Characterization of solid-phase microextraction and gas chromatography for the analysis of gasoline tracers in different microenvironments

Gasoline tracers were collected on solid-phase microextraction (SPME) fibers and analyzed by capillary gas chromatography with photoionization detector (GC/PID). This was part of a larger study to quantify personal exposure to motor vehicle gasoline evaporative and combustive emissions in high-end exposure microenvironments (MEs). The SPME fiber selected for this application was a 75-microm carboxen/polydimethylsiloxane. Sequential 10-min samples were collected for measurement of benzene, toluene, ethylbenzene, and ortho-, meta-, and para-xylene in different MEs in Atlanta, GA, in summer 2002 and Reno, NV, in spring 2003. Field calibrations were performed with certified gas standards in 1-L Tedlar bags for varying concentrations and exposure times. SPME detection limits were approximately 0.2 ppbv with a precision of 3-17% and accuracy of 30%. A dynamic system was designed for temperature and relative humidity calibrations, with corrections for the effects of these variables performed when necessary. SPME data compared satisfactorily with integrated canister samples, continuous PID, and field portable mass spectrometer data.     

Quantification of personal exposure concentrations to gasoline vehicle emissions in high-end exposure microenvironments: Effects of fuel and season

Mobile-source air toxic (MSAT) levels increase in confining microenvironments (MEs) with numerous emission sources of vehicle exhaust or evaporative emissions or during high-load and cold-start conditions. Reformulated fuels are expected to reduce MSAT and ozone precursor emissions. This study, required under the Clean Air Act Section 211b, evaluated high-end exposures in cities using reformulated (methyl tertiary-butyl ether [MTBE] or ethanol [EtOH]) fuels and conventional gasoline blends. The study investigates 13 high-end MEs, sampling under enhanced exposure conditions expected to result in maximal fuel and exhaust component exposures to carbon monoxide (CO), carbon dioxide (CO₂), BTEX (benzene, toluene, ethylbenzene, xylenes), MTBE, 1,3-butadiene (1,3-BD), EtOH, formaldehyde (HCHO), and acetaldehyde (CH₃CHO). The authors found that day-to-day ME variations in high-end benzene, 1,3-BD, HCHO, and CO concentrations are substantial, but independent of gasoline composition and season, and related to the activity and emission rates of ME sources, which differ from day to day.

Implications: Mobile-source air toxic (MSAT) levels increase in confining microenvironments (MEs) in the presence of vehicular exhaust or evaporative emissions. This study, required under the Clean Air Act Section 211b, evaluated high-end exposures in cities using oxygenated (methyl tertiary-butyl ether or ethanol) and conventional gasoline blends. Personal exposure concentrations were quantified in selected MEs representing the upper end of the frequency distribution of potential population exposures. This work presents the first systematic look at high-end/maximal exposures to multiple contaminants, in multiple microenvironments, in multiple cities, over two seasons, for multiple fuels, making it a very complete evaluation of reformulated fuel impacts on MSAT concentrations in confined microenvironments. The study found that day-to-day ME variations of high-end pollutant concentrations are substantial, but independent of gasoline composition and season, and related to the variable daily activity and emission rates of ME sources. The data collected in this study may be used in bounding exposure modeling estimates that account for time spent in similar confining MEs.     

Analysis of Organophosphorus Pesticides in Whole Milk by Solid Phase Microextraction Gas Chromatography Method

Solid phase microextraction (SPME) was used for the extraction of residual coumaphos and dichlorvos in whole milk. The residues were analyzed by capillary gas chromatography equipped with nitrogen phosphorus detector (GC-NPD). A manual SPME holder with a 100-μm polyacrylate fiber was used. The optimized conditions for extraction by SPME method were: sample agitation, absorption temperature of 30°C, absorption time of 40 min, desorption time of 10 min, and sample volume was 16.0 mL in the vial. Under these conditions, the calibration graphs were linear in the range of 0.17 μgL^?1 to 1.75 μgL^?1 for coumaphos and 0.69 μgL^?1 to 6.90 μgL^?1 for dichlorvos. Precision was good with RSD values of 13% for coumaphos and 14% for dichlorvos. The detection limits (LOD) were 0.060 μgL^?1 for dichlorvos and 0.052 for coumaphos. The quantification limits (LOQ) were 0.086 μgL^?1 for dichlorvos and 0.066 μgL^?1 for coumaphos. The results obtained in this study suggest that SPME is a suitable technique for residual pesticide analysis of milk. The data demonstrate that particular OP pesticides used in dairy farming in the region of Minas Gerais were found to contaminate cow whole milk, and the residues are not removed by treating the milk by boiling.     

Comments on the NAS Report: Odors From Stationary and Mobile Sources

ABSTRACT

Solid phase microextraction (SPME) presents many advantages over conventional analytical methods by combining sampling, preconcentration, and direct transfer of the analytes into a standard gas chromatograph (GC). Since its commercial introduction in the early 1990s, SPME has been successfully applied to the sampling and analysis of environmental samples. This paper presents an overview of the current methods for air sampling and analysis with SPME using both grab and time-weighted average (TWA) modes. Methods include total volatile organic compounds (TVOCs), formaldehyde, and several target volatile organic compounds (VOCs). Field sampling data obtained with these methods in indoor air were validated with conventional methods based on sorbent tubes. The advantages and challenges associated with SPME for air sampling are also discussed. SPME is accurate, fast, sensitive, versatile, and cost-efficient, and could serve as a powerful alternative to conventional methods used by the research, industrial, regulatory, and academic communities.     

Concentrations of mobile source air pollutants in urban microenvironments

Human exposures to criteria and hazardous air pollutants (HAPs) in urban areas vary greatly due to temporal-spatial variations in emissions, changing meteorology, varying proximity to sources, as well as due to building, vehicle, and other environmental characteristics that influence the amounts of ambient pollutants that penetrate or infiltrate into these microenvironments. Consequently, the exposure estimates derived from central-site ambient measurements are uncertain and tend to underestimate actual exposures. The Exposure Classification Project (ECP) was conducted to measure pollutant concentrations for common urban microenvironments (MEs) for use in evaluating the results of regulatory human exposure models. Nearly 500 sets of measurements were made in three Los Angeles County communities during fall 2008, winter 2009, and summer 2009. MEs included in-vehicle, near-road, outdoor, and indoor locations accessible to the general public. Contemporaneous 1- to 15-min average personal breathing zone concentrations of carbon monoxide (CO), carbon dioxide (CO₂), volatile organic compounds (VOCs), nitric oxide (NO), nitrogen oxides (NO_x), particulate matter (<2.5 μm diameter; PM_2.5) mass, ultrafine particle (UFP; <100 nm diameter) number, black carbon (BC), speciated HAPs (e.g., benzene, toluene, ethylbenzene, xylenes [BTEX], 1,3-butadiene), and ozone (O₃) were measured continuously. In-vehicle and inside/outside measurements were made in various passenger vehicle types and in public buildings to estimate penetration or infiltration factors. A large fraction of the observed pollutant concentrations for on-road MEs, especially near diesel trucks, was unrelated to ambient measurements at nearby monitors. Comparisons of ME concentrations estimated using the median ME/ambient ratio versus regression slopes and intercepts indicate that the regression approach may be more accurate for on-road MEs. Ranges in the ME/ambient ratios among ME categories were generally greater than differences among the three communities for the same ME category, suggesting that the ME proximity factors may be more broadly applicable to urban MEs.

Implications:Estimates of population exposure to air pollutants extrapolated from ambient measurements at ambient fixed site monitors or exposure surrogates are prone to uncertainty. This study measured concentrations of mobile source air toxics (MSAT) and related criteria pollutants within in-vehicle, outdoor near-road, and indoor urban MEs to provide multipollutant ME measurements that can be used to calibrate regulatory exposure models.     

Determination of organochlorine and organophosphorus pesticide residues in low moisture,nonfatty products using a solid phase extraction cleanup and gas chromatography

Abstract

A multiresidue solid‐phase extraction (SPE) method for the isolation and subsequent gas Chromatographie determination of organochlorine and organophosphorus pesticide residues in low‐moisture, nonfatty products is described. Residues are extracted from samples with an acetonitrile/water mixture. Cleanup of the extract is performed using graphitized carbon black and anion exchange SPE columns, and analysis is performed by gas chromatography with Hall electrolytic conductivity and flame photometric detection. Recovery data was obtained by fortifying corn, oats and wheat with pesticides. The average recoveries were 79–123% for eight organochlorine and 51–122% for 28 organophosphorus pesticide residues. The limit of quantitation for chlorpyriphos was 0.05 ppm using the Hall electrolytic conductivity detector and <0.005 ppm using the flame photometric detector.     

COMPARISON BETWEEN SOLID–PHASE EXTRACTION METHODS FOR THE CHROMATOGRAPHIC DETERMINATION OF ORGANOPHOSPHORUS PESTICIDES IN WATER

A solid-phase microextraction (SPME) procedure has been developed to ex tract eight organophosphorus pesticides (OPs) in water and the method was compared with a conventional solid phase extraction (SPE) technique. The extracted OPs were analyzed by gas chromatography using thermionic specific detection. Both extraction methods presented linear calibration at least over the concentration range investigated (100 to 1000 ng.mL^?1 for SPE and 1 to 100 ng.mL^?1 for SPME). SPME method presented higher sensitivity than SPE. The quantitation limits were between 0.1 to 1.0 ng.mL^?1 for SPME depending upon the analyte, and 100 ng.mL^?1 for SPE. The precision, as measured by the standard deviations (RSD), were in the range 3.6 % to 5.8 % for SPME and 2.4 % to 9.2 % for SPE.

Along with the feature of being a solvent – free sampling technique, SPME offers additional benefits due to its high sensitivity, simplicity, and small size sample required (typically: SPE – 500 mL, SPME – 5 mL).     

Calibration of Sharp Cut Impactors for Indoor and Outdoor Particle Sampling

ABSTRACT

A low-flow rate, sharp cut point inertial impaction sampler was developed in 1986 that has been widely used in PM exposure studies in the United States and several other countries. Although sold commercially as the MS&T Area Sampler, this sampler is widely referred to as the Harvard Impactor, since the initial use was at the Harvard School of Public Health. Impactor nozzles for this sampler have been designed and characterized for flows of 4,10, 20, and 23 L/min and cut points of 1, 2, 5, and 10 |im. An improved method for determining the actual collecting efficiency curve was developed and used for the recent impactor calibrations reported here. It consists of placing a multiplet reduction impactor inline just downstream of the vibrating orifice aerosol generator to remove the multiplets, thus allowing only the singlet particle s to penetrate through to the impactor being calibrated.

This paper documents the techniques and results of recent nozzle calibrations for this sampler and compares it with other size-selective inertial impactors. In general, the impactors were found to have sharp cutoff characteristics. Particle interstage losses for all of the impactors were very low, with the exception of the 10-|im cut size 20 L/ min impactor, which had greater losses due to the higher flow rate. All of the cut nozzle laboratory calibrations compare favorably to the U.S. Environmental Protection Agency (EPA) WINS-96 fine particle mass (PM_{2 5}) impactor calibration data.     

Fine Particulate Organic Material in the Los Angeles Basin - I: Assessment of the High-Volume Brigham Young University Organic Sampling System,BIG BOSS

ABSTRACT

A multi-system, high-volume, parallel plate diffusion dénuder Brigham Young University Organic Sampling System (BIG BOSS) was tested using collocated samplers at the Pico Rivera Monitoring Station of the South Coast Air Quality Management District, South Coast Air Basin, in September 1994. Six-hr daytime and 9-hr nighttime samples were collected with a flow of about 200 L/min through each of the three systems designed to collect particles smaller than 2.5, 0.8, and 0.4 mm in a diffusion denuder sampler. Efficiency for the removal of gas phase organic compounds by the diffusion denuder was evaluated using both theoretical predictions and field measurements. Both measured and calculated data indicate high denuder efficiency for the removal of gas phase aromatic and paraffinic compounds. The precision of the BIG BOSS was evaluated using collocated samplers. The precision of determination of total carbon and elemental carbon retained by a quartz filter or of semi-volatile carbonaceous material lost from particles during sampling averaged ±7%. The precision of determination of individual organic compounds averaged ±10%. An average of 42 and 62% of the particulate organic material was semi-volatile organic compounds (SVOCs) lost from particles during sampling for daytime and nighttime samples, respectively. This “negative” sampling artifact was an order of magnitude larger than the “positive” quartz filter artifact due to adsorption of gas phase organic material. Daytime concentrations of fine particulate elemental carbon and nonvolatile organic carbon were higher than nighttime concentrations, but nighttime fine particles contained more semi-volatile organic material than daytime.     

Development,validation and application of a method to analyze phenols in water samples by solid phase micro extraction-gas chromatography-flame ionization detector

In this work the development, validation and application of method using Solid Phase Microexctration (SPME) for the analyses of five pollutants (phenol, 2-nitrophenol, 2,4-dimethylphenol, 2,4-dichlorophenol and 4-chloro, 3-methyl phenol) in supplying water, using gas chromatography (GC) with flame ionization detector (FID) is described. The optimal conditions obtained for SPME were: fiber type: Poliacrylate (PA); extraction time: 40 minutes; extraction temperature: 70°C; amount of salt added to sample (NaCl): 15%; desorption temperature: 8 minutes. The parameters studied in the method validation were: limit of detection (0.3 and 3.5 μ g.L^{? 1}); precision, measured by the variation coefficient (between 2.1 and 8.8%); calibration curve and linearity, by using the external standardization method (between 1 and 50 50 μ g.L^{? 1}). After the methodology development, samples of water collected in Atibaia River (São Paulo - Brazil) were analyzed, using the optimized methodology. Three water samples collected in the rain season showed a peak with retention time close to 4-chloro, 3 methyl phenol further analyzed by Gas Chromatography-Mass Spectrometry for the identity confirmation. In spite of the fact that none target compounds were found in the river water samples analyzed, the presence of two phenols different from those investigated (p-terc butyl phenol; butylated hydroxytoluene) were detected. These results together with the results of the limit of detection (that showed to be lower than the maximum concentration of phenols demanded by different environment control agencies), and the results of the validation, indicate the applicability of this method for the analysis of selected phenols in river water samples.     

Solventless sample preparation for pesticides analysis in environmental water samples using solid-phase microextraction-high resolution gas chromatography/mass spectrometry (SPME-HRGC/MS)

Solid-phase micro-extraction (SPME) coupled on line with high resolution gas chromatography and mass spectrometric detection is described for the analysis of pesticides in environmental water samples. Experiments were performed in order to optimize the SPME extraction conditions for selected pesticides including tiomethon, trichorfon, dimethoate, diazinon, malathion, dicofol, methidathion, ethion, bromopropylate and pyrazophos from spiked water solutions. To enhance the SPME efficiency, experimental conditions including the fiber composition, stirring rate, temperature, adsorption time, desorption time and salt concentration were optimized. After validation, the SPME-GC/MS methodology was applied to real-world environmental water samples.     

Methyl tert-butyl ether (MTBE) in urban and rural precipitation in Germany

The use of the oxygenate methyl tert-butyl ether (MTBE) in gasoline has led to detectable concentrations in urban and rural air up to 160 ppbV. Results from MTBE measurement in precipitation have not been reported so far. In the present study, 120 samples of precipitation collected at 17 sampling locations all over Germany have been analyzed for their MTBE content. Analysis is performed by a combination of headspace-solid-phase microextraction (HS-SPME) and gas chromatography/mass spectrometry (GC-MS). A 75 μm poly(dimethylsiloxane)/Carboxene fiber and a cryostat is used for SPME. The detection limit is 10 ng/l. In precipitation samples, MTBE was detected in wintertimes only with a maximum concentration of 85 ng/l. Measurement at Frankfurt/M City from 6 September 2000 to 12 March 2001 provided for 49% of the data concentrations in the range of 30–85 ng/l (n=17). Sampling in winter 2000/2001 at several German cities and rural locations showed that MTBE is more often detectable in urban (86%, n=78) than in rural (18%, n=42) precipitation. By comparing the results with corresponding temperatures and amounts of precipitation it can be concluded that the detection of MTBE in urban precipitation is observed at ambient temperatures lower than about 10–15°C. Moreover, the first precipitation after a dry period accumulates more MTBE than precipitation during or at the end of a wet period (wash-out effect). Highest concentrations occurred in snow samples. Corresponding mean air equilibrium concentrations of 0.04 ppbV (urban samples) and 0.01 ppbV (rural samples) are calculated. This is about one magnitude lower than year round and summertime measurements in the US and in Switzerland. Urban runoff (n=12) and corresponding precipitation sampling indicate that urban runoff might be composed of about 20% MTBE that is already transported by air and precipitation, whereas about 80% may be attributed to direct uptake of vehicle emissions and leakage near the road during precipitation.     

A rapid method for determination of Aroclor 1260 in cattle adipose tissue

Abstract

A simple analytical procedure for the determination of Aroclor 1260 in cattle adipose tissue is described. The polychlorinated biphenyls residues are extracted from the tissue using a soxhlet extractor and the extracts are cleaned up using a florisil SEP‐PAK cartridge. The residues are detected using a gas chromatograph equipped with an electron capture detector. The effect of extraction time of the Aroclor 1260 residues from the tissue has been investigated and a period of four hours is found to give satisfactory percent recoveries. Greater than 85 percent recoveries were obtained from adipose tissue spiked with Aroclor 1260. The method can be used to detect Aroclor 1260 residue levels as low as 0.10 parts per million.

The method was used to analyze thirty‐one cattle adipose tissue samples out of which twenty‐six samples were taken from cattle suspected of exposure to a pasture containing electrical transformers and capacitors containing Aroclor 1260. Five control samples were collected from cattle with no known exposure. All twenty‐six samples were found to contain non‐detectable Aroclor 1260 residues.     

Persistence characteristics of operationally sprayed fenitrothion in nearby unsprayed areas of a conifer forest ecosystem in New Brunswick

Abstract

Persistence characteristics of operationally sprayed fenitrothion were investigated in various substrates sampled from neighbouring unsprayed areas in New Brunswick. Air, water, sediment, aquatic plants, fish, balsam fir [Abies balsamea (L.) Mill] foliage, forest soil and litter samples were collected from random sampling locations selected within 200 m from the operational spray blocks. The same substrates were resampled from the same plots and from the same locations about a year later just prior to the commencement of the operational spraying. Control samples were collected from an unsprayed site, near Sault Ste. Marie, Ontario. All samples were analysed for fenitrothion, by gas‐liquid chromatography. Except the fish samples all the substrates collected during the time of operational spraying contained low but detectable levels of fenitrothion. When collected a year later prior to the operational spray program, only balsam fir showed any detectable levels (detection limit, 0.01 ppm) of the chemical. All other samples showed no fenitrothion residues (detection limit for air, 10 ng/m³; for water, 0.01 ppb; and for other samples, 0.01 ppm). The findings confirmed that fenitrothion does not persist for an extended period of time in the aquatic substrates. The conifer foliage, however, showed persistent residues at a level of about 0.55 ppm even after the winter months, although there was no indication of accumulation of the chemical as a result of repeated exposure. The study demonstrated that the conifer needles acted as a micro sink for the chemical which showed a tendency to persist in the leaf tissues for a considerable length of time.     

Alveolar Breath Sampling and Analysis to Assess Exposures to Methyl Tertiary Butyl Ether (MTBE) During Motor Vehicle Refueling

Abstract

Methyl tertiary butyl ether (MTBE) is added to gasoline (15% by volume) in many areas of the U.S. to help control carbon monoxide emissions from motor vehicles. In this study we present a sampling and analytical methodology that can be used to assess consumers' exposures to MTBE that may result from routine vehicle refueling operations. The method is based on the collection of alveolar breath samples using evacuated one-liter stainless steel canisters and analysis using a gas chromatograph-mass spectrometer equipped with a patented "valveless" cryogenic preconcentrator.

To demonstrate the utility of this approach, a series of breath samples was collected from two individuals (the person pumping the fuel and a nearby observer) immediately before and for 64 min after a vehicle was refueled with premium grade gasoline. Results demonstrate low levels of MTBE in both subjects' breaths before refueling, and levels that increased by a factor of 35 to 100 after the exposure. Breath elimination models fitted to the post exposure measurements indicate that the half-life of MTBE in the first physiological compartment was between 1.3 and 2.9 min. Analysis of the resulting models suggests that breath elimination of MTBE during the 64 min monitoring period was approximately 115 jug for the refueling subject while it was only 30 ug for the nearby observer. This analysis also shows that the post exposure breath elimination of other gasoline constituents was consistent with previously published observations.

These results demonstrate that this new methodology can be used effectively in studies designed to assess exposures to MTBE. The method can be used to objectively demonstrate recent exposures, the relative magnitude of an exposure, and the approximate duration of the resulting bloodborne dose. Once a blood/breath partition coefficient for MTBE has been firmly established, the bloodborne concentration of the absorbed material can be determined using these techniques as well.     

Sampling atmospheric pesticides with SPME: Laboratory developments and field study

To estimate the atmospheric exposure of the greenhouse workers to pesticides, solid phase microextraction (SPME) was used under non-equilibrium conditions. Using Fick's law of diffusion, the concentrations of pesticides in the greenhouse can be calculated using pre-determined sampling rates (SRs). Thus the sampling rates (SRs) of two modes of SPME in the lab and in the field were determined and compared. The SRs for six pesticides in the lab were 20.4-48.3 mL min⁻¹ for the exposed fiber and 0.166-0.929 mL min⁻¹ for the retracted fiber. In field sampling, two pesticides, dichlorvos and cyprodinil were detected with exposed SPME. SR with exposed SPME for dichlorvos in the field (32.4 mL min^-1) was consistent with that in the lab (34.5 mL min^-1). SR for dichlorvos in the field (32.4 mL min⁻¹) was consistent with that in the lab (34.5 mL min⁻¹). The trends of temporal concentration and the inhalation exposure were also obtained.     

Filtration of Radioactive Aerosols By Glass Fibers

Abstract

An ozone (O₃) exposure assessment study was conducted in Toronto, Ontario, Canada during the winter and summer of 1992. A new passive O₃ sampler developed by Harvard was used to measure indoor, outdoor, and personal O₃ concentrations. Measurements were taken weekly and daily during the winter and summer, respectively. Indoor samples were collected at a total of 50 homes and workplaces of study participants. Outdoor O₃ concentrations were measured both at home sites using the passive sampler and at 20 ambient monitoring sites with continuous monitors. Personal O₃ measurements were collected from 123 participants, who also completed detailed time-activity diaries. A total of 2,274 O₃ samples were collected. In addition, weekly air exchange rates of homes were measured.

This study demonstrates the performance of our O₃ sampler for exposure assessment. The data obtained are further used to examine the relationships between personal, indoor (home and workplace), and outdoor O₃ concentrations, and to investigate outdoor and indoor spatial variations in O₃ concentrations. Based on home outdoor and indoor, workplace, and ambient O₃ concentrations measured at the Ontario Ministry of the Environment (MOE) sites, the traditional microenvironmental model predicts 72% of the variability in measured personal exposures. An alternative personal O₃ exposure model based on outdoor measurements and time-activity information is able to predict the mean personal exposures in a large population, with the highest R² value of 0.41.     

Characterization of Volatile Organic Chemical Emissions From Carpet Cushions

Abstract

The U.S. Consumer Product Safety Commission is investigating chemical emissions from carpet systems in order to determine whether the emissions may be responsible for the numerous health complaints associated with carpet installation. As part of this effort, a study was conducted to identify and quantify volatile organic compounds (VOCs) released into the air by five major product types of new carpet cushions. Cushion samples were tested in small-volume dynamic chambers over a six-hour exposure period. Airborne VOCs collected on multisorbent samplers were identified using sensitive gas chromatography/mass spectrometry. The emissions of selected VOCs were quantitated with the small-scale chamber method and further characterized in larger environmental chambers conducted over a 96-hour period under conditions more representative of indoor environments. A separate chamber method was developed to screen polyurethane cushions for emissions of toluene diisocyanates (TDI). Over 100 VOCs, spanning a broad range of chemical classes, were emitted from 17 carpet cushions. The pattern of emitted VOCs varied between and among product types, which reflects probable differences in manufacturing processes and ingredients. No significant quantities of TDI or formaldehyde were released by any cushions. Emission profiles were characterized for total VOCs and for the predominant individual VOCs. As a group, the synthetic fiber cushion samples emitted the lowest quantities of VOCs. Cushion samples purchased from carpet retailers released lesser amounts of VOCs than samples of the same cushion types obtained directly from the manufacturing mills, suggesting that chemical losses from the bulk material may ensue as a result of transport, handling, and storage prior to installation. The data suggest that placement of carpet on top of a carpet cushion, as would occur in a residential installation, reduced the rate of some VOC emissions when compared to the cushion alone.     

Development, validation and application of a method to analyze phenols in water samples by solid phase micro extraction-gas chromatography-flame ionization detector

In this work the development, validation and application of method using Solid Phase Microexctration (SPME) for the analyses of five pollutants (phenol, 2-nitrophenol, 2,4-dimethylphenol, 2,4-dichlorophenol and 4-chloro, 3-methyl phenol) in supplying water, using gas chromatography (GC) with flame ionization detector (FID) is described. The optimal conditions obtained for SPME were: fiber type: Poliacrylate (PA); extraction time: 40 minutes; extraction temperature: 70 degrees C; amount of salt added to sample (NaCl): 15%; desorption temperature: 8 minutes. The parameters studied in the method validation were: limit of detection (0.3 and 3.5 microg.L(- 1)); precision, measured by the variation coefficient (between 2.1 and 8.8%); calibration curve and linearity, by using the external standardization method (between 1 and 50 50 microg.L(- 1)). After the methodology development, samples of water collected in Atibaia River (S?o Paulo - Brazil) were analyzed, using the optimized methodology. Three water samples collected in the rain season showed a peak with retention time close to 4-chloro, 3 methyl phenol further analyzed by Gas Chromatography-Mass Spectrometry for the identity confirmation. In spite of the fact that none target compounds were found in the river water samples analyzed, the presence of two phenols different from those investigated (p-terc butyl phenol; butylated hydroxytoluene) were detected. These results together with the results of the limit of detection (that showed to be lower than the maximum concentration of phenols demanded by different environment control agencies), and the results of the validation, indicate the applicability of this method for the analysis of selected phenols in river water samples.