F.J. Santos

Modern developments in gas chromatography-mass spectrometry-based environmental analysis.

Gas chromatography coupled with mass spectrometry (GC-MS) continues to play an important role in the identification and quantification of organic contaminants in environmental samples. GC-MS is one of the most attractive and powerful techniques for routine analysis of some ubiquitous organic pollutants due to its good sensitivity and high selectivity and versatility. This paper presents an overview of recent developments and applications of the GC-MS technique in relation to the analysis in environmental samples of known persistent pollutants and some emerging contaminants. The use of different mass analysers such as linear quadrupole, quadrupole ion-trap, double-focusing sectors and time-of-flight analysers is examined. The advantages and limitations of GC-MS methods for selected applications in the field of environmental analysis are discussed. Recent developments in field-portable GC-MS are also examined.

Determination of chlorophenols by solid-phase microextraction and liquid chromatography with electrochemical detection.

A solid-phase microextraction method has been developed for the determination of 19 chlorophenols (CPs) in environmental samples. The analytical procedure involves direct sampling of CPs from water using solid-phase microextraction (SPME) and determination by liquid chromatography with electrochemical detection (LC-ED). Three kinds of fibre [50 microm carbowax-templated resin (CW-TPR), 60 microm polydimethylsiloxane-divinylbenzene (PDMS-DVB) and 85 microm polyacrylate (PA)] were evaluated for the analysis of CPs. Of these fibres, CW-TPR is the most suitable for the determination of CPs in water. Optimal conditions for both desorption and absorption SPME processes, such as composition of the desorption solvent (water-acetonitrile-methanol, 20:30:50) and desorption time (5 min), extraction time (50 min) and temperature (40 degrees C) as well as pH (3.5) and ionic strength (6 g NaCl) were established. The precision of the SPME-LC-ED method gave relative standard deviations (RSDs) of between 4 and 11%. The method was linear over three to four orders of magnitude and the detection limits, from 3 to 8 ng l(-1), were lower than the European Community legislation limits for drinking water. The method was applied to the analysis of CPs in drinking water and wood samples.

Application of solid-phase microextraction to the analysis of volatile organic compounds in water

Solid-phase microextraction (SPME) was investigated as a solvent-free alternative method for the extraction and analysis of some volatile organic compounds which can be present in industrial effluents. Such compounds are included in the hazardous pollutants list of the US National Institute for Occupational Safety and Health and the US Environmental Protection Agency. The performance of SPME fibres coated with two different stationary phases, such as poly(dimethylsiloxane) 100 μm and 7 μm film thickness and 85 μm poly(acrylic acid) were evaluated. Absorption times of 12 min for 100-μm poly(dimethylsiloxane) and 85-μm poly(acrylic acid) fibres and 5 min for 7-μm poly(dimethylsiloxane) were needed to reach the equilibrium and 2 min was enough for complete desorption of the analytes in the injection port of the gas chromatograph. High recoveries were obtained using the 100-μm poly(dimethylsiloxane) fibre, although for polar compounds better results were found using the 85-μm poly(acrylic acid) fibre. Linear dynamic ranges and a detection limit between 0.3 and 1.5 μg 1−1 were obtained using the 100-μm poly(dimethylsiloxane) fibre and flame ionization detection. The SPME-GC procedure gave good repeatability (R.S.D. = 4.3–10.5%) and reproducibility (R.S.D. = 6.6–12.9%). The proposed SPME-GC method was applied to determine some volatile organic compounds in spiked drinking water and in industrial effluent samples.

Analysis of chlorobenzenes in soils by headspace solid-phase microextraction and gas chromatography-ion trap mass spectrometry

Headspace solid-phase microextraction (SPME) with gas chromatography-ion trap mass spectrometry (GC-IT-MS) was investigated as a possible alternative to Soxhlet extraction in the analysis of chlorobenzenes in soils. A 100 μm polydimethylsiloxane fibre was used for the optimization studies. Maximum sensitivity was obtained at a sampling temperature of 30°C and with an absorption time of 25 min. The effect of the addition of solvents of different polarity was evaluated. Better repeatability (R.S.D. between 5 and 7%) and higher responses were obtained when water was added to the soil. The headspace SPME method was applied to the analysis of the chlorobenzenes, 1,2,3-trichlorobenzene, 1,2,3,4-tetrachlorobenze and pentachlorobenzene, in an industrially contaminated sandy soil, CRM-529 (Candidate Reference Material). The chlorobenzenes in this soil were quantified by standard addition, which led to good reproducibility (R.S.D. between 3 and 5%) and adequate detection limits (0.03 to 0.1 ng g− of soil). The method was validated by comparing the results with those obtained in a European intercomparison exercise.

Development of a sequential supercritical fluid extraction method for the analysis of nitrated and oxygenated derivatives of polycyclic aromatic hydrocarbons in urban aerosols

A two-step supercritical fluid extraction (SFE) method has been developed for the analysis of oxygenated and nitrated polycyclic aromatic hydrocarbons (oxy- and nitro-PAHs, respectively) present in urban aerosol samples. The proposed SFE procedure first involves an extraction step using pure CO2 in order to remove the less polar compounds from the matrix and a second consecutive step using toluene-modified CO2. The oxy- and nitro-PAHs are obtained in the second step. Parameters affecting both collection efficiencies and the selective extraction of oxy- and nitro-PAHs in the second SFE step were optimised. Analysis of the extracts was performed using gas chromatography with electron-capture detection and coupled to mass spectrometry. The proposed SFE method was compared with a conventional extraction technique such as sonication and good agreement in the results was obtained. Nevertheless, clean up of sonication extracts was needed, whereas no purification was necessary for SFE extracts. The SFE method was applied to the analysis of oxy- and nitro-PAHs in urban aerosol samples and 9-fluorenone, 9,10-anthraquinone, 2-methyl-9,10-anthraquinone, benzanthrone, benz[a]anthracene-7,12-dione and 1-nitropyrene were identified at concentrations ranging between 15 and 364 pg m(-3).

Solid-phase microextraction coupled with gas chromatography–ion trap mass spectrometry for the analysis of haloacetic acids in water

Headspace solid-phase microextraction (SPME) was studied as a possible alternative to liquid-liquid extraction for the analysis of haloacetic acids (HAAs) in water. The method involves derivatization of the acids to their ethyl esters using sulphuric acid and ethanol after evaporation, followed by headspace SPME with a polydimethylsiloxane fibre and gas chromatography-ion trap mass spectrometry (GC-IT-MS). The derivatization procedure was optimized: maximum sensitivity was obtained with esterification for 10 min at 50 degrees C in 30 microl of sulphuric acid and 40 microl of ethanol. The headspace SPME conditions were also optimized and good sensitivity was obtained at a sampling temperature of 25 degrees C, an absorption time of 10 min, the addition of 0.1 g of anhydrous sodium sulfate and a desorption time of 2 min. Good precision (RSD lower than 10%) and detection limits in the ng l(-1) range (from 10 to 200 ng l(-1)) were obtained for all the compounds. The optimized procedure was applied to the analysis of HAAs in tap water and the results obtained by standard addition agreed with those of EPA method 552.2, whereas discrepancies due to matrix interferences were observed using external calibration. Consequently, headspace SPME-GC-IT-MS with standard addition is recommended for the analysis of these compounds in drinking water.

Microwave-assisted extraction versus Soxhlet extraction for the analysis of short-chain chlorinated alkanes in sediments.

Microwave-assisted extraction (MAE) was evaluated as a possible alternative to Soxhlet extraction for analysing short-chain chlorinated alkanes (commonly called short-chain chlorinated paraffins, SCCPs) in river sediment samples, using gas chromatography coupled to negative chemical ionisation mass spectrometry. For MAE optimisation, several extraction parameters such as solvent extraction mixture, extraction time and extraction temperature were studied. Maximum extraction efficiencies for SCCPs (90%) and for 12 polychlorinated biphenyl (PCB) congeners (91-95%) were achieved using 5 g of sediment sample, 30 ml of n-hexane-acetone (1:1, v/v) as solvent extraction, and 15 min and 115 degrees C of extraction time and temperature, respectively. Activated Florisil was used to clean-up the extracts, allowing highly selective separation of SCCPs from other organic contaminants such as PCBs. MAE was compared with a conventional extraction technique such as Soxhlet and good agreement in the results was obtained. Quality parameters of the optimised MAE method such as run-to-run (R.S.D. 7%) and day-to-day precision (R.S.D. 9%) were determined using spiked river sediment samples, with LODs of 1.5 ng g(-1). This method was successfully applied to the analysis of SCCPs in river sediment samples at concentrations below the ng g(-1) level. O 2004 Elsevier B.V. All rights reserved.

Occurrence of pesticides in Spanish surface waters. Analysis by high resolution gas chromatography coupled to mass spectrometry

Abstract A general study of the presence of pesticides in Spanish surface waters was carried out. A total of 97 samples were analysed by liquid-liquid extraction followed by HRGC/MS in full scan mode. This procedure allows the detection and identification of several commonly used pesticides at levels of 5–50ng/L. The results obtained are studied with regard to know the most common pesticides found in Spanish surface waters, the percentage of them proposed to be included in the Directive 76/464/EEC and their variability depending on the area (agricultural or industrial) and the period of sampling.

Selective pressurized liquid extraction of polybrominated diphenyl ethers in fish

A fast and simple method for the analysis of polybrominated diphenyl ethers (PBDEs) in fish samples was developed using a one-step extraction and clean-up by means of pressurized liquid extraction (PLE) combined with gas chromatography-ion trap tandem mass spectrometry (GC-ITMS-MS). The selective PLE method provided to obtain ready-to-analyse extracts without any additional clean-up step, using a sorbent as fat retainer inside the PLE cell. Several PLE operating conditions, such as solvent type, extraction temperature and time, number of cycles and type of fat retainer, were studied. Using Florisil as fat retainer, maximum recoveries of PBDEs (83-108%) with minimum presence of matrix-interfering compounds were obtained using a mixture of n-hexane:dichloromethane 90:10 (v/v) as solvent, an extraction temperature of 100 degrees C and a static extraction time of 5 min in combination with three static cycles. Quality parameters of the method were established using standards and fish samples. Limits of detection and quantification ranged from 10 to 34 pg g(-1) wet weight and between 34 and 68 pg g(-1) wet weight, respectively. In addition, good linearity (between 1 and 500 ng ml(-1)) and high precision (RSD %<15%) were achieved. The method was validated using the standard reference material SRM-1945 (whale blubber) and was then applied to the analysis of PBDEs in fish samples.

Occurrence of furan in coffee from Spanish market: Contribution of brewing and roasting

In this work, we evaluated the occurrence of furan in brews obtained from regular, decaffeinated, and instant coffee and commercial packed capsules. For this purpose, a previously developed automated headspace solid-phase microextraction method coupled to gas chromatography-mass spectrometry (HS-SPME-GC-MS) was used. Initially, the influence of HS-SPME conditions on furan formation was evaluated. In addition, the effect of roasting conditions (temperature and time) used for coffee beans on furan formation was also studied. We found that low temperature and long roasting time (140°C and 20min) decreases the final furan content. Furan concentrations in regular ground coffee brews from an espresso coffee machine were higher (43-146ng/ml) than those obtained from a home drip coffee maker (20 and 78ng/ml), while decaffeinated coffee brews from a home drip coffee maker (14-65ng/ml) showed a furan concentration similar to that obtained from regular coffee. Relatively low concentrations of this compound (12-35ng/ml) were found in instant coffee brews, while commercial packed coffee capsules showed the highest concentrations (117-244ng/ml). Finally, the daily intake of furan through coffee consumption in Barcelona (Spain) (0.03-0.38μg/kg of body weight) was estimated.