Full Evaporative Vacuum Extraction─A Quantitative and Green Approach for Analysis of Semivolatile Organic Compounds in Drinking Water and Surface Water Using GC-MS.

Full evaporative vacuum extraction (FEVE) was developed in this work for analysis of a broad range of semivolatile organic compounds (SVOCs) in drinking water and surface water. Sorbent pens are used in a two-stage process that first evaporates the sample matrix through sorbent beds under vacuum to recover the lighter SVOCs, followed by the application of a higher temperature and stronger vacuum to the sample vial to recover the remaining heavier SVOCs once the matrix has evaporated. After extraction, the sorbent pens are desorbed into a GC-MS using a uniquely designed "splitless" delivery system to maximize sensitivity. Critical extraction and desorption parameters that affect the method performance were optimized. After FEVE, the sorbent pens can be stored for 7-10 days at room temperature while maintaining a less than 15% loss in analyte recovery. As a proof of concept, 10 drinking water and surface water samples were analyzed using this method. 69 analytes were detected in these water samples, with the highest concentration of 1986 ng/L for bromacil. Heptachlor epoxide, chlorpyrifos, metolachlor, butachlor, and 2,3',4',5-tetrachlorobiphenyl were detected in four samples. None of the analytes were above the health and safety thresholds set by California Proposition 65.

Capturing Actively Produced Microbial Volatile Organic Compounds from Human-Associated Samples with Vacuum-Assisted Sorbent Extraction.

Volatile organic compounds (VOCs) from biological samples have unknown origins. VOCs may originate from the host or different organisms from within the host's microbial community. To disentangle the origin of microbial VOCs, volatile headspace analysis of bacterial mono- and co-cultures of Staphylococcus aureus, Pseudomonas aeruginosa, and Acinetobacter baumannii, and stable isotope probing in biological samples of feces, saliva, sewage, and sputum were performed. Mono- and co-cultures were used to identify volatile production from individual bacterial species or in combination with stable isotope probing to identify the active metabolism of microbes from the biological samples. Vacuum-assisted sorbent extraction (VASE) was employed to extract the VOCs. VASE is an easy-to-use, commercialized, solvent-free headspace extraction method for semi-volatile and volatile compounds. The lack of solvents and the near-vacuum conditions used during extraction make developing a method relatively easy and fast when compared to other extraction options such as tert-butylation and solid phase microextraction. The workflow described here was used to identify specific volatile signatures from mono- and co-cultures. Furthermore, analysis of the stable isotope probing of human associated biological samples identified VOCs that were either commonly or uniquely produced. This paper presents the general workflow and experimental considerations of VASE in conjunction with stable isotope probing of live microbial cultures.

Vacuum-assisted sorbent extraction: An analytical methodology for the determination of ultraviolet filters in environmental samples.

Vacuum-assisted sorbent extraction (VASE) has been applied in combination with gas chromatography-mass spectrometry for the determination of UV filters in water samples. VASE is a variant of headspace extraction which was developed in conjunction with the sorbent pen (SP) technology. This technique combines the advantages of both stir-bar assisted extraction and headspace solid-phase microextraction. The SP traps allowed both reduced pressure in-vial extraction and direct thermal desorption via a unique gas chromatographic injection port. The main parameters that affect the performance of VASE, including both extraction and desorption conditions, were extensively optimized. Under optimum conditions, extraction required 10 mL of sample within 40 mL vials, pH 3.5, ~30 s of air-evacuation, 14 h incubation at 70 °C, stirring at 200 rpm, and a final water management step conducted at ~ -17 °C for 15 min. Optimal thermal desorption required preheating at 260 °C for 2 min followed by desorption at 300 °C for 2 min. The beneficial effect of reduced-pressure extraction was demonstrated by comparing the UV filter extraction time profiles collected using VASE to an analogous atmospheric pressure procedure, resulting in up to a 3-fold improvement under optimized conditions. The VASE methodology enabled simultaneous extractions using different SPs without compromising the method reproducibility, which increases the overall sample throughput. The method was characterized by low limits of detection, from 0.5 to 80 ng L-1, and adequate reproducibility, with inter-SP and inter-day relative standard deviation lower than 14%. Tap and lake water was successfully analyzed with the proposed methodology, resulting in relative recoveries of spiked samples ranging between 70.0 and 120%.

Long-term measurement of volatile organic compounds in ambient air by canister-based one-week sampling method.

A canister-based 1 week sampling method using a mechanical flow controller and a 6 L fused-silica-lined canister was evaluated for the long-term measurement of 47 VOCs in ambient air at pptv (volume/volume) to ppbv levels by use of a three-stage preconcentation method followed by GC-MS analysis. The GC conditions were initially optimized for complete separations of several pptv-level VOCs (e.g. vinyl chloride, 1,3-butadiene, acrylonitrile, 1,2-dichloroethane and chloroform) in ambient air because the selected ions are easily interfered with by coexisting C4-, C5-hydrocarbons and analytes presented at ppbv levels. Thirty-four VOCs determined by the 1 week and 24 h sampling method in December 16-22 (2002) had concentrations of 6.0-15000 pptv per compound. Concentrations of 28 VOCs (including polar VOCs (e.g. methyl isobutyl ketone and butyl acetate)) obtained by the method were approximately equal to the mean values calculated from 24 h sampling (< +/- 10% deviation). Six VOCs that had low concentrations of 6.0-43 pptv showed more than +/- 10% deviation. Thirteen VOCs were not detected during the entire sampling period. The effect of relative humidity or ozone for the specific VOCs (e.g. MIBK, butyl acetate, vinyl chloride, 1,3-butadiene and styrene) was negligible.

Stabilities of 58 volatile organic compounds in fused-silica-lined and SUMMA polished canisters under various humidified conditions.

Fused-silica-lined (FSL) canisters and SUMMA polished (SUMMA) canisters were compared for the recoveries and the stabilities of 58 volatile organic compounds (VOCs) at low ppbv (volume/volume) levels under various humidified conditions using a three-stage preconcentration method followed by GC-MS analysis. The target VOCs included non-polar VOCs (e.g. halogenated hydrocarbons and aromatic hydrocarbons) and polar VOCs (e.g. alcohols, ketones, esters, ethers, nitriles and thiols). The three-stage preconcentration method was initially optimized for simultaneous analysis of non-polar and polar VOCs because determination of canister stability is dependent on the accuracy of analytical measurements. The method showed good linearity over the concentration range from 1 to 25 ppbv for all target analytes, and the correlation coefficients were higher than 0.9974. The method detection limits ranged from 0.023 to 0.39 ppbv. The test mixtures loaded in both type of canisters (n = 3) had concentrations of 1.7-2.5 ppbv per compound at ambient pressure under various humidified conditions (%RH = 1.6, 8.0, 27, 39, 53 and >99% with excess water present). All canister samples were initially analyzed on day 0 (after 6-12 h). The effect of competitive adsorption of water vapor and polar VOCs on active sites of interior surface was remarkably observed for SUMMA canisters. Polar VOCs had a greater requirement for water vapor to be present. The RH percentages that ensured good recovery on day 0 were RH > 8% for non-polar VOCs and RH > 27% for polar VOCs (except alcohols under the condition of RH > 99%). All thiols were not recovered from SUMMA canisters under all conditions. FSL canisters showed good recoveries of more than 86% for all VOCs under all conditions on day 0 (except alcohols under the condition of RH > 99%). The recoveries of alcohols in both canisters under the condition of RH > 99% displayed relatively low recoveries in the range 25-76% because of the partitioning effect into condensed water. The canister samples under the conditions of RH 8.0, 27, 53 and > 99% were analyzed for the stability test on days 3, 7, 14 and 28 after loading. All non-polar VOCs were reasonably stable in the FSL canisters under all examined conditions over 28 days. However, several polar VOCs that have relatively lower vapor pressure, e.g. MIBK, butyl acetate and alcohols except ethanol, showed unstable characteristics under relatively dry conditions (RH 8 and 27%) during 28 days. RH > 53% was needed to ensure good stabilities of all analytes except thiols with the recoveries of > 80% over 28 days for both canisters. Although the FSL canister showed good recoveries of more than 86% for thiols on day 0, drastic degradations were observed after day 3 and they were not detected after day 14.