Simultaneous determination of endocrine disrupting phenolic compounds and steroids in water by solid-phase extraction-gas chromatography-mass spectrometry

A solid-phase extraction (SPE)-gas chromatography (GC)-mass spectrometry (MS) analytical method for the simultaneous separation and determination of endocrine disrupting chemicals (EDCs) from water samples is described in detail. Important and contrasting EDCs including estrone, 17beta-estradiol, 17beta-ethynylestradiol, 16beta-hydroxyestrone, 4-nonylphenol, bisphenol A and 4-tert-octylphenol were selected as the target compounds. The SPE technique, followed by the derivatisation with bis (trimethylsilyl) trifluoroacetamide was used for the extraction recoveries of target compounds from water samples. A number of parameters that may affect the recovery of EDCs, such as the type of SPE cartridges, eluents, as well as water properties including pH value, and concentration of salts and humic substances were investigated. It is shown that the Oasis cartridges produced the best recoveries of target EDCs while ethyl acetate was efficient in eluting EDCs from SPE cartridges. The recovery of some EDCs was enhanced by the addition of salt, but reduced by the increase in pH value and humic acid concentration. The optimised method was further verified by performing spiking experiments in natural river water and seawater matrices, with good recovery and reproducibility for all the selected compounds. The established method was successfully applied to environmental water samples from East and West Sussex, UK, for the determination of the target EDCs.     

Optimisation of a headspace-solid-phase micro-extraction method for simultaneous determination of organometallic compounds of mercury,lead and tin in water by gas chromatography–tandem mass spectrometry

In this work, a headspace-solid-phase micro-extraction (HS-SPME) combined with gas chromatography–mass spectrometry (GC–MS) method for multielemental speciation of organometallic compounds of mercury, lead and tin in water samples was upgraded by the introduction of tandem mass spectrometry (MS/MS) as detection technique. The analytical method is based on the ethylation with NaBEt₄ and simultaneous headspace-solid-phase micro-extraction of the derivative compounds followed by GC–MS/MS analysis. The main experimental parameters influencing the extraction efficiency such as derivatisation time, extraction time and extraction temperature were optimized. The overall optimum extraction conditions were the following: a 50 μm/30 μm divinyl-benzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) SPME fibre, 150 min derivatisation time, 15 min extraction time, sample agitation at 250 rpm and 40 °C extraction temperature. The analytical characteristics of the HS-SPME method combined with GC–MS and GC–MS/MS were evaluated. The combination of both techniques HS-SPME and GC–MS/MS allowed to attain lower limits of detection (4–33 ng l⁻¹) than those obtained by HS-SPME–GC–MS (17–45 ng l⁻¹). The proposed method presented good linear regression coefficients (r² > 0.9970) and repeatability (4.8–21.0%) for all the compounds under study. The accuracy of the method measured as the average percentage recovery of the compounds in spiked river water and seawater samples was higher than 80% for all the compounds studied, except for monobutyltin in the river water sample. A study of the uncertainty associated with the analytical results was also carried out.     

Simultaneous determination of inorganic mercury and methylmercury compounds in natural waters

The purpose of the present work was to develop a simple, rapid, sensitive and accurate method for the simultaneous determination of inorganic mercury (Hg(2+)) and monomethylmercury compounds (MeHg) in natural water samples at the pg L(-1) level. The method is based on the simultaneous extraction of MeHg and Hg(2+)dithizonates into an organic solvent (toluene) after acidification of about 300 mL of a water sample, followed by back extraction into an aqueous solution of Na(2)S, removal of H(2)S by purging with N(2), subsequent ethylation with sodium tetraethylborate, room temperature precollection on Tenax, isothermal gas chromatographic separation (GC), pyrolysis and cold vapour atomic fluorescence spectrometric detection (CV AFS) of mercury. The limit of detection calculated on the basis of three times the standard deviation of the blank was about 0.006 ng L(-1) for MeHg and 0.06 ng L(-1) for Hg(2+)when 300 mL of water was analysed. The repeatability of the results was about 5% for MeHg and 10% for Hg(2+). Recoveries were 90-110% for both species.     

Simultaneous speciation of mercury and butyltin compounds in natural waters and snow by propylation and species-specific isotope dilution mass spectrometry analysis

A robust method has been developed for simultaneous determination of mercury and butyltin compounds in aqueous samples. This method is capable of providing accurate results for analyte concentrations in the picogram per liter to nanogram per liter range. The simultaneous determination of the mercury and tin compounds is achieved by species-specific isotope dilution, derivatization, and gas chromatography–inductively coupled plasma mass spectrometer (GC–ICP–MS). In derivatization by ethylation and propylation, reaction conditions such as pH and the effect of chloride were carefully studied. Ethylation was found to be more sensitive to matrix effects, especially for mercury compounds. Propylation was thus the preferred derivatization method for simultaneous determination of organomercury and organotin compounds in environmental samples. The analytical method is highly accurate and precise, with RSD values of 1 and 3% for analyte concentrations in the picogram per liter to nanogram per liter range. By use of cleaning procedures and SIDMS blank measurements, detection limits in the range 10–60 pg L^–1 were achieved; these are suitable for determination of background levels of these contaminants in environmental samples. This was demonstrated by using the method for analysis of real snow and seawater samples. This work illustrates the great advantage of species-specific isotope dilution for the validation of an analytical speciation method—the possibility of overcoming species transformations and non-quantitative recovery. Analysis time is saved by use of the simultaneous method, because of the use of a single sample-preparation procedure and one analysis.     

Simultaneous speciation of methylmercury and butyltin species in environmental samples by headspace-stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry

In this work, making use of experimental designs, headspace-stir bar sorptive extraction (HS-SBSE) followed by thermal desorption (TD) coupled to a gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of mercury and tin organometallic compounds present in surface water, sediment and biological tissue was optimized. All solid samples require a previous extraction typically done with diluted HCl or KOH/methanol solutions, and the derivatization, in all the cases, of the organometallic compounds with NaBEt(4). As a consequence, the preconcentration step was carried out in a 0.1 mol L(-1) HOAc/NaOAc buffer solution, with 0.1% (m/v) of NaBEt(4), without the addition of NaCl as a salting out reagent, and with the stir bar (20 mm x 1 mm) located in the headspace (HS). In addition, the desorption step required the following conditions: 250 degrees C (desorption temperature), 15 min (desorption time), 14.1 psi (approximately 97.2 kPa) (vent pressure) and 75 mL min(-1) (vent flow). Finally, to assure the extraction of all the analytes under equilibrium, 5h are required. Inorganic mercury (Hg(2+)) and tripropyltin (TPrT) were used as internal standards to correct for variations in the extraction, derivatization and detection steps. The resulting method provides precise (4-17%) and accurate (against four certified reference materials) results in the ng L(-1) and pg g(-1) range concentrations with recoveries within 80-120% for water samples. The proposed methodology is currently applied in the speciation analysis of specimens obtained in different estuarine sites of the Basque Coast.     

Determination of natural and synthetic estrogenic compounds in coastal lagoon waters by HPLC-electrospray-mass spectrometry

A new analytical method was developed for the simultaneous determination of estrogenic compounds of natural (estradiol, estriol, estrone) and synthetic origin, both steroidal (ethinylestradiol, mestranol) and non-steroidal (benzophenone, bisphenol-A, diethylstilbestrol, octylphenol, nonylphenol, nonylphenol monoethoxylate carboxylate), in environmental aqueous samples by high-performance liquid chromatography coupled with ion trap-mass spectrometry via electrospray interface (HPLC-ESI-IT-MS). Quantitative MS detection was performed in the negative mode for all compounds except mestranol and benzophenone, which were detected under positive ion conditions. Very low method detection limits (MDLs), between 0.1 and 2.6?ng/L, were achieved in coastal lagoon water samples, while the developed solid-phase-extraction (SPE) procedure permitted simultaneous recovery of all analytes from spiked water samples with yields >70% (7–11 RSD%), except estriol and benzophenone, which were recovered with 60% (9 RSD%) and 50% (11 RSD%) yields, respectively. The proposed method was applied to the analysis of Venice (Italy) lagoon waters, where average concentrations of selected compounds in the 2.8–33?ng/L concentration range were found.     

固相萃取柱上衍生气相色谱-质谱法测定水中烷基酚

以烷基酚(APs)主要降解产物辛基酚(4-t-OP)、壬基酚(4-n-NP)为研究对象,建立了固相萃取(SPE)柱上衍生化、气相色谱-质谱(GC-MS)法测定水中APs的分析方法。以C18柱为固相萃取柱、N,O-(三甲基硅)三氟乙酰胺(BSTFA)为硅烷化试剂,设计五因素四水平正交实验L16(45),对衍生化影响因素、衍生化溶剂、衍生化时间以及SPE主要影响因素pH值、盐度和洗脱剂进行优化;在优化条件下,方法的回收率(高于80%)和重现性(RSD低于10%)结果令人满意,4-t-OP和4-n-NP的仪器检出限分别为3.35ng/L和6.38ng/L。采用建立的方法,回收率略高于传统的SPE萃取衍生法,具有有机溶剂用量少,方法简单快速、灵敏度高的特点,适用于河水和海水中痕量烷基酚的快速测定。     

固相萃取高效液相色谱质谱法测定海水中烷基酚和烷基酚聚氧乙烯醚

建立了固相萃取-高效液相色谱-电喷雾质谱分析海水中辛基酚、壬基酚、辛基酚聚氧乙烯醚和壬基酚聚氧乙烯醚的方法。海水样品经C18固相萃取柱富集净化后,以甲醇-水为流动相,在Hypersil GOLD色谱柱上分离,电喷雾质谱在选择离子监测模式下分析目标化合物,采用外标法定量。结果表明,4种化合物的平均加标回收率为59.6%～104.4%,相对标准偏差(RSD, n=3)为1.0%～13.5%;仪器检出限为0.08～3 μg/L。将本方法用于大连海岸6个采样点海水中辛基酚、壬基酚、辛基酚聚氧乙烯醚和壬基酚聚氧乙烯醚的检测发现,样品中壬基酚和壬基酚聚氧乙烯醚均有检出,且油港和海港附近海水中的含量较高。     

Simultaneous determination of the endocrine disrupting compounds nonylphenol, nonylphenol ethoxylates, triclosan and bisphenol A in wastewater and sewage sludge by gas chromatography-mass spectrometry

An integrated analytical method for the simultaneous determination of 4-n-nonylphenol (4-n-NP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), bisphenol A (BPA) and triclosan (TCS) in wastewater (dissolved and particulate phase) and sewage sludge was developed based on gas chromatography-mass spectrometry. Chromatographic analysis was achieved after derivatization with bis(trimethylsilyl)trifluoroacetamide (BSTFA). Extraction from water samples was performed by solid-phase extraction (SPE). The optimization of SPE procedure included the type of sorbent and the type of the organic solvent used for the elution. Referred to solid samples, the target compounds were extracted by sonication. In this case the optimization of the extraction procedure included the variation of the amount of the extracted biomass, the duration and the temperature of sonication and the type of the extraction organic solvent. The developed extraction procedures resulted in good repeatability and reproducibility with relative standard deviations (RSDs) less than 13% for all the tested compounds for both types of samples. Satisfactory recoveries were obtained (>60%) for all the compounds in both liquid and solid samples, except for 4-n-NP, which gave recoveries up to 35% in wastewater samples and up to 63% in sludge samples. The limits of detection (LODs) of the target compounds varied from 0.03 (4-n-NP) to 0.41 microg l(-1) (NP2EO) and from 0.04 (4-n-NP) to 0.96 microg kg(-1) (NP2EO) for liquid and solid samples, respectively. The developed methods were successfully applied to the analysis of the target compounds in real samples.     

Determination of selected natural hormones and endocrine disrupting compounds in domestic wastewater treatment plants by liquid chromatography electrospray ionization tandem mass spectrometry after solid phase extraction

A new analytical method for the simultaneous determination of two natural hormones (progesterone and estrone) and two selected endocrine disrupter compounds (EDCs) (diltiazem and carbamazepine (Cbz)) was developed by liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) after pre-concentration with solid phase extraction (SPE). Influent and effluent samples taken from five different wastewater treatment plants throughout Turkey namely Hurma/Antalya, Lara/Antalya, Kemer-1 and Kemer-2 and METU/Ankara were analyzed for their EDCs contents under the optimum conditions. All of the parameters in the pre-concentration step were optimized and the best recoveries for all compounds of interest were achieved at pH 7 (about 100%). Progesterone was not detected in any of the treatment plants while diltiazem was found in all samples with the exception of Lara effluent.     

超高效液相色谱-串联质谱法同时测定制药废水中10种抗生素

建立了一种同时测定制药废水中3类10种抗生素的超高效液相色谱-串联质谱分析方法。水样用固相萃取柱富集净化,通过比较在不同的固相萃取柱和洗脱液等条件下水样中目标物的回收率,优化了前处理方法。采用Agilent C18色谱柱(75 mm×2.1 mm, 2.7 μm),以0.2%(v/v)甲酸水溶液和乙腈为梯度洗脱的流动相,在电喷雾-多反应监测模式下进行定性定量分析。实验结果表明:在0.1~1000 μg/L范围内,6种氨基糖苷类抗生素、螺旋霉素及3种氟喹诺酮类抗生素的峰面积与质量浓度的线性关系良好(r² > 0.995),方法检出限为0.07~4.37 ng/L,定量限为0.22~14.55 ng/L;目标抗生素的加标水平为0.002~40 μg/L时,平均回收率为50.4%~114.1%,相对标准偏差均不高于9.89%(n=3)。基于上述方法,对江苏省某制药厂废水中相关物质进行检测,在各废水处理单元中检出3种目标抗生素,质量浓度范围为0.46~1033.60 μg/L。该方法准确可靠、灵敏度高,适用于制药厂废水中氨基糖苷类抗生素、螺旋霉素和氟喹诺酮类抗生素的检测。     

Determination of trace benzene derivatives in aqueous samples by ultrasonic enhanced hollow fiber liquid-phase microextraction prior to gas chromatography

A new method was developed for the determination of trace compounds in water samples using ultrasonic-enhanced hollow fiber liquid-phase microextraction (U-HF-LPME). The ultrasonic radiation, which produces mechanical vibration and ultrasonic cavitation, could be used for accelerating the diffusion mass transfer process. Thus, ultrasonic was introduced into the HF-LPME procedure to enhance the mass-transfer rate during the aqueous and extraction solvent phases. Experimental parameters such as the extraction solvent, the extraction time, the ultrasonic frequency and power, the extractant volume, and ionic strength of the sample were assessed and optimized. Under optimal conditions, HF-LPME was achieved within 10 min. The high enrichment factor in the range of 120-666 and a good relative recovery in the range of 97-103% were evaluated with the relative standard deviations (RSDs, n = 5) of 0.3-7.0%. The limit of detection was in the range of 0.8-3.0 μg/L. The method was applied to the analysis of groundwater, lake water, and seawater. The results showed that the method can determine trace benzene derivatives in real samples with RSD values of 1.1-4.2%. The results demonstrated that U-HF- LPME is a rapid, accurate, and effective sample preparation method, and could be successfully applied for the determination of trace compounds in analytical chemistry.     

Extraction and determination of phenolic derivatives in water samples by using polyoxyethylene surfactants and liquid chromatography with photodiode array detection

Methodology based on the cloud-point phenomenon was applied to the comparative study of 3 different polyoxyethylene nonionic surfactants in order to extract and preconcentrate a group of phenolic derivatives in water samples; these phenolic compounds, which were determined by liquid chromatography with UV detection, included 11 pollutants given priority by the U.S. Environmental Protection Agency. The optimum conditions for the extraction and preconcentration of phenolic compounds were established for each surfactant. The surfactant that gave the best extraction and preconcentration of the analytes under study was polyoxyethylene 6 lauryl ether (C12E6) with detection limits of <3.5 microg/L for all the phenolic compounds tested. The method was applied to seawater and depurated wastewater samples.     

Silica gel-immobilized-dithioacetal derivatives as potential solid phase extractors for mercury(II)

Dithioacetal derivatives with different para-substituents, XH, CH(3), OCH(3), Cl and NO(2) were synthesized and chemically immobilized on the surface of silica gel for the formation of five newly synthesized silica gel phases (I-V). Characterization of the silica gel surface modification by the organic compounds was accomplished by both the surface coverage determination as well as the infrared spectroscopic analysis. The metal sorption properties of the silica gel phases were studied to evaluate their performance toward metal-uptake, extraction and selective extraction processes of different metal ions from aqueous solutions based on examination of the various controlling factors. The studied and evaluated factors are the pH effect of metal ion solution on the metal capacity values (mmol g(-1)), equilibration shaking time on the percent extraction as well as the structure and substituent (X) effects on the determined mmol g(-1) values. The results of these studies revealed a general rule of excellent affinity of these silica gel phases-immobilized-dithioacetal derivatives for selective extraction of mercury(II) in presence of other interfering metal ions giving rise to a range of 94-100% extraction of the spiked mercury(II) in the metal ions mixture. The potential application of the newly synthesized silica gel phases (I-V) for selective extraction of mercury(II) from two different natural water samples, namely sea and drinking tap water, spiked with 1.0 and 10.0 ng ml(-1) mercury(II) were also studied by column technique followed by cold vapour atomic absorption analysis of the unretained mercury(II). The results indicated a good percent extraction and removal (90-100+/-3%) of the spiked mercury(II) by all the five silica gel phases. In addition, insignificant contribution by the matrix effect on the processes of selective solid phase extraction of mercury(II) from natural water samples was also evident.     

C_(18)膜萃取/液相色谱-质谱联用法测定极地水体中有机磷酸酯

建立了C_(18)膜萃取/液相色谱-质谱联用技术测定极地水体中10种有机磷酸酯(OPEs)的方法。根据优化后的样品前处理及仪器方法,利用C_(18)膜富集4 L水体中的10种OPEs,经二氯甲烷超声提取,在电喷雾正离子模式下,采用选择反应监测(SRM)模式进行分析,线性相关系数为0.994 4~0.999 9。10种OPEs的加标回收率为64.1%~115%,方法检出限为0.08~0.55 ng/L。该方法适用于极地水体中10种OPEs的分析,利用该方法对北极水体样品中的10种OPEs进行检测,测得冰川融水中∑OPEs的质量浓度为0.64~6.64 ng/L,海水中∑OPEs的质量浓度为0.09~2.03 ng/L。     

Simultaneous determination of arsenic, selenium and mercury in foodstuffs by chemical vapour generation inductively coupled plasma optical emission spectroscopy

A procedure for the simultaneous determination of arsenic, selenium and mercury in foodstuffs has been developed. After a two-step microwave-assisted wet digestion in closed vessels, using concentrated nitric acid and hydrogen peroxide, the solution was analysed by inductively coupled plasma multichannel-based emission spectrometry using chemical vapour generation as the sample introduction system. All steps of the procedure, such as solid sample dissolution, pre-reduction to the suitable oxidation state, vapor generation, transport and atomization have been designed and optimised taking into account the concomitant presence of all the analytes considered. Temporal variation of analytical signals as well as interfering effects due to transition elements were also studied. Under the optimised operating conditions, the achieved detection limits for the simultaneous determination of arsenic, selenium and mercury in foodstuffs were 0.006, 0.023 and 0.018 microg g(-1), respectively, allowing their determination in real samples. Precision of the analytical procedure was 6.8% for arsenic, 5.2% for selenium and 7.7% for mercury (n=7). The accuracy and reliability of the method was verified by the analysis of both standard reference materials (rice flour and spinach leaves) and real samples (natural and Se-enriched rice).     

Model reactions for abiotic mercury(II) methylation: Kinetics of methylation of mercury(II) by mono-, di-, and tri-methyltin in seawater

The usual presence of mercury(II) with monodi-, and tri-methyltin in water, sediments, and plants in estuarine environments suggests possible abiotic formation of methylmercury via methyl transfer from methyltin compounds. Kinetics studies of reactions between mercury(II) and methyltin compounds under pseudo-first-order conditions in seawater show that relative rate of methylmercury formation under the same conditions are: monomethyltin <trimethyltin> dimethyltin. This order is explainable mainly by the speciation and charge of methyltin compounds in seawater and by the existence of mercury(II) as a tetrachloro anion. A factorial experiment with the variables pH and salinity (seawater diluted with deionized water) showed that pH, but not salinity, is significant at the 95% confidence level; and that reaction rates increase as pH increases. These results suggest the possibility of abiotic methylation of mercury(II) in seawater. Additional experiments in seawater demonstrated an absence of methylation of mercury(II) (14 days) and mercury(0) (35 days) by methyl iodide.     

固相萃取-气相色谱-串联质谱法检测水中18种酚类化合物

当前水中酚类化合物种类不清、危害不明，多种酚类化合物的同时检测方法不成熟，因此建立水中多种酚类化合物同时检测的方法具有重要现实意义。该研究建立了固相萃取结合气相色谱-串联质谱同时检测水中18种酚类化合物的分析方法。实验选择超纯水为空白样品，采用固相萃取技术富集、提取水中的酚类化合物，同时对水样初始pH值、洗脱液的种类、洗脱液的用量等条件进行优化，从而确定出最优的前处理方法，最后利用气相色谱-串联质谱法对不同种类的酚类化合物同时进行定量检测。实验结果表明，在初始水样pH值为3.0、不衍生等条件下，使用10 mL乙酸乙酯洗脱，控制洗脱速度为1 mL/min，经固相柱富集净化，氮吹浓缩后，用气相色谱-质谱仪（EI源）测定，选择离子模式监测，外标法定量。结果表明，以3倍信噪比结合浓度外推法确定方法检出限，为0.04~0.6 μg/L；18种酚类化合物的加标回收率为51.7%~117.3%，相对标准偏差为3.1%~7.4%。应用建立的方法分别检测了河流湖泊水、生活用水、生产用水3大类6种不同的水质。检测结果表明，河流湖泊水中酚类化合物所含种类最多，含量最高。研究建立的方法不需要衍生，简化了前处理方法，操作简单，且准确性高，重复性好，可同时检测复杂水体中多种酚类化合物，能显著提高酚类化合物的分析速率。该方法的建立对我国水中酚类化合物残留水平的控制、检测标准的制定和管理措施的采取，都具有重要的理论和现实意义。     

固相微革取-气相色谱-质谱联用测定海水与沉积物中邻苯二甲酸酯类污染物

邻苯二甲酸酯(PAEs)是塑化剂产品中使用最广泛的一类化合物,准确分析海洋中邻苯二甲酸酯的种类、组成及浓度水平,对认识PAEs在海洋环境的迁移变化及生态效应具有重要意义.本研究建立了固相微萃取-气相色谱-质谱联用技术分析海水与沉积物中PAEs的方法,确定了萃取时间、萃取温度等最佳实验条件.本方法测定海水与沉积物中PAEs含量的精密度为±10%,检出限分别为0.04~0.32 ng/L和0.12~1.60μg/kg;除邻苯二甲酸二甲酯(DMP)外,海水中PAEs回收率为68.0%~114.0%,沉积物中PAEs回收率为76.4%~105.0%.利用本方法测得长江口及其邻近海域水体与沉积物中PAEs的浓度分别为0.270~1.39μg/L和0.79~34.8μg/kg.实验表明,本方法操作简单,准确度高,大大缩减了海水萃取体积,能够应用于近岸海水与沉积物中PAEs含量的准确分析.     

Effect of Surfactant Loading on the Extraction Properties of C-18 Bonded Silica used for Solid-Phase Extraction of Phenols

ABSTRACT

A solid phase extraction (SPE) system has been modified with cationic surfactants and evaluated for extraction and preconcentration of trace phenolic compounds contaminants in water at low ppb concentrations. Cationic surfactants such as cetyl trimethyl ammonium bromide (CTAB) has been steadily adsorbed on the surface of C-18 bonded silica, and the ionized functional group of the surfactant can then act as an ion–exchange site to attract the ionized phenolic compounds from water samples. The method includes enrichment of the phenolic compounds by the surfactant-loaded solid phase extraction system, followed by elution of the analyte with methylene chloride and derivatization of the phenolic compounds with acetic anhydride. Thirty-two phenolic analytes were identified and quantitatively determined by this method; identification and quantification of the compounds is performed with GC/FID using 2-bromophenol as internal standard. SPME analysis with this method was linear over 3-6 orders of magnitude, with linear correlation coefficient (R²) greater than 0.96. Experimentally determined FID detection limits ranged from ～30 ppt for methyl-substituted phenols to ～0.1ppb for phenol and chloro-substituted phenols. We tested the influence of sample pH, the loading amount of surfactant on the solid phase, and the volume and matrixes of the sample were studied. Absolute recoveries from pure water spiked with 0.2 ppb phenolic compounds were 96 – 103%. The method has been applied to analysis of various natural waters, including ground water, lake water, seawater, and wastewater. Recoveries from ground water, lake water, seawater, and wastewater were 92 – 106%, 75 – 93%, 87 – 103%, 86 – 99%, respectively. Therefore, the new technique proved to be an excellent tool for trace enrichments of phenolic compounds at low ppb concentration of these analytes, from different natural water samples.