prussian blue nanocomposite electrode and commercially available hydrophilic PVDF membranes. The nanocomposite material combines excellent oxidation/reduction capacity of EPANI with exceptional stability by shuttling of proton between Prussian blue nanoparticles and EPANI redox matrix. The flow rate was highly dependent on the electrode composition but it was linear with applied voltage. The flow rate at 5 V for different nanocomposite, EPANI, EPANI‐A, EPANI‐B, and EPANI‐C were 127.29, 187.41, 148.51, and 95.47 µL/min cm², respectively, which increases substantially with increase in the Prussian blue content. The obtained best electro osmotic flux was 43 µL/min/V/cm² for EPANI‐A. It was higher than most of the EOP assembled using polyquinone and polyanthraquinone redox polymers. The assembled EOP remained exceptionally stable until the electrode charge capacity was fully utilized. The best EOP produces a maximum stall pressure of 1.2 kPa at 2 V. These characteristics make it suitable for a variety of microfluidic/device applications.     

Hollow fiber liquid phase microextraction combined with electrothermal atomic absorption spectrometry for the speciation of arsenic (III) and arsenic (V) in fresh waters and human hair extracts

A new method of hollow fiber liquid phase microextraction (HF-LPME) using ammonium pyrrolidine dithiocarbamate (APDC) as extractant combined with electrothermal atomic absorption spectrometry (ETAAS) using Pd as permanent modifier has been described for the speciation of As(III) and As(V). In a pH range of 3.0-4.0, the complex of As(III)-APDC complex can be extracted using toluene as the extraction solvent leaving As(V) in the aqueous layer. The post extraction organic phase was directly injected into ETAAS for the determination of As(III). To determine total arsenic in the samples, first As(V) was reduced to As(III) by l-cysteine, and then a microextraction method was performed prior to the determination of total arsenic. As(V) assay was based on subtracting As(III) form the total arsenic. All parameters, such as pH of solution, type of organic solvent, the amount of APDC, stirring rate and extraction time, affecting the separation of As(III) from As(V) and the extraction efficiency of As(III) were investigated, and the optimized extraction conditions were established. Under optimized conditions, a detection limit of 0.12 ng mL⁻¹ with enrichment factor of 78 was achieved. The relative standard deviation (R.S.D.) of the method for five replicate determinations of 5 ng mL⁻¹ As(III) was 8%. The developed method was applied to the speciation of As(III) and As(V) in fresh water and human hair extracts, and the recoveries for the spiked samples are 86-109%. In order to validate the developed method, three certified reference materials such as GBW07601 human hair, BW3209 and BW3210 environmental water were analyzed, and the results obtained were in good agreement with the certified values provided.