Ken Li

Headspace solid phase microextraction (HSSPME) for the determination of volatile and semivolatile pollutants in soils.

We have investigated the use of headspace solid phase microextraction (HSSPME) as a sample concentration and preparation technique for the analysis of volatile and semivolatile pollutants in soil samples. Soil samples were suspended in solvent and the SPME fibre suspended in the headspace above the slurry. Finally, the fibre was desorbed in the Gas Chromatograph (GC) injection port and the analysis of the samples was carried out. Since the transfer of contaminants from the soil to the SPME fibre involves four separate phases (soil-solvent-headspace and fibre coating), parameters affecting the distribution of the analytes were investigated. Using a well-aged artificially spiked garden soil, different solvents (both organic and aqueous) were used to enhance the release of the contaminants from the solid matrix to the headspace. It was found that simple addition of water is adequate for the purpose of analysing the target volatile organic chemicals (VOCs) in soil. The addition of 1 ml of water to 1 g of soil yielded maximum response. Without water addition, the target VOCs were almost not released from the matrix and a poor response was observed. The effect of headspace volume on response as well as the addition of salt were also investigated. Comparison studies between conventional static headspace (HS) at high temperature (95 degrees C) and the new technology HSSPME at room temperature ( approximately 20 degrees C) were performed. The results obtained with both techniques were in good agreement. HSSPME precision and linearity were found to be better than automated headspace method and HSSPME also produced a significant enhancement in response. The detection and quantification limits for the target VOCs in soils were in the sub-ng g(-1) level. Finally, we tried to extend the applicability of the method to the analysis of semivolatiles. For these studies, two natural soils contaminated with diesel fuel and wood preservative, as well as a standard urban dust contaminated with polyaromatic hydrocarbons (PAHs) were tested. Discrimination in the response for the heaviest compounds studied was clearly observed, due to the poor partition in the headspace and to the slow kinetics of all the processes involved in HSSPME.

Characterization and source identification of hydrocarbons in water samples using multiple analytical techniques.

This paper describes a case study in which multiple analytical techniques were used to identify and characterize trace petroleum-related hydrocarbons and other volatile organic compounds in groundwater samples collected in a bedrock aquifer exploited for drinking water purposes. The objective of the study was to confirm the presence of gasoline and other petroleum products or other volatile organic pollutants in those samples in order to assess the respective implication of each of the potentially responsible parties to the contamination of the aquifer. In addition, the degree of contamination at different depths in the aquifer was also of interest. The analytical techniques used for analyses of water samples included gas chromatography-mass spectrometry (GC-MS) and capillary GC with flame-ionization detection, solid-phase microextraction and headspace GC-MS techniques. Chemical characterization results revealed the following: (1) The hydrocarbons in sample A (near-surface groundwater, 0-5 m) were clearly of two types, one being gasoline and the other a heavy petroleum product. The significant distribution of five target petroleum-characteristic alkylkated polycyclic aromatic hydrocarbon homologues and biomarkers confirmed the presence of another heavy petroleum product. The concentrations of the TPHs (total petroleum hydrocarbons) and BTEX (collective name of benzene, toluene, ethylbenzene, and p-, m-, and o-xylenes) were determined to be 1070 and 155 microg/kg of water for sample A, respectively. (2) The deepest groundwater (sample B, collected at a depth ranging between 15 and 60 m) was also contaminated, but to a much lesser degree. The concentrations of the TPH and BTEX were determined to be only 130 and 2.6 microg/kg of water for sample B, respectively. (3) The presence of a variety of volatile chlorinated compounds to the groundwater was also clearly identified.

Evaluation of supercritical fluid extraction, microwave-assisted extraction and sonication in the determination of some phenolic compounds from various soil matrices

Abstract Extraction methods using supercritical fluid extraction (SFE) and microwave-assisted process (MAP) techniques, with or without a one-step in situ derivatisation, were evaluated for the extraction of phenol, o-cresol, m-cresol and p-cresol from soils. Five artificially spiked soil matrices were prepared; three of them were prepared by adding various amounts of activated charcoal in order to increase the degree of analyte–matrix interaction. We also applied the methods to a real phenol contaminated soil with a high carbon content (18%). To provide a basis for comparison, all the soils were extracted using an US Environmental Protection Agency-approved sonication protocol. The extracts obtained were analyzed on a GC–MS system without any preliminary clean-up or concentration steps. The results showed that SFE and MAP are more efficient than sonication with at least twice the recovery in all the soils tested. MAP and MAP-derivatisation showed the best recoveries (>80%) for the five spiked matrices studied with the exception of o-cresol in soils with activated charcoal content higher than 5%. In these specific soils, SFE showed very low recoveries for the four phenols. However, recoveries were significantly improved when a derivatisation step was combined to SFE. In the real soil tested, the recoveries using derivatisation–extraction process were lower than the recoveries using extraction process. In general, derivatisation–extractions perform better and do not require extreme extraction conditions.

Headspace solid-phase microextraction for the determination of volatile and semi-volatile pollutants in water and air.

In this work we report the use of solid-phase microextraction (SPME) to extract and concentrate water-soluble volatile as well as semi-volatile pollutants. Both methods of exposing the SPME fibre were utilised: immersion in the aqueous solution (SPME) and in the headspace over the solution (HSSPME). The proposed HSSPME procedure was compared to conventional static headspace (HS) analysis for artificially spiked water as well as real water samples, which had been, equilibrated with various oil and petroleum products. Both techniques gave similar results but HSSPME was much more sensitive and exhibited better precision. Detection limits were found to be in the sub-ng/ml level, with precision better than 5% R.S.D. in most cases. To evaluate the suitability of SPME for relatively high contamination level analysis, the proposed HSSPME method was applied to the screening of run-off water samples that had heavy oil suspended in them from a tire fire incident. HSSPME results were compared with liquid--liquid extraction. Library searches were conducted on the resulting GC-MS total ion chromatograms to determine the types of compounds found in such samples. Both techniques found similar composition in the water samples with the exception of alkylnaphthalenes that were detected only by HSSPME. A brief study was carried out to assess using SPME for air monitoring. By sampling and concentrating the volatile organic compounds in the coating of the SPME fibre without any other equipment, this new technique is useful as an alternative to active air monitoring by means of sampling pumps and sorbent tubes.

Accelerated solvent extraction (ASE) of environmental organic compounds in soils using a modified supercritical fluid extractor

Accelerated solvent extraction (ASE) has been applied to the quantitative extraction of a selected list of semi-volatiles, which include polycyclic aromatic hydrocarbons (PAHs), phenols, polychlorinated biphenyls (PCBs) and total petroleum hydrocarbons. Two conventional supercritical fluid extraction (SFE) systems, the Suprex Prep Master and SFE/50 systems have been modified to function as ASE systems. Using solvent instead of supercritical fluid, extraction in an enclosed system proceeded under high pressure and temperature. Parameters such as extraction temperature and effect of modifiers were investigated. Although limited by a 150 degrees C maximum oven temperature, effective extraction could be carried out in less than 25 min for all the compounds studied. The technique was applied to a variety of real matrices contaminated with hydrocarbons, PAHs and phenols. Validations of the technique were performed using standard reference materials. Recoveries for these matrices were good (>75%) and precision (R.S.D.) was generally less than 10%. Primarily a rapid field extraction technique, comparison with other rapid extraction such as sonication and microwave assisted extraction (MAP) were made. Recoveries were found to be comparable to MAP and superior to sonication. On the present ASE system, only sequential extraction can be carried out but given the rapid nature of the process, about 15 samples can be carried out in a working day.

The Newfoundland Offshore Burn Experiment : NOBE

ABSTRACT A group of 25 agencies from Canada and the United States conducted a major offshore burn experiment near Newfoundland, Canada. Two lots of oil, about 50 cubic meters (50 tons) each, were released into a fireproof boom. Each burn lasted over an hour and was monitored for emissions and physical parameters. Over 200 sensors or samplers were employed to yield data on over 2000 parameters or substances. The operation was extensive; more than 20 vessels, 7 aircraft and 230 people were involved in the operation at sea. The quantitative analytical data show that the emissions from this in-situ oil fire were less than expected. All compounds and parameters measured more than about 150 meters from the fire were below occupational health exposure levels; very little was detected beyond 500 meters. Pollutants were found to be at lower values in the Newfoundland offshore burn than they were in previous pan tests. Polyaromatic hydrocarbons (PAHs) were found to be lower in the soot than in the starting oil and ...

Phenol and methylphenol isomers determination in soils by in-situ microwave-assisted extraction and derivatisation

A simultaneous microwave-assisted extraction-derivatisation procedure was developed and optimised for phenol and methyl phenol isomers from soil samples. Both spiked and real soil samples (carbon content of 18%) were irradiated with microwaves in a closed-vessel system while immersed in hexane that had been previously doped with acetic anhydride and pyridine so as to effect an in situ catalytic acetylation of the target phenolic compounds. Spiked samples were prepared at least 20 days before treatment to simulate natural weathering processes and allow for the formation of analyte-matrix interactions. Optimization of the method was achieved by using a factorial design approach on parameters such as the volume of solvent, the quantity of acetic anhydride and the extraction temperature. Comparison with ultrasonic extraction procedures indicated that microwave-assisted methods gave superior recoveries (ca. two-fold) and greater precision in addition to being characterised by shorter extraction times. The procedure using microwaves yielded samples that could be analyzed directly on a GC-MS system without any preliminary clean-up or concentration steps. The detection limit of this novel method was found to be in the low-ppb range.

Solvent vapour monitoring in work space by solid phase micro extraction

Solid phase micro extraction (SPME) is a fast, solvent-less alternative to conventional charcoal tube sampling/carbon disulfide extraction for volatile organic compounds (VOC). In this work, SPME was compared to the active sampling technique in a typical lab atmosphere. Two different types of fibre coatings were evaluated for solvent vapour at ambient concentration. A general purpose 100 microm film polydimethylsiloxane (PDMS) fibre was found to be unsuitable for VOC work, despite the thick coating. The mixed-phase carboxen/PDMS fibre was found to be suitable. Sensitivity of the SPME was far greater than charcoal sorbent tube method. Calibration studies using typical solvent such as dichloromethane (DCM), benzene (B) and toluene (T) showed an optimal exposure time of 5 min, with a repeatability of less than 20% for a broad spectrum of organic vapour. Minimum detectable amount for DCM is in the range of 0.01 microg/l (0.003 ppmv). Variation among different fibres was generally within 30% at a vapour concentration of 1 microg DCM/l, which was more than adequate for field monitoring purpose. Adsorption characteristics and calibration procedures were studied. An actual application of SPME was carried out to measure background level of solvent vapour at a bench where DCM was used extensively. Agreement between the SPME and the charcoal sampling method was generally within a factor of two. No DCM concentration was found to be above the regulatory limit of 50 ppmv.

Emissions from mesoscale in situ oil fires: the mobile 1991 experiments

A series of 14 mesoscale burns were conducted in 1991 to study various aspects of oil burning in situ. Extensive sampling and monitoring of these burns were conducted to determine the emissions. This was done at two downwind ground stations, one upwind ground station and in the smoke plume using a blimp and a remote-controlled helicopter. Particulate samples in air were taken and analyzed for polycyclic aromatic hydrocarbons (PAHs). PAHs were found to be lower in the soot than in the starting oil. Metals in the oil were found concentrated in the residue and could not be measured in soot samples using conventional industrial hygiene sampling techniques. Particulates in the air were measured by several means and found to be greater than recommended exposure levels only up to 150 m downwind at ground level. Combustion gases including carbon dioxide, sulphur dioxide and carbon monoxide did not reach exposure level maximums. These gases were emitted over a broad area around the fire and are not directly associated with the plume trajectory. Volatile organic compound (VOCs) emissions are extensive from fires, but the levels are less than those emitted from a non-burning test spill. Over 50 compounds were identified and quantified, several at possible levels of concern up to 200 m downwind. Water under the burns was analyzed; no analytes of concern could be found at the detection levels of the methods. The burn residue was analyzed for the same compounds as the air particulate samples. The residue contained elevated amounts of metals. PAHs were at a lower concentration in the residue than in the starting oil, however there is a slight differential concentration increase in some higher molecular weight species. Overall, indications from these mesoscale trials are that emissions from in situ burning are low in comparison to other sources of emissions and result in concentrations of air contaminants that are below exposure limits beyond 500 m downwind.

Studies of Emissions From Oil Fires

ABSTRACT Over 35 meso-scale burns were conducted to study various aspects of diesel and crude oil burning in situ. Extensive sampling and monitoring of these burns were conducted at downwind statio...