Programmed Temperature Vaporizer Research Articles

Trace Explosives Vapor Generation and Quantitation at Parts per Quadrillion Concentrations

The generation of trace 2,4,6-trinitrotoluene (TNT), cyclotrimethylenetrinitramine (RDX), and pentaerythritol tetranitrate (PETN) vapors using a pneumatically modulated liquid delivery system (PMLDS) coupled to a polytetrafluoroethylene (PTFE) total-consumption micronebulizer is presented. The vapor generator operates in a continuous manner with final vapor concentrations proportional to the explosive concentration in aqueous solution delivered through the nebulizer and the diluent air flow rate. For quantitation of concentrations in the parts per billionvolume (ppbv) to parts per trillionvolume (pptrv) range, Tenax-TA thermal desorption tubes were used for vapor collection with subsequent analysis on a thermal-desorption system programmable-temperature vaporization gas chromatograph (TDS-PTV-GC) with a μ-ECD detector. With 30 min sample times and an average sampling rate of 100 mL min(-1), vapor concentrations of 38 pptrv for TNT, 25 pptrv for RDX, and 26 pptrv for PETN were determined. For parts per quadrillionvolume (ppqv) vapor quantitation of TNT and RDX, an online PTV-GC system with a negative-ion chemical ionization mass spectrometer (methane reagent gas) was used for direct sampling and capture of the vapor on the PTV inlet. Vapor concentrations as low as 160 ppqv and 710 ppqv for TNT and RDX were quantified, respectively, with an instrument duty cycle as low as 4 min.

Determination of ultratrace levels of tributyltin in waters by isotope dilution and gas chromatography coupled to tandem mass spectrometry

The current EU legislation lays down the Environmental Quality Standards (EQS) of 45 priority substances in surface water bodies. In particular, the concentration of tributyltin (TBT) must not exceed 0.2ngL−1 and analytical methodologies with a Limit of Quantification (LOQ) equal or below 0.06ngL−1 are urged to be developed. This work presents a procedure for the determination of ultratrace levels of TBT in water samples by Isotope Dilution and GC–MS/MS operating in Selected Reaction Monitoring (SRM) mode which meets current EU requirements. The method requires the monitorization of five consecutive transitions (287>175 to 291>179) for the sensitive and selective detection of TBT. The measured isotopic distribution of TBT fragment ions was in agreement with the theoretical values computed by a polynomial expansion algorithm. The combined use of Tandem Mass Spectrometry, a sample volume of 250mL, the preconcentration of 1mL of organic phase to 30μL and an injection volume of 25μL by Programmed Temperature Vaporization provided a LOQ of 0.0426ngL−1 for TBT (calculated as ten times the standard deviation of nine independent blanks). The recovery for TBT calculated in Milli-Q water at the EQS level was 106.3±4%. A similar procedure was also developed for the quantification of dibutyltin (DBT) and monobutyltin (MBT) in water samples showing satisfactory results. The method was finally implemented in a routine testing laboratory to demonstrate its applicability to real samples obtaining quantitative recoveries for TBT at the EQS level in mineral water, river water and seawater.

Modification of a commercial gas chromatography isotope ratio mass spectrometer for on-line carbon isotope dilution: Evaluation of its analytical characteristics for the quantification of organic compounds

We describe the instrumental modification of a commercial gas chromatography isotope ratio mass spectrometer (GC–IRMS) and its application for on-line carbon isotope dilution. The main modification consisted in the addition of a constant flow of enriched 13CO2 diluted in helium after the chromatographic column through the splitter holder located inside the chromatographic oven of the instrument. In addition, and in contrast to the conventional mode of operation of GC–IRMS instruments where the signal at m/z 45 is amplified 100-fold with respect to the signal at m/z 44, the same signal amplification was used in both Faraday cups at m/z 44 and 45. Under these conditions isotope ratio precision for the ratio 44/45 was around 0.05% RSD (n=50). The evaluation of the instrument was performed with mixtures of organic compounds including 11 n-alkanes, 16 PAHs, 12 PCBs and 3 benzothiophenes. It was observed that compounds of very different boiling points could be analysed without discrimination in the injector when a Programmable Temperature Vaporizer (PTV) injector was employed. Moreover, the presence of heteroatoms (Cl or S) in the structure of the organic compounds did not affect their combustion efficiency and therefore the trueness of the results. Quantitative results obtained for all the analytes assayed were excellent in terms of precision (<3% RSD) and accuracy (average relative error≤4%) and what is more important using a single and simple generic internal standard for quantification.

Improved sensitivity gas chromatography–mass spectrometry determination of parabens in waters using ionic liquids

A new procedure for the introduction of ionic liquid samples in gas chromatography (GC) is proposed. This procedure, based on microvial insert thermal desorption, allows the direct analysis of the compounds preconcentrated by ionic liquid based liquid–liquid microextraction (IL-LLME) using the combination of a thermal desorption unit (TDU) and a programmed temperature vaporization injector (PTV). Two different IL-LLME methodologies, one based on the formation of a microdroplet emulsion by dispersive liquid–liquid microextraction (DLLME) and other through ultrasound-assisted emulsification microextraction (USAEME) were studied and evaluated. IL-DLLME proved advantageous and consequently, it was adopted for preconcentration purposes. This easy to apply approach was used for the determination of five parabens (methyl-, ethyl-, propyl-, butyl- and isobutyl paraben) in swimming pool waters, after in situ acetylation. The optimized conditions of TDU/PTV allowed the analytes contained in 20µL of the enriched IL to be transferred to the capillary column. Quantification of the samples was carried out against aqueous standards, and quantification limits of between 4.3 and 8.1ngL−1 were obtained, depending on the compound. Concentrations of between 9 and 47ngL−1 for some analytes were obtained in the analysis of ten samples.

Extension of a dynamic headspace multi-volatile method to milliliter injection volumes with full sample evaporation: Application to green tea

An extension of multi-volatile method (MVM) technology using the combination of a standard dynamic headspace (DHS) configuration, and a modified DHS configuration incorporating an additional vacuum module, was developed for milliliter injection volume of aqueous sample with full sample evaporation. A prior step involved investigation of water management by weighing of the water residue in the adsorbent trap. The extended MVM for 1mL aqueous sample consists of five different DHS method parameter sets including choice of the replaceable adsorbent trap. An initial two DHS sampling sets at 25°C with the standard DHS configuration using a carbon-based adsorbent trap target very volatile solutes with high vapor pressure (>10kPa) and volatile solutes with moderate vapor pressure (1–10kPa). Subsequent three DHS sampling sets at 80°C with the modified DHS configuration using a Tenax TA trap target solutes with low vapor pressure (<1kPa) and/or hydrophilic characteristics. After the five sequential DHS samplings using the same HS vial, the five traps are sequentially desorbed with thermal desorption in reverse order of the DHS sampling and the desorbed compounds are trapped and concentrated in a programmed temperature vaporizing (PTV) inlet and subsequently analyzed in a single GC–MS run. Recoveries of 21 test aroma compounds in 1mL water for each separate DHS sampling and the combined MVM procedure were evaluated as a function of vapor pressure in the range of 0.000088–120kPa. The MVM procedure provided high recoveries (>88%) for 17 test aroma compounds and moderate recoveries (44–71%) for 4 test compounds. The method showed good linearity (r2>0.9913) and high sensitivity (limit of detection: 0.1–0.5ngmL−1) even with MS scan mode. The improved sensitivity of the method was demonstrated with analysis of a wide variety of aroma compounds in brewed green tea. Compared to the original 100μL MVM procedure, this extension to 1mL MVM allowed detection of nearly twice the number of aroma compounds, including 18 potent aroma compounds from top-note to base-note (e.g. 2,3-butanedione, coumarin, furaneol, guaiacol, cis-3-hexenol, linalool, maltol, methional, 3-methyl butanal, 2,3,5-trimethyl pyrazine, and vanillin). Sensitivity for 23 compounds improved by a factor of 3.4–15 under 1mL MVM conditions.

Focused ultrasound solid–liquid extraction for the determination of organic biomarkers in beachrocks

Beachrocks are consolidated coastal sedimentary formations resulting mainly from the relative rapid cementation of beach sediments by different calcium carbonate polymorphs. Although previous works have already studied the elemental composition and the mineral phases composing these cements, few of them have focused their attention on the organic matter present therein. This work describes an extraction methodology based on focused ultrasound solid–liquid extraction (FUSLE), followed by analysis using large volume injection (LVI) in a programmable temperature vaporizer (PTV) combined with gas chromatography–mass spectrometry (GC–MS) in order to determine organics such as polycyclic aromatic hydrocarbons (PAHs) and biomarkers (hopanes), which can increase and confirm the information obtained so far. This goal has been achieved after the optimization of the main parameters affecting the extraction procedure, such as, extraction solvent, FUSLE variables (amplitude, extraction time and pulse time) and also variables affecting the LVI–PTV (vent time, injection speed and cryo-focusing temperature). The developed method rendered results comparable to traditional extraction methods in terms of accuracy (77–109%) and repeatability (RSD<23%). Finally, the analyses performed over real beachrock samples from the Bay of Biscay (Northern Spain) revealed the presence of the 16 EPA priority PAHs, as well as some organic biomarkers which could increase the knowledge about such beachrock formation.

Matrix solid phase dispersion method for determination of polycyclic aromatic hydrocarbons in moss

In this work a matrix solid-phase dispersion extraction method, followed by programmed temperature vaporization–gas chromatography–tandem mass spectrometry determination is proposed for the analysis of polycyclic aromatic hydrocarbons (PAHs) in moss samples. A devitalized, cultivated Sphagnum palustre L. moss clone obtained from the “Mossclone” EU-FP7 Project was used for the optimization and validation of the proposed method. Good trueness (84–116%), precision (intermediate precision lower than 11%) and sensitivity (quantitation limits lower than 1.7ngg−1) were obtained. The proposed method was compared with other procedures applied for this complex matrix, achieving a considerable reduction of sample amount, solvent volume and time consumption. The procedure was successfully tested for the analysis of PAHs in exposed moss clone samples for the monitoring of air pollution. Finally, the method was also tested for its suitability in the analysis of PAHs in other moss species as well as a lichen species.

Evolution of in-cylinder polycyclic aromatic hydrocarbons in a diesel engine fueled with n-heptane and n-heptane/toluene

Abstract This work studied the evolution of in-cylinder polycyclic aromatic hydrocarbons (PAHs) in a diesel engine fueled with n -heptane, and explored the effects of adding toluene to n -heptane on in-cylinder PAHs. In-cylinder PAHs were sampled in a direct injection diesel engine using a total cylinder sampling system. PAHs were analyzed by gas chromatography–mass spectrometry with programmed temperature vaporization in the solvent vent mode. For n -heptane, the mass of total in-cylinder PAHs ( Σ M PAHs ) increased in premixed and late diffusion combustion phases, and decreased in early diffusion and late combustion phases. Among the 16 PAHs detected, Naphthalene (Nap) was the most abundant. PAHs with two benzene rings and one five-membered ring, such as Acenaphthylene, Acenaphthene and Fluorene, were also plentiful, implying that PAHs with five-membered ring could play an important role in the growth of in-cylinder PAHs. When adding 20 vol.% toluene to n -heptane, the evolution of ΣM PAHs was varied. The Σ M PAHs for n -heptane/toluene increased in premixed and early diffusion combustion phases, and decreased in late diffusion and late combustion phases. Toluene addition reduced the ΣM PAHs in the premixed combustion phase by up to 48% but increased ΣM PAHs by 30% in the early diffusion combustion phase. In the subsequent combustion phase, the ΣM PAHs was reduced by approximately 67%. For in-cylinder individual PAHs, toluene addition generally reduced the percentages of Nap in ΣM PAHs during the engine combustion process but increased the percentages of larger PAHs, indicating that toluene addition was conducive to the growth of PAHs to form larger PAHs.

Comparison of different injection modes in edible oil minor components analysis

Waxes and fatty acid alkyl esters are minor components used as official parameters to control the authenticity and quality of a high-value olive oil product. A poor measurement can lead to a misleading classification of the oil. The official method requires their analysis together by capillary gas chromatography equipped with a flame ionization detector and an on-column injector to avoid discrimination and thermal degradation. The degradation can occur to a different extent if different (and not properly optimized) injectors are used. However, other injection techniques, such as programmed-temperature vaporizer, are much more versatile and more widespread. The aim of the present work was to compare the performance of a programmed-temperature vaporizer injector, in on-column and splitless mode, with the on-column injector to analyze alkyl esters and waxes. Discrimination among high-boiling compounds was evaluated, as well as the occurrence of thermal degradation, especially of sterols and diterpene alcohol (phytyl and geranylgeraniol) esters. A proper optimization of a programmed-temperature vaporizer injection, with particular attention to the liner selection, was proven to provide comparable results to the traditional on-column injection. A performance comparison was carried out both on standard mixtures and on real oil samples.

Multi-Pesticide Analysis in Sediment by GC-EI-MS/MS Using Programmed Temperature Vaporization–Large Volume Injection Technique

A sensitive, selective and high throughput gas chromatography–tandem mass spectrometry method using programmable temperature vaporization–large volume injection mode (PTV-LVI-GC-MS/MS) for the analysis of 30 organochlorine pesticides (OCPs) including toxaphenes in sediments was developed. The PTV-LV injection settings, viz. inlet temperature, split flow, injection phase time, and injection speed were optimized for 50 µL injection. A significant increase in sensitivity was accomplished as compared with that obtained by the conventional 1 µL cold splitless injection. Average LVI recoveries for OCPs were in the range 58–133 % with low % RSD in instrument precision (<12 %). The method detection limits achieved were 0.04–0.92 µg kg−1. The method recovery ranged from 80 to 120 % with <10 % RSD for more than 83 % of targeted analytes fortified at 10 µg kg−1 in sediments. The PTV-LVI-GC-MS/MS allows simultaneous determination and unambiguous confirmation of trace OCPs and toxaphene congeners, which significantly streamlines and improves the trace organic analysis in the environmental surveillance and monitoring.

Determination of pesticide residues in animal origin baby foods by gas chromatography coupled with triple quadrupole mass spectrometry

A simple, fast and multiresidue method for the determination of pesticide residues in baby foods of animal origin has been developed in order to check the compliance with the Maximum Residue Levels (MRLs) set at a general value of 0.01 mg/kg by Commission Directive 2006/125/EC for infant foods. The main classes of organochlorine, organophosphorus and pyrethroid compounds have been considered, which are mainly fat soluble pesticides. The analytical procedure consists in the extraction of baby food samples by acetonitrile (ACN) followed by a clean up using C18 solid-phase extraction column eluted with ACN. The compounds were determined by gas chromatography-triple quadrupole mass spectrometry equipped with a Programmed Temperature Vaporizer (PTV) injection and a backflush system. In order to compensate for matrix effects PTV and matrix matched standard calibrations have been used. The method has been fully validated for 57 pesticides according to the Document SANCO/12571/2013. Accuracy and precision (repeatability) have been studied by recoveries at two spiking levels, the Limit of Quantitation (LOQ) (0.003–0.008 mg/kg) and 10 time greater (0.03–0.08 mg/kg), and the results were in the acceptable range of 70–120% with Relative Standards Deviations (RSD) ≤20%. Selectivity, linearity, LOQ and uncertainty of measurement were also determined for all the compounds. The method has been also applied for the analysis of 18 baby food animal origin samples, bought form the local market in Rome (Italy), and no pesticide in the scope of the method has been found above the MRL or the LOQ.

On-line combination of high performance liquid chromatography with comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry: a proof of principle study.

The present contribution is focused on the on-line combination of high performance liquid chromatography (HPLC), cryogenically modulated comprehensive two-dimensional gas chromatography (GC × GC), and triple quadrupole mass spectrometry (QqQ MS), generating a very powerful unified separation-science tool. The instrument can be used in seven different combinations ranging from one-dimensional HPLC with a photodiode array detector to on-line LC × GC × GC/QqQ MS. The main focus of the present research is directed to the LC-GC × GC/QqQ MS configuration, with its analytical potential shown in a proof-of-principle study involving a very complex sample, namely, coal tar. Specifically, a normal-phase LC process enabled the separation of three classes of coal tar compounds: (1) nonaromatic hydrocarbons; (2) unsaturated compounds (with and without S); (3) oxygenated constituents. The HPLC fractions were transferred to the GC × GC instrument via a syringe-based interface mounted on an autosampler. Each fraction was subjected to a specific programmed temperature vaporizer GC × GC/QqQ MS untargeted or targeted analysis. For example, the coal tar S-containing compounds were pinpointed through multiple-reaction-monitoring analysis, while full-scan information was attained for the oxygenated constituents.

Coupling of a headspace autosampler with a programmed temperature vaporizer for stable carbon and hydrogen isotope analysis of volatile organic compounds at microgram per liter concentrations.

One major challenge for the environmental application of compound-specific stable isotope analysis (CSIA) is the necessity of efficient sample treatment methods, allowing isolation of a sufficient mass of organic contaminants needed for accurate measurement of the isotope ratios. Here, we present a novel preconcentration technique--the coupling of a headspace (HS) autosampler with a programmed temperature vaporizer (PTV)--for carbon (δ(13)C) and hydrogen (δ(2)H) isotope analysis of volatile organic compounds in water at concentrations of tens of micrograms per liter. The technique permits large-volume injection of headspace samples, maintaining the principle of simple static HS extraction. We developed the method for multielement isotope analysis (δ(13)C and δ(2)H) of methyl tert-butyl ether (MTBE), benzene, toluene, ethylbenzene, and o-xylene (BTEX), and analysis of δ(13)C for chlorinated benzenes and ethenes. Extraction and injection conditions were optimized for maximum sensitivity and minimum isotope effects. Injection of up to 5 mL of headspace sample from a 20 mL vial containing 13 mL of aqueous solution and 5 g of NaCl (10 min of incubation at 90 °C) resulted in accurate δ(13)C and δ(2)H values. The method detection limits (MDLs) for δ(13)C were from 2 to 60 μg/L (MTBE, BTEX, chlorinated ethenes, and benzenes) and 60-97 μg/L for δ(2)H (MTBE and BTEX). Overall, the HS-PTV technique is faster, simpler, isotope effect-free, and requires fewer treatment steps and less sample volume than other extraction techniques used for CSIA. The environmental applicability was proved by the analysis of groundwater samples containing BTEX and chlorinated contaminants at microgram per liter concentrations.

Polycyclic aromatic hydrocarbon emissions in diesel exhaust using gas chromatography–mass spectrometry with programmed temperature vaporization and large volume injection

Diesel engines are significant sources of Polycyclic Aromatic Compounds (PAHs) in urban atmospheres. These compounds are widely known for their carcinogenic potential and mutagenic properties. In this study, a method was developed for the analysis of 16 priorities PAHs using gas chromatography–mass spectrometry (GC–MS) with programmable temperature vaporizer large volume injection (PTV–LVI), which allowed to be obtained detection limits below 2.0 ng mL−1. This method was evaluated in samples from stratified particulate matter and gas phase from the emissions of diesel vehicle employing diesel commercial S10 (sulfur 10 mg L−1) and B5 (biodiesel 5% v/v). A sampling system that does not employ exhaust products dilution was used to evaluate the PAHs gas-particle partition. Six PAHs were identified in extracts and gas-phase PAHs took percentage of 80% in the total PAHs emissions. The sampling system without dilution not caused a strong nucleation/condensation of the most volatile PAHs. PAHs size-particle distribution was found in higher levels in the accumulation mode.

Multi-volatile method for aroma analysis using sequential dynamic headspace sampling with an application to brewed coffee

A novel multi-volatile method (MVM) using sequential dynamic headspace (DHS) sampling for analysis of aroma compounds in aqueous sample was developed. The MVM consists of three different DHS method parameters sets including choice of the replaceable adsorbent trap. The first DHS sampling at 25°C using a carbon-based adsorbent trap targets very volatile solutes with high vapor pressure (>20kPa). The second DHS sampling at 25°C using the same type of carbon-based adsorbent trap targets volatile solutes with moderate vapor pressure (1–20kPa). The third DHS sampling using a Tenax TA trap at 80°C targets solutes with low vapor pressure (<1kPa) and/or hydrophilic characteristics. After the 3 sequential DHS samplings using the same HS vial, the three traps are sequentially desorbed with thermal desorption in reverse order of the DHS sampling and the desorbed compounds are trapped and concentrated in a programmed temperature vaporizing (PTV) inlet and subsequently analyzed in a single GC-MS run. Recoveries of the 21 test aroma compounds for each DHS sampling and the combined MVM procedure were evaluated as a function of vapor pressure in the range of 0.000088–120kPa. The MVM provided very good recoveries in the range of 91–111%. The method showed good linearity (r2>0.9910) and high sensitivity (limit of detection: 1.0–7.5ngmL−1) even with MS scan mode. The feasibility and benefit of the method was demonstrated with analysis of a wide variety of aroma compounds in brewed coffee. Ten potent aroma compounds from top-note to base-note (acetaldehyde, 2,3-butanedione, 4-ethyl guaiacol, furaneol, guaiacol, 3-methyl butanal, 2,3-pentanedione, 2,3,5-trimethyl pyrazine, vanillin, and 4-vinyl guaiacol) could be identified together with an additional 72 aroma compounds. Thirty compounds including 9 potent aroma compounds were quantified in the range of 74–4300ngmL−1 (RSD<10%, n=5).

Targeted Screening and Quantification of dl-PCBs and Dioxins in Various Foodstuffs by Programmed-temperature Vaporizer Large-volume Injection Coupled to GC-MS.

In 2009, high concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were found in soils located near the municipal garbage incinerator of Geneva. The matter of food contamination in this area was raised. Based on exposure criteria, a strategy of analysis of animal fats has been established with farmers in the Geneva area. Most methods of analysis of dl-PCBs, dioxins and furans, are based on gas chromatography coupled to high-resolution mass spectrometry (GC-HRMS) and considered as the reference methodology. An innovative approach was developed by programmed-temperature vaporizer large-volume injection (PTV-LV) and gas chromatography coupled with triple quadrupole mass spectrometry (GC-MS/MS) analysis. This analytical method was validated and was found suitable for screening and quantification of target compounds in animal fats (beef, pork, sheep, etc. ). PTV-LV coupled to GC-MS/MS appeared to be a good alternative compared to the GC-HRMS strategy, offering a good compromise between sensitivity, versatility of instrumentation, and economical aspects. A survey of 121 samples was conducted.

Headspace generation coupled to gas chromatography–mass spectrometry for the automated determination and quantification of endogenous compounds in urine. Aldehydes as possible markers of oxidative stress

A methodology for the determination of five aldehydes in urine has been developed based on the coupling of a headspace generation sampler with a gas chromatography–mass spectrometry system equipped with a programmed temperature vaporizer. This instrumental configuration minimizes sample manipulation and allows the determination of these compounds without the need for a derivatization step so that the methodology is largely shortened and simplified. An experimental design was carried out in order to optimize the headspace sampling. Sample matrix effect was eliminated by means of dilution of urine samples. The calibration models displayed good linearity (0.1–10μg/L) and their validity was checked using ANOVA, and it was observed that they did not exhibit any lack of fit. The LODs obtained ranged between 0.04 and 0.08μg/L and the LOQs between 0.12 and 0.24μg/L. The accuracy of the method was evaluated in terms of apparent recoveries which were between 86 and 120%. The method developed was applied to the analysis of 17 samples of urine from different subjects in order to quantify these endogenous compounds.

Sensitivity Enhancement in the Determination of Volatile Biomarkers in Saliva Using a Mass Spectrometry-Based Electronic Nose with a Programmed Temperature Vaporizer

With a view to improving the sensitivity of direct coupling of a headspace sampler (HS) with a mass spectrometer (MS), here we propose the use of a programmed temperature vaporizer (PTV) in solvent-vent injection mode before the sample is introduced into the MS. This preconcentration scheme has been used for some time in many methods based on gas chromatography (GC), but to the best of our knowledge it has not yet been used in an electronic nose based on MS. The increase in the S/N ratio with the proposed instrumental configuration (HS-PTV/MS) lies between 6.9- and 22-fold. The main advantage of using this injector lies in the fact that it does not involve time-consuming steps. To check the possibilities of this methodology, saliva samples from healthy volunteers and patients with different types of illnesses (including some types of cancer) were analyzed. None of the compounds studied was detected in the samples corresponding to the healthy volunteers. One or more biomarkers, at levels ranging from 13 to 500 μg/L, were found in five of the samples from the patients. Additionally, separative analysis by HS-PTV-GC/MS was performed for confirmatory purposes and both methods provided similar results. The main advantage of the proposed methodology is that no prior chromatographic separation and no sample manipulation are required.

Salt-assisted dispersive liquid–liquid microextraction coupled with programmed temperature vaporization gas chromatography–mass spectrometry for the determination of haloacetonitriles in drinking water

We report here a new analytical method for the simultaneous determination of seven haloacetonitriles (HANs) in drinking water by coupling salt-assisted dispersive liquid–liquid microextraction (SADLLME) with programmed temperature vaporizer-gas chromatography–mass spectrometry (PTV-GC–MS). The newly developed method involves the dispersion of the extractant in aqueous sample by addition of a few grams of salt and no dispersion liquid was required as compared to the traditional DLLME methods. The extractant (CH2Cl2, 50μL) and the salt (Na2SO4, 2.4g) were successively added to water (8mL) in a conical centrifuge tube that was shaken for 1min and centrifuged (3500rpm, 3min). The aliquot of sedimented phase (4μL) was then directly injected into the PTV-GC–MS system. The limits of detection and quantification for the HANs were 0.4–13.2ngL−1 and 1.2–43.9ngL−1, respectively. The calibration curves showed good linearity (r2≥0.9904) over 3 orders of magnitude. The repeatability of the method was investigated by evaluating the intra- and inter-day precisions. The relative standard deviations (RSDs) obtained were lower than 10.2% and 7.8% at low and high concentration levels. The relative recoveries ranged from 79.3% to 105.1%. The developed methodology was applied for the analysis of seven HANs in several drinking water samples in coastal and inland cities of China. It was demonstrated to be a simple, sensible, reproducible and environment friendly method for the determination of trace HANs in drinking water samples.

Eco-friendly microextraction method for the quantitative speciation of 13 haloacetic acids in water

This paper describes the first micro liquid–liquid extraction (MLLE) gas chromatography–mass spectrometry (GC–MS) method for the speciation of emerging iodinated acetic acids, along with conventional chlorinated and brominated acids in water. The haloacetic acids (HAAs) were derivatised using 3 reagents for their methylation, both in aqueous and organic media. The acidic methanol derivatisation in aqueous medium provided the best efficiency, requiring minimal sample manipulation. The derivatisation yield was improved through the use of microwave energy that drastically reduced reaction time (2min). The HAA methyl esters were finally extracted using 250μL of methyl tert-butyl ether. This MLLE combined with the use of a large-volume sample injection coupled to a programmed temperature vaporiser–GC–MS improved the sensitivity of the method and minimised the generation of hazardous residues in accordance with the principles of “Green Chemistry”. Detection and quantification limits (excepting tribromoacetic acid) within the range of 0.01–0.15μg/L and 0.03–0.5μg/L, respectively, were obtained and the relative standard deviation was lower than 10%. The eco-friendly method was applied to the speciation of the 13 HAAs in treated (chlorinated and chloraminated water) and untreated water. Up to 8 HAAs were found at detectable levels in treated water. The highly toxic monoiodoacetic acid was detected in almost all the chloraminated water.