Determination of total petroleum hydrocarbons in soil from different locations using infrared spectrophotometry and gas chromatography

Total petroleum hydrocarbons (TPH) are important environmental contaminants which are toxic to human and environmental receptors. Several analytical methods have been used to quantify TPH levels in contaminated soils, specifically through infrared spectrometry (IR) and gas chromatography (GC). Despite being two of the most used techniques, some issues remain that have been inadequately studied: a) applicability of both techniques to soils contaminated with two distinct types of fuel (petrol and diesel), b) influence of the soil natural organic matter content on the results achieved by various analytical methods, and c) evaluation of the performance of both techniques in analyses of soils with different levels of contamination (presumably non-contaminated and potentially contaminated). The main objectives of this work were to answer these questions and to provide more complete information about the potentials and limitations of GC and IR techniques. The results led us to the following conclusions: a) IR analysis of soils contaminated with petrol is not suitable due to volatilisation losses, b) there is a significant influence of organic matter in IR analysis, and c) both techniques demonstrated the capacity to accurately quantify TPH in soils, irrespective of their contamination levels.

Mass spectrometry parameters optimization for the 46 multiclass pesticides determination in strawberries with gas chromatography ion-trap tandem mass spectrometry

Multiclass analysis method was optimized in order to analyze pesticides traces by gas chromatography with ion-trap and tandem mass spectrometry (GC-MS/MS). The influence of some analytical parameters on pesticide signal response was explored. Five ion trap mass spectrometry (IT-MS) operating parameters, including isolation time (IT), excitation voltage (EV), excitation time (ET),maximum excitation energy or “q” value (q), and isolationmass window (IMW) were numerically tested in order to maximize the instrument analytical signal response. For this, multiple linear regression was used in data analysis to evaluate the influence of the five parameters on the analytical response in the ion trap mass spectrometer and to predict its response. The assessment of the five parameters based on the regression equations substantially increased the sensitivity of IT-MS/MS in the MS/MS mode. The results obtained show that for most of the pesticides, these parameters have a strong influence on both signal response and detection limit.Using the optimized method, a multiclass pesticide analysis was performed for 46 pesticides in a strawberry matrix. Levels higher than the limit established for strawberries by the European Union were found in some samples.

Analysis of PCBs in soils and sediments by microwave-assisted extraction, headspace-SPME and high resolution gas chromatography with ion-trap tandem mass spectrometry

A procedure for the determination of seven indicator PCBs in soils and sediments using microwave-assisted extraction (MAE) and headspace solid-phase microextraction (HS-SPME) prior to GC-MS/MS is described. Optimization of the HS-SPME was carried out for the most important parameters such as extraction time, sample volume and temperature. The adopted methodology has reduced consumption of organic solvents and analysis runtime. Under the optimized conditions, the method detection limit ranged from 0.6 to 1 ng/g when 5 g of sample was extracted, the precision on real samples ranged from 4 to 21% and the recovery from 69 to 104%. The proposed method, which included the analysis of a certified reference material in its validation procedure, can be extended to several other PCBs and used in the monitoring of soil or sediments for the presence of PCBs.

Indirect hydrogen analysis by gas chromatography coupled to mass spectrometry (GC-MS).

Gas chromatography (GC) is an analytical tool very useful to investigate the composition of gaseous mixtures. The different gases are separated by specific columns but, if hydrogen (H2 ) is present in the sample, its detection can be performed by a thermal conductivity detector or a helium ionization detector. Indeed, coupled to GC, no other detector can perform this detection except the expensive atomic emission detector. Based on the detection and analysis of H2 isotopes by low-pressure chemical ionization mass spectrometry (MS), a new method for H2 detection by GC coupled to MS with an electron ionization ion source and a quadrupole analyser is presented. The presence of H2 in a gaseous mixture could easily be put in evidence by the monitoring of the molecular ion of the protonated carrier gas. Copyright © 2013 John Wiley & Sons, Ltd.

Validation of an analytical method for nitrous oxide (N2O) laughing gas by headspace gas chromatography coupled to mass spectrometry (HS-GC-MS): Forensic application to a lethal intoxication.

Drug abuse is a widespread problem affecting both teenagers and adults. Nitrous oxide is becoming increasingly popular as an inhalation drug, causing harmful neurological and hematological effects. Some gas chromatography-mass spectrometry (GC-MS) methods for nitrous oxide measurement have been previously described. The main drawbacks of these methods include a lack of sensitivity for forensic applications; including an inability to quantitatively determine the concentration of gas present. The following study provides a validated method using HS-GC-MS which incorporates hydrogen sulfide as a suitable internal standard allowing the quantification of nitrous oxide. Upon analysis, sample and internal standard have similar retention times and are eluted quickly from the molecular sieve 5Å PLOT capillary column and the Porabond Q column therefore providing rapid data collection whilst preserving well defined peaks. After validation, the method has been applied to a real case of N2O intoxication indicating concentrations in a mono-intoxication.

Rapid high-performance liquid chromatographic determination with fluorescence detection of furosemide in human body fluids and its confirmation by gas chromatography-mass spectrometry.

Furosemide (FD: Lasix) is a loop diuretic which strongly increases both urine flow and electrolyte urinary excretion. Healthy volunteers were administered 40 mg orally (dissolved in water) and concentrations of FD were determined in serum and urine for up to 6 h for eight subjects, who absorbed water at a rate of 400 ml/h. Quantification was performed by HPLC with fluorescence detection (excitation at 233 nm, emission at 389 nm) with a limit of detection of 5 ng/ml for a 300-microliters sample. The elution of FD was completed within 4 min using a gradient of acetonitrile concentration rising from 30 to 50% in 0.08 M phosphoric acid. The delay to the peak serum concentration ranged from 60 to 120 min. FD was still easily measurable in the sera from all subjects 6 h after administration. In urine, the excretion rates reached their maximum between 1 and 3 h. The total amount of FD excreted in the urine averaged 11.2 mg (range 7.6-14.0 mg), with a mean urine volume of 3024 ml (range 2620-3596 ml). Moreover, the urine density was lower than 1.010 (recommended as an upper limit in doping analysis to screen diuretics) only for 2 h. An additional volunteer was administered 40 mg of FD and his urine was collected over a longer period. FD was still detectable 48 h after intake. Gas chromatography-mass spectrometry with different types of ionization was used to confirm the occurrence of FD after permethylation of the extract. Negative-ion chemical ionization, with ammonia as reactant gas, was found to be the most sensitive method of detection.

Investigations into the extraction and the determination of polycyclic aromatic hydrocarbons (PAHs) from water by solid-phase extraction and capillary gas chromatography/ mass spectrometry

Factors affecting the detennination of PAHs by capillary GC/MS were studied. The effect of the initial column temperature and the injection solvent on the peak areas and heights of sixteen PAHs, considered as priority pollutants, USillg crosslinked methyl silicone (DB!) and 5% diphenyl, 94% dimethyl, 1% vinyl polysiloxane (DBS) columns was examined. The possibility of using high boiling point alcohols especially butanol, pentanol, cyclopentanol, and hexanol as injection solvents was investigated. Studies were carried out to optimize the initial column temperature for each of the alcohols. It was found that the optimum initial column temperature is dependent on the solvent employed. The peak areas and heights of the PAHs are enhanced when the initial column temperature is 10-20 c above the boiling point of the solvent using DB5 column, and the same or 10 C above the boiling point of the solvent using DB1 column. Comparing the peak signals of the PAHs using the alcohols, p-xylene, n-octane, and nonane as injection solvents, hexanol gave the greatest peak areas and heights of the PAHs particularly the late-eluted peaks. The detection limits were at low pg levels, ranging from 6.0 pg for fluorene t9 83.6 pg for benzo(a)pyrene. The effect of the initial column temperature on the peak shape and the separation efficiency of the PARs was also studied using DB1 and DB5 columns. Fronting or splitting of the peaks was obseIVed at very low initial column temperature. When high initial column temperature was used, tailing of the peaks appeared. Great difference between DB! and.DB5 columns in the range of the initial column temperature in which symmetrical.peaks of PAHs can be obtained is observed. Wider ranges were shown using DB5 column. Resolution of the closely-eluted PAHs was also affected by the initial column temperature depending on the stationary phase employed. In the case of DB5, only the earlyeluted PAHs were affected; whereas, with DB1, all PAHs were affected. An analytical procedure utilizing solid phase extraction with bonded phase silica (C8) cartridges combined with GC/MS was developed to analyze PAHs in water as an alternative method to those based on the extraction with organic solvent. This simple procedure involved passing a 50 ml of spiked water sample through C8 bonded phase silica cartridges at 10 ml/min, dried by passing a gentle flow of nitrogen at 20 ml/min for 30 sec, and eluting the trapped PAHs with 500 Jll of p-xylene at 0.3 ml/min. The recoveries of PAHs were greater than 80%, with less than 10% relative standard deviations of nine determinations. No major contaminants were present that could interfere with the recognition of PAHs. It was also found that these bonded phase silica cartridges can be re-used for the extraction of PAHs from water.

Residues in soils : a gas chromatography - mass spectrometry study

Combined gas chromatography and mass spectrometry has been used to identify unknown residues in soils (especially pesticides). The effect of U.V. light on DDT and linuron and quantitative estimation of elemental sulfur in different soils has also been carried out.

Investigations into the determination of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) by capillary gas chromatography

Factors involved in the determination of PAHs (16 priority PAHs as an example) and PCBs (10 PCB congeners, representing 10 isomeric groups) by capillary gas chromatography coupled with mass spectrometry (GC/MS, for PAHs) and electron capture detection (GC/ECD , for PCBs) were studied, with emphasis on the effect of solvent. Having various volatilities and different polarities, solvent studied included dichloromethane, acetonitrile, hexan e, cyclohexane, isooctane, octane, nonane, dodecane, benzene, toluene, p-xylene, o-xylene, and mesitylene. Temperatures of the capillary column, the injection port, the GC/MS interface, the flow rates of carrier gas and make-up gas, and the injection volume were optimized by one factor at a time method or simplex optimization method. Under the optimized conditions, both peak height and peak area of 16 PAHs, especially the late-eluting PAHs, were significantly enhanced (1 to 500 times) by using relatively higher boiling point solvents such as p-xylene and nonane, compared with commonly used solvents like benzene and isooctane. With the improved sensitivity, detection limits of between 4.4 pg for naphthalene and 30.8 pg for benzo[g,h,i]perylene were obtained when p-xylene was used as an injection solvent. Effect of solvent on peak shape and peak intensity were found to be greatly dependent on temperature parameters, especially the initial temperature of the capillary column. The relationship between initial temperature and shape of peaks from 16 PAHs and 10 PCBs were studied and compared when toluene, p-xylene, isooctane, and nonane were used as injection solvents. If a too low initial temperature was used, fronting or split of peaks was observed. On the other hand, peak tailing occurred at a too high initial column temperature. The optimum initial temperature, at which both peak fronting and tailing were avoided and symmetrical peaks were obtained, depended on both solvents and the stationary phase of the column used. On a methyl silicone column, the alkane solvents provided wider optimum ranges of initial temperature than aromatic solvents did, for achieving well-shaped symmetrical GC peaks. On a 5% diphenyl: 1% vinyl: 94% dimethyl polysiloxane column, when the aromatic solvents were used, the optimum initial temperature ranges for solutes to form symmetrical peaks were improved to a similar degree as those when the alkanes were used as injection solvents. A mechanism, based on the properties of and possible interactions among the analyte, the injection solvent, and the stationary phase of the capillary column, was proposed to explain these observations. The effect of initial temperature on peak height and peak area of the 16 PAHs and the 10 PCBs was also studied. The optimum initial temperature was found to be dependent on the physical properties of the solvent used and the amount of the solvent injected. Generally, from the boiling point of the solvent to 10 0C above its boiling point was an optimum range of initial temperature at which cthe highest peak height and peak area were obtained.

Gas chromatographic electron capture negative ionization mass spectrometric (GC/ECNI/MS) determination of unique fluorinated compounds in the sediments of Lake Ontario and the effect of high-boiling alcohols (as injection solvents) on chromatographic behaviour of polycyclic aromatic hydrocarbons in gas chromatography

Part I - Fluorinated Compounds A method has been developed for the extraction, concentration, and determination of two unique fluorinated compounds from the sediments of Lake Ontario. These compounds originated from a common industrial landfill, and have been carried to Lake Ontario by the Niagara River. Sediment samples from the Mississauga basin of Lake Ontario have been evaluated for these compounds and a depositional trend was established. The sediments were extracted by accelerated solvent extraction (ASE) and then underwent clean-up, fractionation, solvent exchange, and were concentrated by reduction under nitrogen gas. The concentrated extracts were analyzed by gas chromatography - electron capture negative ionization - mass spectrometry. The depositional profile determined here is reflective of the operation of the landfill and shows that these compounds are still found at concentrations well above background levels. These increased levels have been attributed to physical disturbances of previously deposited contaminated sediments, and probable continued leaching from the dumpsite. Part II - Polycyclic Aromatic Hydrocarbons Gas chromatography/mass spectrometry is the most common method for the determination of polycyclic aromatic hydrocarbons (PAHs) from various matrices. Mass discrimination of high-boiling compounds in gas chromatographic methods is well known. The use of high-boiling injection solvents shows substantial increase in the response of late-eluting peaks. These solvents have an increased efficiently in the transfer of solutes from the injector to the analytical column. The effect of I-butanol, I-pentanol, cyclopentanol, I-hexanol, toluene and n-octane, as injection solvents, was studied. Higher-boiling solvents yield increased response for all PAHs. I -Hexanol is the best solvent, in terms of P AH response, but in this solvent P AHs were more susceptible to chromatographic problems such as peak splitting and tailing. Toluene was found to be the most forgiving solvent in terms of peak symmetry and response. It offered the smallest discrepancies in response, and symmetry over a wide range of initial column temperatures.

Determination of volatile organic compounds in recycled polyethylene terephthalate and high-density polyethylene by headspace solid phase microextraction gas chromatography mass spectrometry to evaluate the efficiency of recycling processes

A method for the determination of volatile organic compounds (VOCs) in recycled polyethylene terephthalate and high-density polyethylene using headspace sampling by solid-phase microextraction and gas chromatography coupled to mass spectrometry detection is presented. This method was used to evaluate the efficiency of cleaning processes for VOC removal from recycled PET. In addition, the method was also employed to evaluate the level of VOC contamination in multilayer packaging material containing recycled HDPE material. The optimisation of the extraction procedure for volatile compounds was performed and the best extraction conditions were found using a 75 mu m carboxen-polydimethylsiloxane (CAR-PDMS) fibre for 20 min at 60 degrees C. The validation parameters for the established method were linear range, linearity, sensitivity, precision (repeatability), accuracy (recovery) and detection and quantification limits. The results indicated that the method could easily be used in quality control for the production of recycled PET and HDPE. (C) 2011 Elsevier B.V. All rights reserved.

Quantitative ester analysis in cachaca and distilled spirits by gas chromatography-mass spectrometry (GC-MS)

An analytical procedure for the separation and quantification of ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, isoamyl octanoate, and ethyl laurate in cachaca, rum, and whisky by direct injection gas chromatography-mass spectrometry was developed. The analytical method is simple, selective, and appropriated for the determination of esters in distilled spirits. The limit of detection ranged from 29 (ethyl hexanoate) to 530 (ethyl acetate) mu g L-1, whereas the standard deviation for repeatability was between 0.774% (ethyl hexanoate) and 5.05% (isoamyl octanoate). Relative standard deviation values for accuracy vary from 90.3 to 98.5% for ethyl butyrate and ethyl acetate, respectively. Ethyl acetate was shown to be the major ester in cachaca (median content of 22.6 mg 100 mL(-1) anhydrous alcohol), followed by ethyl lactate (median content of 8.32 mg 100 mL(-1) anhydrous alcohol). Cachaca produced in copper and hybrid alembic present a higher content of ethyl acetate and ethyl lactate than those produced in a stainless-steel column, whereas cachaca produced by distillation in a stainless-steel column present a higher content of ethyl octanoate, ethyl decanoate, and ethyl laurate. As expected, ethyl acetate is the major ester in whiskey and rum, followed by ethyl lactate for samples of rum. Nevertheless, whiskey samples exhibit ethyl lactate at contents lower or at the same order of magnitude of the fatty esters.

Determination of fluoxetine in plasma by gas chromatography-mass spectrometry using stir bar sorptive extraction

This article presents a method employing stir bar sorptive extraction (SBSE) with in situ derivatization, in combination with either thermal or liquid desorption on-line coupled to gas chromatography-mass spectrometry for the analysis of fluoxetine in plasma samples. Ethyl chloroformate was employed as derivatizing agent producing symmetrical peaks. Parameters such as solvent polarity, time for analyte desorption, and extraction time, were evaluated. During the validation process, the developed method presented specificity, linearity (R-2 > 0.99), precision (R.S.D. < 15%), and limits of quantification (LOQ) of 30 and 1.37 pg mL(-1), when liquid and thermal desorption were employed, respectively. This simple and highly sensitive method showed to be adequate for the measurement-of fluoxetine in typical and trace concentration levels. (c) 2008 Elsevier B.V. All rights reserved.

Evaluation of the QuEChERS Method and Gas Chromatography-Mass Spectrometry for the Analysis Pesticide Residues in Water and Sediment

A method for the determination of pesticide residues in water and sediment was developed using the QuEChERS method followed by gas chromatography - mass spectrometry. The method was validated in terms of accuracy, specificity, linearity, detection and quantification limits. The recovery percentages obtained for the pesticides in water at different concentrations ranged from 63 to 116%, with relative standard deviations below 12%. The corresponding results from the sediment ranged from 48 to 115% with relative standard deviations below 16%. The limits of detection for the pesticides in water and sediment were below 0.003 mg L(-1) and 0.02 mg kg(-1), respectively.

Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction as a powerful tool for quantification of ethyl carbamate in fortified wines. The case study of Madeira wine

An analytical methodology based on headspace solid phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography—time-of-flight mass spectrometry (GC × GC–ToFMS) was developed for the identification and quantification of the toxic contaminant ethyl carbamate (EC) directly in fortified wines. The method performance was assessed for dry/medium dry and sweet/medium sweet model wines, and for quantification purposes, calibration plots were performed for both matrices using the ion extraction chromatography (IEC) mode (m/z 62). Good linearity was obtained with a regression coefficient (r2) higher than 0.981. A good precision was attained (R.S.D. <20%) and low detection limits (LOD) were achieved for dry (4.31 μg/L) and sweet (2.75 μg/L) model wines. The quantification limits (LOQ) and recovery for dry wines were 14.38 μg/L and 88.6%, whereas for sweet wines were 9.16 μg/L and 99.4%, respectively. The higher performance was attainted with sweet model wine, as increasing of glucose content improves the volatile compound in headspace, and a better linearity, recovery and precision were achieved. The analytical methodology was applied to analyse 20 fortified Madeira wines including different types of wine (dry, medium dry, sweet, and medium sweet) obtained from several harvests in Madeira Island (Portugal). The EC levels ranged from 54.1 μg/L (medium dry) to 162.5 μg/L (medium sweet).