Air sampling and analysis of volatile organic compounds with solid phase microextraction

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.     

热解析-固相微萃取-气相色谱法测定空气样品中挥发性有机化合物

建立了热解析-固相微萃取-气相色谱法测定空气样品中挥发性有机化合物的分析方法,并对色谱分离条件、玻璃针筒保存样品的稳定性、固相微萃取萃取纤维、萃取时间、色谱进样时间等条件进行了优化,9种挥发性有机化合物的峰面积与其质量浓度在所测范围内有较好的线性关系,相对标准偏差＜8.8%,检出限为0.05～0.75 μg/100 mL,满足实际空气样品测定需要。     

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.     

Analysis of volatile fatty acids in wastewater collected from a pig farm by a solid phase microextraction method

The main purpose of this study is to develop a reliable Solid Phase Microextraction (SPME) method for monitoring the concentration of volatile fatty acid (VFA) in the wastewater collected from pig farms. Ten volatile fatty acid species were spiked in 2 ml of swine wastewater and extracted with a carbowax coated extraction fiber to evaluate the accuracy and precision of the method. The fiber was introduced into a gas chromatography system by thermal desorption and detected by a mass spectrometer detector. The estimated method detection limits ranged from 11.5 mM/L for formic acid to 0.03 mM/L for heptanoic acid. The method is more sensitive than the sample direct injection method. The percentage recovery of analytes ranged from 77.3 for propanoic acid to 114.1 for formic acid at the spike level of 19.09 mM/L. The compound absorption rate varied significantly with the fiber absorption time for n-Valeric, isocaproic, n-caproic and heptanoic acids. An SPME method with twenty minutes fiber absorption and three minutes thermal desorption was tested in this study and resulted in good reproducibility for analyzing VFAs in swine wastewater. The method may be applied for scanning a wide spectrum of polar organic compounds in environmental samples.     

Analysis of volatile and semivolatile organic compounds in municipal wastewater using headspace solid-phase microextraction and gas chromatography.

The aim of this work was to develop a simple and fast analytical method for the determination of a wide range of organic compounds (volatile and semivolatile compounds) in municipal wastewater. The headspace-solid-phase microextraction (HS-SPME) and gas chromatography (with mass spectroscopy) was used for determination of the organic compounds. In this study, 39 organic compounds were determined, including 3 sulfur compounds, 28 substituted benzenes, and 8 substituted phenols. The extraction parameters, such as types of SPME fiber, extraction temperature, extraction time, desorption time, salt effect, and magnetic stirring, were investigated. The method had very good repeatability, because the relative standard deviations ranged from 0.5 to 12%. The detection limit of each compound was at or below the microgram-per-liter level. This method was applied for determination of the organic compounds in raw wastewater, primary effluent, secondary effluent, and chlorinated secondary effluent samples from the Chania Municipal Wastewater Treatment Plant (Crete, Greece).     

Gas chromatographic analysis of organic marker compounds in fine particulate matter using solid-phase microextraction

A gas chromatographic method that uses solid-phase microextraction for analysis of organic marker compounds in fine particulate matter (PM2.5) is reported. The target marker compounds were selected for specificity toward emission from wood smoke, diesel or gasoline combustion, or meat cooking. Temperature-programmed volatilization analysis was used to characterize the thermal stabilities and volatile properties of the compounds of interest. The compounds were thermally evaporated from a quartz filter, sorbed to a solid phase microextraction (SPME) fiber, and thermally desorbed at 280 degrees C in a gas chromatograph injection port connected via a DB 1701 capillary separating column. Various experimental parameters (fiber type, time, and temperature of sorption) were optimized. It was found that high extraction yield could be achieved using a polyacrylate fiber for polar substances, such as levoglucosan, and a 7-microm polydimethylsiloxane (PDMS)-coated fiber for nonpolar compounds, such as hopanes and polyaromatic hydrocarbon. A compromise was made by selecting a carboxen/PDMS fiber, which can simultaneously extract all of the analytes of interest with moderate-to-high efficiency at 180 degrees C within a 30-min accumulation period. The optimized method was applied to the determination of levoglucosan in pine wood combustion emissions. The simplicity, rapidity, and selectivity of sample collection with a polymer-coated SPME coupled to capillary gas chromatography (GC) made this method potentially useful for atmospheric chemistry studies.     

Matrix effect on the performance of headspace solid phase microextraction method for the analysis of target volatile organic compounds (VOCs) in environmental samples

Solid phase microextraction (SPME) is a fast, cheap and solvent free methodology widely used for environmental analysis. A SPME methodology has been optimized for the analysis of VOCs in a range of matrices covering different soils of varying textures, organic matrices from manures and composts from different origins, and biochars. The performance of the technique was compared for the different matrices spiked with a multicomponent VOC mixture, selected to cover different VOC groups of environmental relevance (ketone, terpene, alcohol, aliphatic hydrocarbons and alkylbenzenes). VOC recovery was dependent on the nature itself of the VOC and the matrix characteristics. The SPME analysis of non-polar compounds, such as alkylbenzenes, terpenes and aliphatic hydrocarbons, was markedly affected by the type of matrix as a consequence of the competition for the adsorption sites in the SPME fiber. These non-polar compounds were strongly retained in the biochar surfaces limiting the use of SPME for this type of matrices. However, this adsorption capacity was not evident when biochar had undergone a weathering/aging process through composting. Polar compounds (alcohol and ketone) showed a similar behavior in all matrices, as a consequence of the hydrophilic characteristics, affected by water content in the matrix. SPME showed a good performance for soils and organic matrices especially for non-polar compounds, achieving a limit of detection (LD) and limit of quantification (LQ) of 0.02 and 0.03 ng g⁻¹ for non-polar compounds and poor extraction for more hydrophilic and polar compounds (LD and LQ higher 310 and 490 ng g⁻¹). The characteristics of the matrix, especially pH and organic matter, had a marked impact on SPME, due to the competition of the analytes for active sites in the fiber, but VOC biodegradation should not be discarded in matrices with active microbial biomass.     

Determination of pesticides of different chemical classes in drinking water of the state of Santa Catarina (Brazil) using solid-phase microextraction coupled to chromatographic determinations

The evaluation of the concentration of pesticides in drinking water presents a real concern. In this study, a simple and rapid method based on solid-phase microextraction (SPME) followed by gas chromatography–mass spectrometry and electron capture detectors was developed aiming at multiclass determination of 23 pesticides regulated by the Brazilian legislation. The extraction was carried out by direct immersion mode (DI-SPME) using DVB/Car/PDMS fiber coating. In order to improve the extraction efficiency, parameters such as temperature, salting-out effect, and extraction time were optimized. The method was evaluated using drinking water samples spiked with the analytes at different concentrations, and it showed good linearity in the range studied. The values obtained for limits of quantification (LOQ) were below the limits established by Brazilian regulations. Accuracy and precision of the method exhibited satisfactory results, providing relative recoveries from 70 to 123.34% at three spiked levels, and the relative standard deviations ranged from 0.53 to 24.8%. The method was applied in 20 drinking water samples from 13 cities in the State of Santa Catarina, Brazil.

     

Molecular indicators for pollution source identification in marine and terrestrial water of the industrial area of Kavala city, North Greece

Eight terrestrial and four marine water samples were collected from the industrial section of the city of Kavala in northern Greece to determine the occurrence and distribution of organic contaminants, as well as to identify the molecular markers of different emission sources. The samples were analyzed by means of non-target screening analyses. The analytical procedure included a sequential extraction of the samples, GC-FID, GC/MS analyses, and additional quantitative analyses of selected pollutants. The results show a wide variety of compounds including halogenated compounds, technical additives and metabolites, phosphates, phthalates, benzothiazoles, etc. A close relationship between many of the contaminants and their emission sources was determined based on their molecular structures and information on technical applications.     

Application of a purge and trap TDS-GC/MS procedure for the determination of emissions from flame retarded polymers

Emissions of volatile organic compounds (VOCs) from different thermoplastic polymers used in electrotechnical applications were investigated using a purge and trap procedure that involved adsorption on Tenax GR. Results were compared to those for an operating TV set monitored in a test chamber. The analyses were in both cases carried out using thermodesorption gas chromatography with mass spectrometric detection (TDS-GC/MS). Substances identified were monomers, volatile additives, or related compounds. Special attention was given to the detection of halogenated compounds. Their origin was studied using reference samples and synthetic standards.     

Measurement of trihalomethanes in potable and recreational waters using solid phase micro extraction with gas chromatography-mass spectrometry

Solid phase micro extraction (SPME) was applied to the determination of selected trihalomethanes (THMs), chloroform, bromodichloromethane, dibromochloromethane, bromoform, in potable and recreational waters. The selected samples were environmentally significant due to mandatory limits imposed by regulatory agencies. Extraction of the analytes was performed using headspace SPME (fused silica fibre with a 100 microm poly(dimethylsiloxane coating) followed by thermal desorption at 220 degrees C and GC-MS analysis. A linear working range of 10-160 microg/l was established with relative standard deviations (%RSD) within the range, 0.9-19%. Limits of detection (LOD) were 1.0-2.8 microg/l. The highest THM concentration was 61.8 microg/l which was well within the proposed European Union directive of 100 microg/l. The total THMs determined in swimming pool waters ranged from 105-134 microg/l, with chloroform accounting for 84-86% of total THM.     

Dynamic air sampling of volatile organic compounds using solid phase microextraction

A new dynamic air sampling system was devised and evaluated in conjunction with solid phase microextraction (SPME) fiber materials for extracting odor-causing volatile organic compounds (VOCs) present in swine building environments. Utilizing a standard solution consisting of 11 compounds (i.e., volatile fatty acids, indoles, and phenol), sampling times, volumes, and flow rates were adjusted to establish optimal extraction conditions. Results indicated that the sampling system was effective with the Carboxen/Polydimethylsiloxane (CAR/PDMS) fiber in extracting all 11 standard compounds. The best sampling conditions for the extraction were a 100-mL sampling vial subjected to a continuous flow of 100 mL/min for 60 min. The gas chromatographic analysis showed that the reproducibility was within acceptable ranges for all compounds (RSD=4.24-17.26% by peak areas). In addition, field tests revealed that the sampling system was capable of detecting over 60 VOCs in a swine house whose major components were identified by gas chromatography-mass spectrometry (GC-MS) and by their retention times as volatile fatty acids, phenols, indole, and skatole. The field tests also showed that considerably different levels of VOCs were present in various parts of the swine building.     

Microwave/SPME method to quantify pesticide residues in tomato fruits

A new analytical method using focused microwave-assisted extraction (FMAE), coupled with solid phase micro-extraction (SPME), has been elaborated to determine 25 pesticides used in tomato cultivation. Microwave energy was used for a fast and controlled heating of solvent to selectively extract compounds. Calibration curves were plotted from blank tomato samples spiked at different concentrations with standards. A linear response was obtained between 10 and 1000 μ g/Kg for pyrethroids and between 0.1 and 5000 μ g/Kg for other compounds. For all studied substances, the resulting correlation coefficient (r²) was greater than 0.99. Limits of detection (LOD) and quantification (LOQ) were measured lower than 8 and 25 μ g/Kg, respectively. The relative standard deviation (RSD) was determined below 15% for all pesticides. Field incurred tomato samples were used to validate the new FMAE/SPME method. Observed analysis results by using this technique were in good agreement compared to those obtained by two accredited trading laboratories using traditional methods. Four tomato samples, bought in a local market, were also tested with the FMAE/SPME method.     

A laboratory technique for investigation of diffusion and transformation of volatile organic compounds in low permeability media

A laboratory diffusion cell technique that permits spatial and temporal estimates of porewater concentrations over short intervals suitable for estimation of effective diffusion coefficients (De) and degradation rate constants (k) of volatile organic compounds (VOCs) in saturated low permeability media is presented. The diffusion cell is a sealed cylinder containing vapour reservoirs for sampling, including a vapour reservoir source and an array of vapour-filled "mini-boreholes", which are maintained water- and sediment-free by slightly negative porewater pressures. The vapour reservoirs were sampled by Solid Phase Micro-Extraction (SPME), resulting in minimal disturbance to the experimental system. Porewater concentrations are estimated from the measured vapour concentrations. Experiments were conducted using a non-reactive medium and five VOCs with a range in partitioning properties. Calibration experiments showed that equilibrium partition coefficients could be used for calculating concentrations in the vapour reservoir source from concentrations in the SPME coating after a 1-min microextraction and that the reservoir concentration was insignificantly affected by sampling. However, equilibrium was not reached during the one-min extraction of the boreholes; the microextraction reduced the borehole vapour concentrations, leading to diffusion of VOCs from porewater into the vapour-filled borehole. Thus, empirical partitioning coefficients were required for the determination of porewater VOC concentrations. The experimental data and numerical modelling indicate masses extracted by SPME extraction are relatively small, with minimal perturbation on processes studied in diffusion experiments. This technique shows promise for laboratory investigation of diffusion and transformation processes in low permeability media.     

Analysing selected VVOCs in indoor air with solid phase microextraction (SPME): a case study

A multi-storey building with great diversity of room use was monitored after extensive renovation to remove mould growth secondary to a leaky roof. Tests for volatile organic compounds (VOC) with activated charcoal showed a successfully renovation. Solid phase microextraction (SPME) for detection of selected very volatile organic compounds (VVOCs) revealed indoor air concentrations ranging from 550 to 4,600 microg m(-3). The SPME technique also successfully detected emissions from working and building materials and documented the results of remedial measures in offices. The prior and current use of acetone, methyl acetate and 2-methylpentane within the building resulted in their elevated concentrations in other building floors.     

Microtox testing of pentachlorophenol in soil extracts and quantification by capillary electrochromatography (CEC)--a rapid screening approach for contaminated land

An approach to rapid soil testing which involved the use of simple solvent extraction methods was developed. The analytes of interest were priority pollutants of low water solubility which could not be readily removed from the soil using water. Direct toxicity testing of the soil samples by Microtox showed a high background toxicity which prevented realistic toxicity data from being obtained for the contaminants present. A range of different extraction solutions was used in an attempt to extract the contaminants while eliminating the matrix effects of the soil. It was necessary that the solvents selected for extraction of the soil samples were not of significant toxicity, as this could potentially mask the toxic effects of any compounds extracted from the soil. The extraction efficiencies of solvent systems were evaluated using pentachlorophenol (PCP) as a model compound of known toxicity in the Microtox assay. A rapid and cost-effective method was developed in order to determine the amount of PCP recovered from the soil by the extraction solvents employed. This method consisted of a solid phase extraction (SPE) step followed by quantification using capillary electrochromatography (CEC). Recoveries were greater when a higher proportion of organic solvent (methanol) was used in the extraction process, and lowest when water was used. An extraction based on water could provide information on the potential for leaching of contaminants from the soil into nearby water bodies in an environmental setting. An organic solvent extraction method could indicate how much toxicity soil-dependent organisms might be exposed to through ingestion. Extraction based on 50% (v/v) methanol in water was considered to be the most suitable overall extraction solution for soil screening, given that this permitted extraction of the water-insoluble compound PCP at a level which was clearly toxic in the Microtox assay while also retaining the capability to extract water-soluble contaminants.     

Analysis of acidic pesticides using in situ derivatization with alkylchloroformate and solid-phase microextraction (SPME) for GC-MS.

A solid-phase microextraction (SPME) method was developed for the analysis of acidic pesticide residues in water. The method utilizes in situ derivatization with butylchloroformate (BuCF), followed by on-line SPME extraction using a PDMS fibre, and analysis by GC-MS. Derivatives of the phenoxy acids mechlorprop (MCPP), dichlorprop (DCPP), MCPA and 2,4-D and their phenol degradation products 4-chloro-2-methylphenol and 2,4-dichlorophenol (DCP) were identified. Detection limits at 0.16-2.3 microg/l were achieved. Optimization of derivatization, ion strength, extraction time, SPME-fibre, desorption time and temperature are described. Standard curves in the range 0.5-10.0 microg/l were fitted to a second-degree polynomial. Standard deviation (n = 5) was below 10% for the phenol derivatives, but 20-50% for the phenoxy acids. For method verification groundwater samples from a field experiment were screened for content of MCPP and compared to the results from the HPLC analysis. A good agreement was obtained with respect to identification of positive samples, even though concentrations measured by the SPME were lower than with HPLC. Even if the precision and accuracy do not meet the demands for a strictly quantitative analysis, the SPME method is suitable for screening, because it is cheap, it can be automated, and uses smaller amounts of potential harmful solvents. Also, the method is less labour-intensive, as it requires a minimum of sample preparation when compared to traditional analyses. The acidic pesticides bentazon, dicamba, bromoxynil, ioxynil, dinoseb and DNOC were included in the study but could not be analysed by the current method.     

Chemical-sensory characterization of dairy manure odor using headspace solid-phase microextraction and multidimensional gas chromatography mass spectrometry-olfactometry

Livestock operations are associated with emissions of odor, gases, and particulate matter. The majority of previous livestock odor studies focused on swine operations whereas relatively few relate to dairy cattle. Identifying the compounds responsible for the primary odor impact is a demanding analytical challenge because many critical odor components are frequently present at very low concentrations within a complex matrix of numerous insignificant volatiles. The objective of this study was to describe a chemical-sensory profile of dairy manure odor using headspace solid-phase microextraction (HS-SPME) and multidimensional gas chromatography-mass spectrometry-olfactometry (MDGC-MS-O). Two analytical approaches were used: (1) HS-SPME time-series extractions (from seconds up to 20 hr) followed by gas chromatography-mass spectrometry-olfactometry (GC-MS-O) analyses, and (2) relatively short HS-SPME extractions (30 min) followed by MDGC-MS-O analyses on selected chromatogram heart-cuts. Dairy manure was collected at research dairy farms in the United States and Israel. Volatile organic compounds (VOCs) resolved from multiple analyses included sulfur-containing compounds, volatile fatty acids, ketones, esters, and phenol/indole derivatives. A total of 86 potential odorants were identified. Of them, 17 compounds were detected by the human nose only. A greater number of VOCs and odorous compounds were detected, as well as higher mass loading, on solid-phase microextraction (SPME) fibers observed for longer extractions with SPME. However, besides sulfur-containing compounds, other selected compounds showed no apparent competition and displacement on the SPME fiber. The use of MDGC-MS-O increased chromatographic resolution even at relatively short extractions and revealed 22 additional odorants in one of the regions of the chromatogram. The two analytical approaches were found to be parallel to some extent whereas MDGC-MS-O can also be considered as a complementary approach by resolving more detailed chemical-sensory odor profiles.     

Packed in-tube solid phase microextraction with graphene oxide supported on aminopropyl silica: Determination of target triazines in water samples

On-line in-tube solid phase microextraction (in-tube SPME) coupled to high performance liquid chromatography and tandem mass spectrometry (HPLC-MS/MS) was successfully applied to the determination of selected triazines in water samples. The method based on the employment of a packed column containing graphene oxide (GO) supported on aminopropyl silica (Si) showed that the extraction phase has a high potential for triazines extraction aiming to its physical-chemical properties including ultrahigh specific surface area, good mechanical and thermal stability and high fracture strength. Injection volume and loading time were both investigated and optimized. The method validation using Si-GO to extract and concentrate the analytes showed satisfactory results, good sensitivity, good linearity (0.2–4.0 µg L^?1) and low detection limits (1.1–2.9 ng L^?1). The high extraction efficiency was determined with enrichment factors ranging from 1.2–2.9 for the lowest level, 1.3–4.9 intermediate level and 1.2–3.0 highest level (n = 3). Although the analytes were not detected in the real samples evaluated, the method has demonstrated to be efficient through its application in the analysis of spiked triazines in ground and mineral water samples.     

Assessment of spatial variation of ambient volatile organic compound levels at a power station in Kuwait

Twenty-four-hour integrated ambient air samples were collected in canisters at 10 locations within Kuwait’s major power station: Doha West Power Station to assess the spatial distribution of volatile organic compounds (VOCs) within the perimeter of the station. A total of 30 samples, i.e., three samples per location, were collected during February and March. The samples were analyzed using a gas chromatography with flame ionization detection (GC-FID) system and following the U.S. EPA Method TO-14A with modification. The results reflected the emission activities on the site and the meteorological conditions during sampling. Generally speaking, there was a negative correlation between the ambient temperature and the VOC concentrations, which indicates the sources were local. The halogenated compounds formed the highest proportion (i.e. 50–75 %) of the total VOC concentrations at the ten locations. 1,2,4-Trichlorobenzene and Vinyl Chloride concentrations were the highest amongst the other halogenated compounds. The aromatic compounds formed the least proportion (i.e. 1–4%) of the total VOC levels at all locations with Toluene having the highest concentrations amongst the aromatic compounds at seven locations. Propene, which is a major constituent of the fuel used, was the highest amongst the aliphatic compounds. The findings of this study and other relevant work suggests the measured VOC levels were the highest over the year, nevertheless, further work is required to assess the precisely temporal variation of VOC due to change in meteorological conditions and the emission rates.

Implications: Assessment of VOC concentrations around a power plant in Kuwait during the peak season showed halogenated compounds to be the dominant group. The calculated indoor concentrations were lower than those reported in a residential area about 12 km away.