Multi-residue analysis of PAH, PCB, and OCP optimized for organic matter of forest soil

Purpose

Analyzing organic pollutants in forest soil is challenging because they are strongly physical and chemical bound to soil organic matter (SOM). Within the framework of a forest soil inventory, an analytical protocol for the determination of polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), and organochlorine pesticides (OCP) should be established and validated using one and the same extraction and cleanup procedure. The protocol should be applicable for reliable analysis of a high number of samples in a short timeframe.

Materials and methods

Two different soil samples representative for the humic layer from a typical mixed and coniferous forest soil had been used for the analysis. Three solvents of different polarity, namely cyclohexane (CH), ethylacetate (EA)/CH (1/1, v/v), and acetone (AC)/CH (2/1, v/v), and the six standard extraction techniques (pressurized liquid extraction (PLE), soxhlet extraction, fluidized bed extraction, sonication, shaking, and one-step extraction recommended for analyzing agricultural soil in Germany (VDLUFA 2008)) were compared concerning their extraction efficiency. For additional matrix separation, two different cleanup procedures (gel permeation chromatography (GPC) and solid-phase extraction (SPE) with different sorbents) were tested. Quantification was carried out using gas chromatography combined with mass spectrometry (GC–MS) and two different injection systems (split/splitless injection and programmable temperature vaporizer (PTV) injection). Labeled internal standards, added prior to extraction, were used for method evaluation.

Results and discussion

For the simultaneous extraction of PAH, PCB, and OCP from organic forest soil PLE with acetone/cyclohexane (2/1, v/v) provided the highest extraction efficiency. A two-step cleanup procedure consisting of GPC followed by SPE with silica gel was entirely sufficient for the separation of humic substances without discrimination of analytes. Recovery rates for the different extraction and cleanup steps ranged between 89% and 106%. For quantification, a GC–MS method was developed using two different injection systems and two capillary columns of different selectivity.

Conclusions

By comparing six standard extraction techniques for PAH, PCB, and OCP from forest soil, we obtained the highest extraction efficiency when using PLE with AC/CH (2/1). For sample injection, we achieved best results using an optimized PTV injection system as it highly reduced the breakdown of thermolabile pesticides. Using this combination of technical equipment, it is possible to determine a concentration of the analytes in the trace level range of 1–2 μg kg^?1 in humic soil.     

PAK-Abnahmen in Bodenproben verschiedener Altlaststandorte bei Aktivierung der autochthonen Mikroflora

PAH decrease in soil samples from different polluted industrial sites by activating the autochthonous microflora In pot experiments under field conditions the PAH decrease in ten different soil samples from former industrial sites with differing PAH load were investigated over a period of 74 and 168 weeks. 15 out of 16 PAH according to US EPA (without acenaphthylene) were determined. Easily degradable organic matter, mineral fertilizers, synthetic surfactants and in some experiments also lime were added to the soil samples in varying amounts. Depending on the nature and quantity of the amendments, the biological activity and (co-)metabolic decomposition of PAH by soil microorganisms could considerably be increased. In the different soil samples a decrease of the initial PAH contents between 12 and 90% was achieved within 74 weeks. Even from 74 up to 168 weeks for some soil samples a remarkable further decrease of the PAH contents could be observed. The decrease of the extractable PAH with time is mainly caused by microbial decomposition and formation of nonextractable residues. This behavior can be fitted by two coupled exponential functions, one for an initial phase of rapid decomposition and the other for a subsequent phase of slow decomposition. Therefore, two different processes (I, II) determine the decrease of PAH. In the first week of the experiment the decomposition rates for process I amount to 4.2–88.3 and for process II to 0.06–5.3 mg PAH ? kg^?1 soil ? week^?1; in the 168th week they are no longer determinable for process I and amount to 0.05–2.3 mg ? kg^?1 ? week' for process II. Higher initial PAH contents often led to higher relative PAH decreases, but also to absolute higher contents of residues. The persistence of PAH is mainly determined by their bioavailability. PAH degradation is increased by the soil treatments. The addition of easily degradable organic matter (C/N ratio < 20) in a quantity of 30g ? kg^?1 (w/w) combined with the addition of nitrate and a surfactant most effectively increased the degradation of PAH. Raising the pH of a very strongly acidic soil sample revealed a maximum PAH decomposition at a pH of 6.     

Optimizing conditions for the extraction of pigments in cochineals (Dactylopius coccus Costa) using response surface methodology

A simple method was developed for the extraction and determination of color pigments in cochineals (Dactylopius coccus Costa). The procedure was based on the solvent extraction of pigments in insect samples using methanol:water (65:35, v:v) as extractant. Two-level factorial design was used in order to optimize the solvent extraction parameters: temperature, time, methanol concentration in the extractant mixture, and the number of extractions. The results suggest that the number of extractions is statistically the most significant factor. The separation and determination of the pigments was carried out by high-performance liquid chromatography with UV-visible detection. Because the absorption spectra of different pigments are different in the visible region, it is convenient to use a diode array detector to obtain chromatographic profiles that allow for the characterization of the extracted pigments.     

Evaluation of a modified QuEChERS extraction of multiple classes of pesticides from a rice paddy soil by LC-APCI-MS/MS

A new method for the determination of clomazone, fipronil, tebuconazole, propiconazole, and azoxystrobin in samples of rice paddy soil is presented. The extraction of the pesticides from soil samples was performed by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. Some extraction conditions such as salt addition, sample acidification, use of buffer, and cleanup step were evaluated. The optimized method dealt with a single extraction of the compounds under study with acidified acetonitrile, followed by the addition of MgSO(4) and NaCl prior to the final determination by liquid chromatography-atmospheric chemical pressure ionization-tandem mass spectrometry. Validation studies were carried out in soil samples. Recoveries of the spiked samples ranged between 70.3 and 120% with relative standard deviation lower than 18.2%. The limits of quantification were between 10 and 50 μg kg(-1). The method was applied to the analysis of real samples of soils where rice is cultivated.     

Analysis of nitrate ion in nettle (Urtica dioica L.) by ion-pair chromatographic method on a C30 stationary phase

Nitrate ion is a frequent pollutant not only in soil and natural water resources but in vegetables and foods as well. In our study we focused on nettle due to its increased ability to accumulate nitrate ions. A new, simple method for the separation and determination of nitrate ion based on reversed-phase ion-pair chromatography has been elaborated. A new four-step sample pretreatment method enables the precipitation of proteins and oxidative degradation of compounds that may disturb the identification of the nitrate ion: (1) extraction of the total nitrate content, (2) precipitation of proteins with acetonitrile, (3) oxidative degradation of the organic contaminants with H2O2, (4) evaporation of the solvent and taking up of the residue in water. The chromatographic separations were carried out on a high-density C30 stationary phase under isocratic conditions. The optimal mobile-phase composition was 10% (v/v) acetonitrile and 90% (v/v) 20 mmol L(-1) phosphate buffer, containing 2 mmol of tetrabutylammonium hydroxide at pH 6.0. The method could also be used for the separation of IO3(-), SeO3(2-), BrO3(-), NO2(-), Br-, SeO4(2-), and I- ions. The validated method is sensitive (the detection limit is 0.18 ng of nitrate ion). The method is linear in a high concentration range (0.031-30.66 microg mL(-1)). Recoveries varied between 98% and 103%. Reproducibility of the elaborated sample pretreatment method showed 1.54%. The method can be used for the determination of nitrate ion from different plants.     

Electrochemical Method for the Rapid on Site Screening of Cadmium and Lead in Soil and Water Samples

Rapid field-based screening methods for the semi-quantitative determination of heavy metals are desirable to support the increasing demand for the rapid characterization of contaminated sites. Single-use sensors have been fabricated using low-cost screen-printing (thick film) technology. These electrodes, coupled with differential pulse anodic stripping voltammetry (DPASV), have provided a rapid, inexpensive on site screening device for the simultaneous field-based determination of cadmium (Cd) and lead (Pb) in soil and water samples in the microgram per litre/kilogram range. A simplified soil extraction procedure, using 1 mol l^?1 aqua regia and a 3 min ultrasonic sample agitation, has been developed to allow field-based device usage. Extraction efficiency was evaluated using a soil certified reference material (CRM). Recoveries of 64% and 52% for Cd and Pb respectively were obtained, with a relative standard deviation (RSD) of <8% for both analytes (n = 10). Soil samples (82) were tested using the combined extraction-DPASV procedure and compared against standard ICP-AES analysis. Correlation coefficients of 0.9782 and 0.9728 for Cd and Pb respectively demonstrate good correlation between methods. Analytical data is also reported for copper (Cu), but significant peak distortions reduce the confidence of the method for this metal. Results indicate that the combined extraction-DPASV method yields semi-quantitative data for rapid field-based site screening purposes.     

昆明地区碳酸盐岩发育红土载磁矿物的提取与鉴定

利用重液分离工艺对昆明地区磁化率最高的碳酸盐岩发育的红土进行载磁矿物的分离提取,并对提取出的样品进行X射线衍射(XRD)鉴定,结果显示碳酸盐岩发育红土的主要载磁矿物为磁赤铁矿(γ-Fe2O3)、赤铁矿(α-Fe2O3)和针铁矿(α-FeOOH),它们占总载磁矿物的半定量比例分别为30％、37％和33％,这些测定结果大体...     

Extraction and separation of water-soluble proteins from different wheat species by acidic capillary electrophoresis

Optimization of protein extraction and a capillary zone electrophoresis method for water-soluble protein analysis in wheat is described. The optimal separation was obtained with a 50 microm i.d. x 27 cm (20 cm to detector) uncoated capillary filled with 0.1 M phosphoric acid/beta-alanine, pH 2.5, buffer containing urea (1 M), 0.05% (w/v) hydroxypropylmethylcellulose, and 20% (v/v) acetonitrile. Separation was carried out at 15 kV and 35 degrees C for 9 min. Extract stability was also investigated within 2 h from the extraction. Good visual peak parameters and a higher sensitivity can be obtained when 30% ethanol is used as an extraction medium. The method was successfully used to analyze extracts obtained from whole and refined meals of six Triticum spp. Moreover, the described methodology could be applied to the discrimination of species with different ploidy levels and to the detection of durum wheat adulteration, as well as to screen wheat collections for enzymes involved with the quality of wheat derivatives.     

Development of a new method for the complete extraction of carotenoids from cereals with special reference to durum wheat (Triticum durum Desf.)

Due to the growing interest in the role of carotenoids in human health, their qualitative and quantitative analysis in foods is becoming more and more important. High-performance liquid chromatography has become the method of choice for the determination of these phytochemicals. A crucial step prior to the chromatographic separation is the quantitative extraction from the food matrix which was proven to be impeded in durum wheat. To optimize the extraction procedure, several factors with influence on extractability of carotenoids were investigated. Finally, it was shown that soaking of samples in water for 5 min prior to extraction with organic solvents had the strongest impact on extraction yield and led to the most rapid and gentle method. Contents of carotenoids in the extracts of several durum wheat and corn samples were doubled by soaking in water before extracting with methanol/tetrahydrofuran (1/1, v/v). In light of these findings, literature data on contents of carotenoids in cereal grains have to be viewed critically regarding the extraction procedures employed.     

Large volume TENAX® extraction of the bioaccessible fraction of sediment-associated organic compounds for a subsequent effect-directed analysis

Background, Aims and Scope

Effect-directed analysis (EDA) is a powerful tool for the identification of key toxicants in complex environmental samples. In most cases, EDA is based on total extraction of organic contaminants, which may lead to an erroneous prioritisation with regard to hazard and risk. Bioaccessibility-directed extraction aims to discriminate between contaminants that take part in partitioning between sediment and biota in a relevant time frame and those that are enclosed in structures that do not allow rapid desorption. Standard protocols of targeted extraction of the rapidly desorbing, and thus bioaccessible, fraction using TENAX® are based only on small amounts of sediment. In order to obtain sufficient extract for subsequent biotesting, fractionation and structure elucidation, a large volume extraction technique needs to be developed applying one selected extraction time and excluding toxic procedural blanks.

Methods

Desorption behaviour of sediment contaminants was determined by combining consecutive extraction of sediment using TENAX® with a three-compartment desorption model. Time needed to remove the rapidly desorbing fraction, t_rap, was calculated to select a fixed extraction time for single extraction procedures. Up-scaling by about a factor of 125 provided a large volume extraction technique for EDA. Reproducibility and comparability to the small volume approach were analysed. TENAX® blanks and sediment extracts were tested for toxicity using Scenedesmus vacuolatus and Artemia salina as test organisms.

Results and Discussion

Desorption kinetics showed that 12 to 30% of sediment-associated pollutants were available for rapid desorption, while 70 to 90% of PAHs found in the sediment belong to the slowly and very slowly desorbing pool with very limited bioavailability. t_rap is compound dependent and covers a range of 2 to 18 h. A fixed extraction time of 24 h was selected as a time at which even the rapidly desorbing fraction of big hydrophobic compounds should be fully desorbed. High reproducibility of the large volume approach and good agreement with the small consecutive approach were found. Significant toxicity of procedural TENAX® blanks was found with Scenedesmus vacuolatus, which is in agreement with chemical analysis and could be reduced by pre-cleaning of TENAX® with Accelerated Solvent Extraction (ASE). Toxicity of blanks prior to ASE-clean up was about three orders of magnitude below the toxicity of sediment extracts.

Conclusions

For consideration of bioaccessibility in EDA, a large volume TENAX® extraction method was presented. Although several other solid phases can be used to extract the bioaccessible fraction, TENAX® has unique properties for depletive extraction of the rapidly desorbing fraction from large amounts of sediment. Toxicity and chemical blanks due to production residues are shortcomings of the method that can be overcome by accurate pre-cleaning, e.g. with ASE.

Recommendations and Perspectives

Higher purity of TENAX® guaranteed by the manufacturers would significantly enhance the applicability of the method. Using TENAX® instead of total extraction may improve key toxicant prioritisation by considering exposure and effect rather than effect only.

     

Fast determination of Sudan dyes in chilli tomato sauces using partial filling micellar electrokinetic chromatography

A new method based on partial filling micellar electrokinetic chromatography (MEKC) for the quantitative determination of Sudan dyes (I, II, III, and IV) in chilli sauces is presented. The separation is achieved filling 25% of the capillary with a MEKC buffer composed of 40 mM NH(4)HCO(3), 25 mM sodium dodecyl sulfate, and 32.5% (v/v) acetonitrile (ACN). The rest of the capillary is filled using a capillary zone electrophoresis (CZE) buffer composed of 40 mM NH(4)HCO(3) and 32.5% (v/v) ACN. Under optimized conditions, the azo dyes are baseline separated in less than 8 min with limits of detection ranging from 0.57 to 0.71 μg mL(-1) (S/N > 3). Using an internal standard, the repeatability of the quantitative determination is improved almost four times. The applicability of the method for rapid screening and determination of Sudan dyes is corroborated by analyzing spiked chilli sauce samples with recoveries from 85 to 99%. The reported conditions are demonstrated to be compatible with mass spectrometry detection.     

Assessment of polycyclic aromatic hydrocarbon content of smoked fish by means of a fast HPLC/HPLC method

Polycyclic aromatic hydrocarbon (PAH) concentrations in smoked food can reach levels hazardous for the human health, especially when the smoking procedure is carried out under uncontrolled conditions. In this work a simple and rapid method for the determination of PAHs in smoked fish samples is described. PAHs were extracted from the insoluble samples (together with fat substances) by homogenization with acidified chloroform. The fat extract was then submitted to a first LC sample preparation step (performed on a large silica column) to isolate PAHs from triglycerides. After reconcentration, the PAH fraction was finally injected into the reverse-phase analytical column. The proposed method, which presents good characteristics of recoveries and repeatability, was also used to analyze PAH content of some smoked trout samples packed under vacuum.     

Simultaneous determination of ethidimuron, methabenzthiazuron, and their two major degradation products in soil

An analytical method has been developed for the quantification of two herbicides (ethidimuron and methabenzthiazuron) and their two main soil derivatives. This method involves fluidized-bed extraction (FBE) prior to cleanup and analysis by reverse-phase liquid chromatography with UV detection at 282 nm. FBE conditions were established to provide efficient extraction without degradation of the four analytes. (14)C-labeled compounds were used for the optimization of extraction and purification steps and for the determination of related efficiencies. Extraction was optimal using a fexIKA extractor operating at 110 degrees C for three cycles (total time = 95 min) with 75 g of soil and 150 mL of a 60:40 v/v acetone/water mixture. Extracts were further purified on a 500 mg silica SPE cartridge. Separation was performed on a C18 Purosphere column (250 mm x 4 mm i.d.), at 0.8 mL min(-1) and 30 degrees C with an elution gradient made up of phosphoric acid aqueous solution (pH 2.2) and acetonitrile. Calibration curves were found to be linear in the 0.5-50 mg L(-1) concentration range. Besides freshly spiked soil samples, method validation included the analysis of samples with aged residues. Recovery values, determined from spiked samples, were close to 100%. Limits of detection ranged between 2 and 3 microg kg(-1) of dry soil and limits of quantification between 8 and 10 microg kg(-1) of dry soil. An attempt to improve these performances by using fluorescence detection following postcolumn derivatization by orthophthalaldehyde-mercaptoethanol reagent was unsuccessful.     

Enhanced bioremediation of PAH-contaminated soil by wheat bran and microbial community response

ABSTRACT

Microcosms were set up containing a PAH polluted soil to investigate biostimulation (addition of wheat bran and fertilizer) and bioaugmentation (inoculation with Pseudomonas sp. SB). After 60 d the fertilizer + wheat bran gave the highest PAH degradation. The degradation rate was 42.2%, significantly higher than the 18.7% in the fertilizer only treatment. Principal coordinate analysis (PCoA) indicates that wheat bran treatment can significantly alter soil bacterial and fungal communities. In addition, wheat bran promoted the enrichment of some soil bacteria such as Bacillaceae, Xanthomonadaceae, Streptomycetaceae, and Chitinophagaceae, and the fungi Talaromyces, Humicola, unclassified_Chaetomiaceae and Mortierella. These results highlight the potential of wheat bran application to reduce the PAHs detected in soil.     

Bestimmung cellulosisch und nichtcellulosisch gebundener Neutralzucker in Bodenhydrolysaten mit Hilfe von Hochleistungsdünnschichtchromatographie

Determination of cellulosic and noncellulosic neutral sugars occurring in soil hydrolysates by means of high-performance thin-layer chromatography Analytical methods for soil samples are described, which allow the differentiation between monosaccharides bound in cellulosic and noncellulosic polysaccharides of the plant cell wall. The four step procedure includes hydrolysis of total polysaccharides (72 % H₂SO₄, 2N H₂SO₄), hydrolysis of the noncellulosic fraction (2N trifluoroacetic acid), separation of the monomers by high-performance thin-layer chromatography (HPTLC) and scanning of the plates for quantification. The amount of cellulose can be calculated by the difference of total glucose and glucose hydrolyzed by trifluoroacetic acid. Hydrolysis of soil samples by trifluoroacetic acid is a simple method for the determination of noncellulosic cell wall polysaccharides. Losses of sugars during the whole analytical procedure (hydrolysis, separation by HPTLC and quantification) are below 10 % for all sugars studied (galactose, glucose, mannose, arabinose, xylose). Standard deviations do not overstep this value, too. By HPTLC a large number of samples are chromatographed together; therefore, the total analysis time per sample is very short. As example the depth functions of hydrolyzed sugars in a Lithic Borofolist are discussed.     

Polycyclic Aromatic Hydrocarbons Content in Contaminated Forest Soils with Different Humus Types

The aim of the study was to determine polycyclic aromatic hydrocarbon (PAH) content in different forest humus types. The investigation was carried out in Chrzanów Forest District in southern Poland. Twenty research plots with different humus types (mor and mull) were selected. The samples for analysis were taken after litter horizons removing from a depth of 0–10 cm (from the Of- and Oh-horizon total or A-horizon). pH, organic carbon and total nitrogen content, base cations, acidity, and heavy metal content were determined. In the natural moisture state, the activity of dehydrogenase was determined. The study included the determination of PAH content. The conducted research confirms strong contamination of study soil by PAHs and heavy metals. Our experiment provided evidence that different forest humus types accumulate different PAH amounts. The highest content of PAHs and heavy metals was recorded in mor humus type. The content of PAHs in forest humus horizon depends on the content and quality of soil organic matter. Weaker degradation of hydrocarbons is associated with lower biological activity of soils. The mull humus type showed lower content of PAHs and at the same time the highest biological activity confirmed by high dehydrogenase activity.     

Accelerated solvent extraction and gas chromatography/mass spectrometry for determination of polycyclic aromatic hydrocarbons in smoked food samples.

Accelerated solvent extraction (ASE) is a new sample extraction method offering a number of advantages such as low pe -extraction cost, reduced solvent and time consumption, and simplified extraction protocols. In this study, the ASE method was applied to the extraction of polycyclic aromatic hydrocarbons (PAHs) from biological samples. For recovery studies, fish tissues and ground pork were used as sample matrices. Sample aliquots fortified with 16 PAHs were extracted by ASE, and the extracts were treated with sulfuric acid and Florisil, followed by gas chromatography-mass spectrometry analysis. The PAH recoveries by the ASE method were found to be comparable with or better than those by Soxhlet extraction. The extraction and quantitation method was then applied to the determination of PAHs in several smoked meat samples obtained from a local market. Up to 12 PAHs were found to be present at concentrations ranging from 3 to 52 ng/g wet sample.     

Influence of Long-Term Soils Flooding by Distilled and Post-Sewage Water on Polycyclic Aromatic Hydrocarbons (PAHs) Changes

The aim of presented study was to determine the influence of long-term inundation on the changes in the content of polycyclic aromatic hydrocarbons. Two soils (B, MS) with differentiated properties were selected for the presented study. The experiment was carried out in 5-l containers, irrigated with distilled or post-sewage water for seven days. The study samples were collected directly after the water had been drained and then after seven, 14, 28 and 50 days. In the material collected, the content of polycyclic aromatic hydrocarbons was determined by means of the HPLC-UV method. The soils used for the presented experiment were characterised by differentiated PAH content levels. However, in both soils 28 days after water had been drained, a gradual increase of the PAH sum was noted. This increase was in relation to beginning of the experiment significantly higher in soil MS characterised by a lower PAH content (43% and 86%, respectively in the experiment with distilled and post-sewage water). The range of the PAH sum increase in soil B was from 28% to 38%. After the 28th day of the experiment, a decreasing trend was noted. The trend persisted until the last experimental date. Only in soil B, a decrease in the PAH up to a level close to the PAH level on the onset of the experiment was observed. In soil MS, PAH content on the last experimental date was still 25% (distilled water) and 52% (post-sewage water) higher than at the beginning of the experiment. In control soils (non-flooded), PAH content did not undergo any significant changes during the whole experimental period. In the presented studies, significant relationships between the values of some PAH content levels and Ca²⁺ ions content was noted.     

Rapid assay for analyzing biogenic amines in cheese: matrix solid-phase dispersion followed by liquid chromatography-electrospray-tandem mass spectrometry

A new rapid and sensitive method based on matrix solid-phase dispersion (MSPD) followed by liquid chromatography-electrospray-tandem mass spectrometry was devised for the determination of biogenic amines at trace levels in cheese samples. The method required 0.25 g of sample, CN-bonded silica as a dispersant sorbent, and a formic acid aqueous solution/methanol mixture as an eluting solvent. Extraction recoveries from soft cheese products were calculated in the 98 +/- 4-110 +/- 6% range. A procedure based on solid-phase extraction was also evaluated for the extraction of these compounds in cheese. Chromatographic separation was performed using a C18 column with an aqueous ammonium acetate/methanol mixture as the mobile phase under gradient conditions. The method was validated in terms of detection limits (LOD), quantitation limits (LOQ), linearity, recovery, precision, and trueness. Results in the 0.05-0.25 mg kg(-1) range were obtained for the LOD of histamine, tyramine, and beta-phenylethylamine in soft cheese samples. Linearity was established over 2 orders of magnitude. Excellent precision in terms of intra-day repeatability was calculated (RSD% < 5). The applicability of the method to the determination of biogenic amines in cheese products was demonstrated.     

Comparison of strategies for extraction of high molecular weight polycyclic aromatic hydrocarbons from drinking waters

Simple, rapid, and inexpensive methods have been developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in drinking waters without interferences from other chemical contaminants by use of two different extraction techniques and analysis by an optimized reverse-phase (RP) high-performance liquid chromatography followed by fluorescence detection (HPLC-FLD) method. The feasibility of SPE (solid-phase extraction) and SPME (solid-phase microextraction) for the determination of PAH in drinking water samples has been evaluated. Several parameters have been studied and optimized for both extraction procedures. The relationship between the nature of the fibers and the quantity of extracted compounds and the effects of organic solvent, salt addition, sampling temperature, and sampling time was studied for SPME. Acetonitrile percentage added to the sample, sample storage conditions (temperature and time), and type of organic elution solvent and elution volume were evaluated for SPE. The results show that both extraction procedures can be used to determine PAHs in drinking waters, but SPE gives better performance (recovery, precision, and quantification limits) for the determination of PAHs in drinking water at the levels established by the legislation.