Determination of cadmium, chromium, copper and lead in sediments and soil samples by electrothermal atomic absorption spectrometry using zirconium containing chemical modifiers.

A method for direct determination of cadmium, chromium, copper and lead in sediments and soil samples by electrothermal atomic absorption spectrometry using Zr, Ir, etylenediamine acetic acid (EDTA), Zr + EDTA, Ir + EDTA, Zr + Ir and Zr + Ir + EDTA as chemical modifiers in 0.5% (v/v) Triton X-100 plus 0.2% (v/v) nitric acid mixture used as diluent was developed. The effects of mass and mass ratio of modifiers on analytes in sample solutions were studied. The optimum masses and mass ratios of modifiers: 20 microg of Zr, 4 microg of Ir, 100 microg of EDTA and 20 microg of Zr + 4 microg of Ir + 100 microg of EDTA, were used to enhance the analyte signals. Pyrolysis and atomization temperatures, atomization and background absorption profiles, characteristic masses, and detection limits of analytes in samples were compared in the presence or absence of a modifier. The detection limits and characteristic masses of analytes in a 0.5% (m/v) dissolved sample (dilution factor of 200 ml g(-1)) obtained with Zr + Ir + EDTA are 8.0 ng g(-1) and 1.2 pg for Cd, 61 ng g(-1) and 4.3 pg for Cr, 32 ng g(-1) and 23 pg for Cu, and 3.4 ng g(-1) and 19 pg for Pb, respectively. The Zr + Ir + EDTA modifier mixture was found to be preferable for the determination of analytes in sediment and soil-certified and standard reference materials. Depending on the sample type, the percent recoveries of analytes were increased from 81 to 103% by using the proposed modifier mixture; the results obtained are in good agreement with the certified values.     

Cloud point extraction for the determination of cadmium and lead in biological samples by graphite furnace atomic absorption spectrometry

The phase-separation phenomenon of non-ionic surfactants occurring in aqueous solution was used for the extraction of Cd and Pb from digested biological samples. After complexation with O,O-diethyldithiophosphate (DDTP) in hydrochloric acid medium, the analytes are quantitatively extracted to the phase rich in the non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114) after centrifugation. Methanol acidified with 0.1 mol L⁻¹ HNO₃ was added to the surfactant-rich phase prior to its analysis by electrothermal atomic absorption spectrometry (ET AAS). The adopted concentrations for DDTP, Triton X-114 and hydrochloric acid were all optimized. Pyrolysis and atomization temperatures were optimized using the extracts and pyrolysis temperatures of 700 °C for both elements and atomization temperatures of 1400 and 1600 °C for cadmium and lead, respectively, were used without adding any modifier, which shows that considerable analyte stabilization is provided by the medium itself. A more detailed investigation was carried out to determine which components of the extract were responsible for the high thermal stability achieved and it revealed that the amount of DDTP added and the phosphorus content of the digested samples contributed significantly to this phenomenon. Detection limits (3σ_B) of 6 and 40 ng g⁻¹, along with enrichment factors of 129 and 18 for Cd and Pb, respectively, were achieved. The proposed procedure was applied to the analysis of five certified biological reference materials after microwave-assisted acid digestion in a mixture of H₂O₂ and HNO₃. Comparison with certified values was performed for accuracy evaluation, resulting in good agreement according to the t-test for a 95% confidence level. The high efficiency of cloud point extraction to carry out the determination of the studied analytes in complex matrices was, therefore, demonstrated.     

Simultaneous direct determination of aluminum, calcium and iron in silicon carbide and silicon nitride powders by slurry-sampling graphite furnace AAS.

A fast and accurate analytical method was established for the simultaneous direct determination of aluminum, calcium and iron in silicon carbide and silicon nitride powders by graphite furnace atomic absorption spectrometry using a slurry sampling technique and a Hitachi Model Z-9000 atomic absorption spectrometer. The slurry samples were prepared by the ultrasonication of silicon carbide or silicon nitride powders with 0.1 M nitric acid. Calibration curves were prepared by using a mixed standard solution containing aluminum, calcium, iron and 0.1 M nitric acid. The analytical results of the proposed method for aluminum, calcium and iron in silicon carbide and silicon nitride reference materials were in good agreement with the reference values. The detection limits for aluminum, calcium and iron were 0.6 microg/g, 0.15 microg/g and 2.5 microg/g, respectively, in solid samples, when 200 mg of powdered samples were suspended in 20 ml of 0.1 M nitric acid and a 10 microl portion of the slurry sample was then measured. The relative standard deviation of the determination of aluminum, calcium and iron was 5 - 33%.     

Alkali metal fluoride matrix modifiers for the determination of trace levels of silicon by graphite furnace atomic absorption spectrometry

A method is described for the determination of silicon by graphite-furnace atomic absorption spectrometry with alkali metal fluorides as matrix modifiers. Alkali metal fluorides react with silicon to produce metal hexafluorosilicates, which are stable at temperatures as high as 1120– 1300°C, depending on the particular metal used. At higher temperatures, alkali metal hexafluorosilicates decompose into the metal fluoride and silicon tetrafluoride. The subsequent gas-phase atomization of silicon tetrafluoride occurs rapidly, and produces clean, sharp absorption peaks. When used in conjunction with a zirconium-treated graphite tube, this method has a sensitivity of 50 pg Si at a confidence interval of 95%. There is no evidence of silicon carbide formation in the graphite tube, and very little evidence of any deterioration of the zirconium-treated surface, as demonstrated by the fact that more than 200 samples can be processed on a single graphite tube without a decrease in sensitivity or change in the baseline.     

On the re-assessment of the optimum conditions for the determination of platinum, palladium and rhodium in environmental samples by electrothermal atomic absorption spectrometry and microwave digestion

The experimental conditions for the determination of platinum, palladium and rhodium by graphite furnace atomic absorption spectrometry (GFAAS) are re-assessed. A certified material (BCR-723) was used as a working sample and analyzed using various extraction and atomization procedures in order to find the optimal experimental conditions that enable the quantitative and reproducible detection of platinum, palladium and rhodium in environmental matrices. Evidently, literature observations regarding the atomization conditions were proven fairly adequate. However, the provision of the optimum extraction conditions revealed several parameters that lie behind the reported uncertainties. The appropriate combination between extraction conditions and atomization programs afforded a considerable improvement in the recoveries and analytical features of platinum, palladium and rhodium determination with GFAAS. Cross-examination of the analytical data with various CRMs (certified reference materials) was used to validate the robustness of the method in heterogeneous matrices bearing different element levels. Under the optimum experimental conditions the method permits the determination at concentrations as low as (LOD(3S/N)) 1.9 ng g(-1), 0.45 ng g(-1) and 0.6 ng g(-1) for Pt, Pd and Rh, respectively affording recoveries in the range of 93-101%. The method was successfully applied to the assessment of Pt, Pd and Rh accumulation in real road dust and soil samples in Greece.     

Determination of Impurity Silicon in Anticancer Drug (Ge-132) by Electrothermally Atomised Atomic Absorption Spectrometry with Optical Temperature Control Accessory

The present paper describes the ashing and atomization processes in silicon analysis by electrothermally atomised atomic absorption spectrometry(EAAAS) with an uncoat-ed graphite tube, a pyrolytically coated graphite tube and a tungsten-coated graphitetube. The sensitivity and linear range of three graphite tubes were compared. By using optical temperature control accessory, the signals are enhanced by a factor of 2 and the germanium interferences in the determination of silicon are eliminated. The effects of time constant and carrier gas flow-rate on the determination of silicon were also tested. The sample can be directly analyzed in its aqueous solution without any pretreatment. The measurements of samples containing 0. 2 μg/mL and 0. 4 μg/mL silicon were run ten times and the variation coefficient is 4. 9% and 2.6%, respectively. The recovery tests for carboxyethyl germanium sesquioxide(Ge-132) synthesized and imported were performed, and the recoveries are 97. 0% and 110%, respectively. Keywords     

Analysis of phenoxyalkanoic acid herbicides and their phenolic conversion products in soil by microwave assisted solvent extraction and subsequent analysis of extracts by on-line solid-phase extraction-liquid chromatography

A multiresidue method for the determination of phenoxyalkanoic acid herbicides and their phenolic conversion products in soil was developed. The method was based on microwave-assisted solvent extraction (MASE) of soil samples by an aqueous methanolic mixture and subsequent analysis of extracts by automated solid-phase extraction followed by on-line high-performance liquid chromatography and diode array detection. MASE parameters (extraction temperature and time, composition of the extraction mixture and extraction volume) were optimized with respect to analyte recoveries. The method was validated with two types of soils containing 1.5 and 3.5% organic matter, respectively, both types containing fresh and aged residues of sought analytes. Under the selected analytical conditions when soils with fresh residues were analyzed all target analytes were recovered above 80% from the soil containing 1.5% organic matter, while limits of identification at the level of 20-40 ng/g were achieved. From the soil containing 3.5% organic matter the least polar phenolic analytes exhibited slightly reduced recoveries, while identification limits of 30-50 ng/g were achieved. Samples with aged residues exhibited reduced recoveries for some analytes, the reduction amounting up to 6-12% within 1 month of aging period depending on soil organic matter.     

Determination of trace impurities in titanium dioxide by direct solid sampling electrothermal atomic absorption spectrometry

A true direct solid sampling electrothermal atomic absorption spectrometry method with Zeeman-effect background correction (Analytik Jena ZEEnit 60 AAS) was developed for the determination of As, Cd, Hg, Pb, Sb and Zn in powdered titanium dioxide of pharmaceutical, food and cosmetics grade. The interaction of the titanium matrix and graphite surface of the sample carrier boat in a transversely heated graphite tube atomizer was investigated. Conversion of titanium dioxide to interfering TiO₂–TiC-liquid phase, running out the sampling boat, was observed at temperatures above 2000 °C. The temperature program was optimized accordingly for these volatile analytes in atomization and cleaning steps in order to prevent this interference and to prolong significantly the analytical lifetime of the boat to more than one thousand runs. For all elements, calibration by aqueous standard addition method, by wet-chemically analyzed samples with different content of analytes and/or by dosing one sample in different amounts, were proved as adequate quantification procedures. Linear dynamic calibration working ranges can be considerably expanded up to two orders of magnitude within one measurement run by applying three-field dynamic mode of the Zeeman background correction system. The results obtained by true direct solid sampling technique are compared with those of other independent, mostly wet-chemical methods. Very low limits of detection (3σ criterion) of true solid sampling technique of 21, 0.27, 24, 3.9, 6.3 and 0.9 ng g^− 1 were achieved for As, Cd, Hg, Pb, Sb and Zn, respectively.     

Trapping of hydride forming elements within miniature electrothermal devices. Part 2. Investigation of collection of arsenic and selenium hydrides on a surface and in a cavity of a graphite rod

The interaction of arsenic and selenium hydrides with bare and modified graphite was investigated by atomic absorption spectrometry and by radiotracer technique using ⁷⁵Se radionuclide in a laboratory made brass cylindrical chamber equipped with a vertical quartz tube torch for supporting miniature hydrogen diffusion flame atomizer. Strong interaction was observed at elevated temperatures above 800 °C. In contrast to the very often-reported data for conventional graphite tube atomizers, this high temperature interaction was also accompanied by a pronounced trapping of analytes at elevated temperatures close to 1100–1200 °C when modified graphite was used. Comparing modifiers tested (Ir, Pt and Rh), iridium appeared the only useful permanent modifier. Among various graphite-rod traps designed, the most efficient trapping of analytes was achieved in a graphite cavity. The net selenium trapping efficiencies of approximately 53% and 70% were found by radiotracer technique for the iridium-treated graphite surface and the iridium-treated graphite cavity, respectively. In contrast to the molybdenum surface, bare graphite did not exhibit any significant trapping effect. Trapping isotherms obtained at different temperatures displayed non-linear course in the range up to the upper limit of the analytical relevance of 100 ng of an analyte, indicating a limited trapping capacity of the modified graphite surface and the same trapping mechanism at low and elevated temperatures applied (300–1300 °C). Radiography experiments with ⁷⁵Se radiotracer showed that a major part of selenium was collected within the small cavity of the graphite rod and that selenium was also deposited after the trapping and vaporization steps in the trap chamber and on the quartz tube wall of the burner. Complementary experiments performed with the conventional transversally heated graphite tube and with bare and thermally shielded injection capillaries for hydride introduction, showed that the pronounced trapping effect could not be observed at elevated temperatures in conventional systems equipped with the bare capillary. The losses of analytes in the non-shielded bare introduction capillary exposed to the heat decrease the transport efficiency of hydrides into the graphite tube, and consequently they cause reduction of the overall trapping efficiency at elevated temperatures.     

Spectrophotometric determination of etodolac in pure form and pharmaceutical formulations

Background

A routine method for the quantification of beryllium in biological fluids is essential for the development of a chelation therapy for Chronic Beryllium Disease (CBD). We describe a procedure for the direct determination of beryllium in undigested micro quantities of human blood and serum using graphite furnace atomic absorption spectrometry. Blood and serum samples are prepared respectively by a simple 8-fold and 5-fold dilution with a Nash Reagent. Three experimental setups are compared: using no modifier, using magnesium nitrate and using palladium/citric acid as chemical modifiers.

Results

In serum, both modifiers did not improve the method sensitivity, the optimal pyrolysis and atomization temperatures are 1000°C and 2900°C, respectively. In blood, 6 μg of magnesium nitrate was found to improve the method sensitivity. The optimal pyrolysis and atomization temperatures were 800°C and 2800°C respectively.

Conclusion

In serum, the method detection limit was 2 ng l^-1, the characteristic mass was 0.22 (± 0.07) pg and the accuracy ranged from 95 to 100%. In blood, the detection limit was 7 ng l^-1, the characteristic mass was 0.20 (± 0.02) pg and the accuracy ranged from 99 to 101%.     

Graphite furnace for alternative combination with d.c. arc or inductively coupled plasma. Introduction and analysis of solid samples

Summary A graphite furnace and d.c. arc combined source with the use of halogenating atmosphere in the furnace is described. The construction makes possible the introduction and analysis of both liquid and solid samples at minimum risk of contamination. Spectrographic detection resulted in background equivalent mass values below 10 ng for 22 from 36 elements applied in solution (Ar + CCl₄ atmosphere and NaCl matrix). The intensity-time profiles indicated high rates of distillation of the impurities (including B, Cr, Hf, Mo, Ti, V, W and Zr) from silicon carbide and silicon nitride samples in the first 40 s of heating under chlorination (CCl₄ vapour). Two versions of the exit part of the furnace are described for coupling to an ICP source; one of them has been used for the determination of titanium in alumina (spectrometric detection). Standardization with solution standards for solid sample analysis was unsuccessful. Based on the analytical curve obtained with variable amounts of solid standards (5–20 mg), a detection limit of 0.32 g/g Ti was found for 20 mg alumina.     

用ETV-ICP-MS研究Cr、Ni、Zr、Nb、Yb在石墨炉中的蒸发/原子化机理

本文以电热蒸发电感耦合等离子体质谱（ETV-ICP-MS）为手段,探讨了Cr、Ni、Zr、Nb和Yb在石墨炉中的蒸发/原子化机理;比较了不同化学改进剂存在条件下,Cr、Ni、Zr、Nb和Yb的蒸发行为和在石墨炉原子吸收（GFAAS）中的原子化行为;考察了石墨炉温度和ICP功率等实验参数对上述元素发射强度及轮廓的影响.结果表明,Pd和Mg化合物的存在对Cr、Ni、Zr、Nb和Yb的蒸发/原子化行为没有明显的化学改进作用;然而,以聚四氟乙烯（PTFE）为化学改进剂时,可显著改善Cr、Ni、Zr、Nb和Yb的蒸发行为,避免难熔碳化物的形成,降低待测物的蒸发温度;对Cr和Ni的GFAAS信号强度略有增强;但是,由于Yb、Nb和Zr氟化物的离解键能很高,难以离解/原子化,PTFE的存在反而降低了Yb、Nb和Zr在GFAAS中的信号强度.     

Kinetics of indium atomization from different atomizer surfaces in electrothermal atomic absorption spectrometry (ETAAS)

The kinetic parameters of indium atomization in electrothermal atomic absorption spectrometry (ETAAS) have been determined by a newly proposed method. Effect of the atomizer surface and the palladium modifier on the kinetics of indium atomization has been investigated. The mechanisms of indium atomization seem to be identical for the pyrolytically coated graphite and the uncoated graphite tubes, i.e. the rate-limiting step for the atomization changes from a first order kinetics at lower temperatures into a nearly 1/3 order kinetics at higher temperatures, which may suggest that the analyte moves from a dispersed state to agglomates with increasing temperature. However, for the zirconium coated graphite tube, the atomization of indium is controlled by a single mechanism with the kinetic order of near 2/3 and the activation energy of 186 ± 13 kJ/mol. Relatively weak indium—zirconium carbide interactions and the release of indium from the sphere of molten indium metal on the zirconium coated surface are suggested. In the presence of palladium, a simple mechanism, i.e. the release of indium from the solid solution of the In and the Pd on the pyrolytically coated graphite surface, is proposed to account for the observed first order kinetics and the activation energy of 421 ± 27 kJ/mol.     

Application of colloidal palladium modifier for the determination of As, Sb and Pb in a spiked sea water sample by electrothermal atomic absorption spectrometry

Colloidal palladium was used as a chemical modifier for analysis of complex samples by electrothermal atomic absorption spectrometry. In order to demonstrate high potential of the modifier, optimization of the time–temperature program of the atomizer was limited with only pyrolysis and atomization temperatures. Fixed palladium modifier masses were applied (6 μg for pure analyte solutions and 15 μg for matrix-containing solutions). It was shown that in the presence of colloidal palladium, interference-free determinations of As, Sb and Pb are possible up to at least 450 μg of chloride ion, or 40 μg of sulfate ion (as their sodium salts) in the atomizer. Colloidal palladium was used for the direct determination of As, Sb and Pb in a spiked sea water sample (from Bosphorus channel near Istanbul) by means of the calibration graphs prepared with pure analyte solutions. The detection limits for As, Sb and Pb in a sea water matrix calculated according to 2σ criteria are 5.4, 3.6 and 1.1 ng ml⁻¹, respectively (for sample volume 10 μl). In unspiked sea water, the contents of As, Sb and Pb were found to be below the detection limits. Recoveries of spiked analytes (25 and 50 ng ml⁻¹) were in the region of 98–112% depending on the nature of analyte and the concentration of spike.     

Direct determination of Cr and Cu in urine samples by electrothermal atomic absorption spectrometry using ruthenium as permanent modifier (R1)

In this study Ru, deposited thermally on an integrated platform pyrolytic graphite tube, is proposed as a permanent modifier for the determination of Cu and Cr in urine samples by electrothermal atomic absorption spectrometry. The samples were diluted 1:1 with nitric acid (1% v/v). Pyrolysis and atomization temperatures for spiked urine samples were 1,100 degrees C and 1,900 degrees C respectively for Cu, and 1,400 degrees C and 2,500 degrees C respectively for Cr. For comparison purposes, the conventional modification with Pd+Mg was also studied. The sensitivity for Ru as permanent modifier was higher for the two analytes. The characteristic masses were 7.3 and 17.7 for Cr and Cu. The detection limits (3sigma) were 0.22 and 0.32 microg/L, for Cr and Cu, respectively. Good agreement was obtained with certified urine samples for the two elements.     

Simultaneous determination of copper and iron by second derivative spectrophotometry using mixtures of ligands

A highly sensitive and selective second derivative spectrophotometric method has been developed for the determination of copper and iron in mixtures. The method is based on the separation of the analytes by liquid-liquid extraction as picrate ion pairs. Iron-picrate, reacts in the organic phase of DCE with 5-phenyl-3-(4-phenyl-2-pyridinyl)-1,2,4-triazine (PPT). Similarly the copper-picrate reacts with 2,9-dimethyl-4,7-diphenyl-1,10-phenantroline (bathocuproine). The extracts were evaluated directly by derivative spectrophotometric measurement, using the zero-crossing approach for determination of copper and graphic method for iron. Iron and copper were thus determined in the ranges 8-120 ng ml(-1) and 8-125 ng ml(-1), respectively, in the presence of one another. The detection limits achieved (3sigma) were 2.9 ng ml(-1) of iron and 2.8 ng ml(-1) of copper. The relative standard deviations were in all instances less than 2.1%. The proposed method was applied to the determination of both analytes in river and tap water and the results were consistent with those provided by the AAS standard method.     

Direct As,Bi, Ge,Hg and Se(IV) cold vapor/hydride generation from coal fly ash slurry samples and determination by electrothermal atomic absorption spectrometry

Direct cold vapor and hydride generation procedures for As, Bi, Ge, Hg and Se(IV) from aqueous slurry of coal fly ash samples have been developed by using a batch mode generation system. Ir-treated graphite tubes have been used as a preconcentration and atomization medium of the vapors generated. A Plackett–Burman experimental design has been used as a strategy for evaluation of the effects of several parameters affecting the vapor generation efficiency from solid particles, vapor trapping and atomization efficiency from Ir-treated graphite tubes. The effects of parameters such as hydrochloric acid and sodium tetrahydroborate, argon flow rate, trapping and atomization temperatures, trapping time, acid solution volume and mean particle size have been investigated. The significant parameters obtained (trapping and atomization temperatures for As and Ge; trapping temperature and trapping time for Bi; argon flow rate and atomization temperature for Se) have been optimized by 2²+star central composite design. For Hg, the trapping temperature has been also significant. Optimum values of the parameters have been selected for the development of direct cold vapor/hydride generation methods from slurry particles. The accuracy of methods have been verified by using NIST-1633a coal fly ash certified reference material. Absolute detection limits of 11.5, 48.0, 600, 55.0 and 11.0 ng l⁻¹ for As, Bi, Ge, Hg and Se have been achieved, respectively. A particle size less than 50 μm has shown to be adequate to obtain total cold vapor/hydride generation of metals content in the aqueous slurry particles.     

多孔SiC纳米片的原位合成及光催化性能

以可膨胀石墨作为原材料,通过高温膨化和机械砂磨得到石墨薄片,再以石墨薄片作为模板合成了不同比表面积的碳化硅纳米片(SiCNSs)。探究了比表面积对SiCNSs光催化制氢性能的影响。结果表明,SiCNSs的比表面积对其产氢性能影响显著,提高光催化剂的比表面积有利于增强其产氢活性。SiCNSs的最大比表面积可达149 m²·g^-1,其光解水产氢速率为51.0μL·g^-1·h^-1。在对石墨薄片和SiCNSs结构、形貌分析的基础上,提出了以石墨薄片为模板原位生成SiCNSs的形成机理,该过程主要遵循气固反应机制。高温下,气态的SiO和Si与石墨薄片反应生成SiCNSs,产物较好地继承了石墨薄片的片状结构。大尺寸石墨片上未反应部分除碳之后留下了大量纳米尺寸穿孔,使得所生成SiC的比表面积反而比小尺寸石墨片产物的高。     

Trace analysis of high-purity graphite by LA-ICP-MS

Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been established as a very efficient and sensitive technique for the direct analysis of solids. In this work the capability of LA-ICP-MS was investigated for determination of trace elements in high-purity graphite. Synthetic laboratory standards with a graphite matrix were prepared for the purpose of quantifying the analytical results. Doped trace elements, concentration 0.5 microg g(-1), in a laboratory standard were determined with an accuracy of 1% to +/- 7% and a relative standard deviation (RSD) of 2-13%. Solution-based calibration was also used for quantitative analysis of high-purity graphite. It was found that such calibration led to analytical results for trace-element determination in graphite with accuracy similar to that obtained by use of synthetic laboratory standards for quantification of analytical results. Results from quantitative determination of trace impurities in a real reactor-graphite sample, using both quantification approaches, were in good agreement. Detection limits for all elements of interest were determined in the low ng g(-1) concentration range. Improvement of detection limits by a factor of 10 was achieved for analyses of high-purity graphite with LA-ICP-MS under wet plasma conditions, because the lower background signal and increased element sensitivity.     

Trace analysis of diethylstilbestrol, dienestrol and hexestrol in environmental water by Nylon 6 nanofibers mat-based solid-phase extraction coupled with liquid chromatography-mass spectrometry

A simple, rapid and sensitive method for the determination of diethylstilbestrol (DES), dienestrol (DE) and hexestrol (HEX) was developed by using the Nylon 6 nanofibers mat-based solid-phase extraction (SPE) coupled with liquid chromatography-tandem mass spectrometry (LC-MS). These estrogens were separated within 8 min by LC using an ODS column and methanol/water (80/20, v/v) at a flow rate of 1.0 mL min(-1). Electrospray ionization conditions in the negative ion mode were optimized for MS detection of the estrogens. Under the optimum SPE conditions, all target analytes in 50 mL environmental water samples can be completely extracted by 1.5 mg Nylon 6 nanofibers mat at flow rate of 3.0 mL min(-1) and easily eluted by passage of 500 μL mobile phase. By using the novel SPE-LC/MS method, good linearity of the calibration curve (r(2) ≥ 0.9992) was obtained in the concentration range from 0.10 ng L(-1) to 1.0 mg L(-1) (except for DE which was 0.20 ng L(-1) to 1.0 mg L(-1)) for all analytes examined. The limits of detection (S/N = 3) of the three estrogens ranged from 0.05 ng L(-1) to 0.10 ng L(-1). This method was applied successfully to the analysis of environmental water samples without any other pretreatment and interference peaks. Several water samples were collected from Jinchuan River and Xuanwu Lake, and in Jinchuan River water DES was detected at 0.13 ng L(-1). The recoveries of estrogens spiked into tap water were above 98.2%, and the relative standard deviations were below 4.78%.