Aqueous solubility calculation for petroleum mixtures in soil using comprehensive two-dimensional gas chromatography analysis data

An assessment of aqueous solubility (leaching potential) of soil contaminations with petroleum hydrocarbons (TPH) is important in the context of the evaluation of (migration) risks and soil/groundwater remediation. Field measurements using monitoring wells often overestimate real TPH concentrations in case of presence of pure oil in the screened interval of the well. This paper presents a method to calculate TPH equilibrium concentrations in groundwater using soil analysis by high-performance liquid chromatography followed by comprehensive two-dimensional gas chromatography (HPLC-GCXGC). The oil in the soil sample is divided into 79 defined hydrocarbon fractions on two GCXGC color plots. To each of these fractions a representative water solubility is assigned. Overall equilibrium water solubility of the non-aqueous phase liquid (NAPL) present in the sample and the water phase's chemical composition (in terms of the 79 fractions defined) are then calculated using Raoult's law. The calculation method was validated using soil spiked with 13 different TPH mixtures and 1 field-contaminated soil. Measured water solubilities using a column recirculation equilibration experiment agreed well to calculated equilibrium concentrations and water phase TPH composition.     

High-performance liquid chromatography fractionation using a silver-modified column followed by two-dimensional comprehensive gas chromatography for detailed group-type characterization of oils and oil pollutions

Successful remediation of oil-contaminated soils relies on a sound preceding characterization of the oil chemical composition and physicochemical properties. Comprehensive two-dimensional gas chromatography with flame ionization detection (GCxGC/FID) is known to be very suitable for the analysis of complex samples such as petroleum hydrocarbons. However, in spite of the high-separation power offered by GCxGC, it fails to completely separate certain hydrocarbon groups in petroleum hydrocarbon mixtures. This hampers a detailed chemical composition assessment which can lead to wrong conclusions on the behaviour of the oil in soil systems, e.g. biological degradability and water solubility. This paper describes a high-performance liquid chromatography (HPLC) system with a silver-modified column as a prefractionation step to GCxGC to improve chemical identification. With HPLC, the petroleum hydrocarbons were baseline separated into a saturated fraction (including alkanes and cycloalkanes) and an unsaturated fraction (including alkenes, aromatic hydrocarbons and heterocyclic components). Each fraction eluted in a small time window limiting the dilution caused by HPLC. The two fractions were collected and quantitatively analyzed with GCxGC/FID. Cold splitless injection of 4 microl was adopted to compensate the dilution caused by the prefractionation step. With oil-spiked soil samples, a good reproducibility was obtained (RSD=3.5%; n=7) and the recovery was satisfactory (87.7%).     

高效液相色谱-气相色谱在线联用同时测定土壤中饱和烃和芳香烃

为加强对土壤中石油烃类污染物的风险管控,生态环境部已将石油烃类列为土壤中的重点监测项目.石油烃源于石油与合成油,是涵盖一定碳数范围的碳氢化合物,主要分为饱和烃和芳香烃两大类.芳香烃通常是高度烷基化的单环、双环与多环芳烃,其对人和动物的毒性较饱和烃大很多,因此,仅仅测定土壤中总石油烃含量难以准确评估其环境毒性.目前环境领...     

Determination of aromatic hydrocarbons in petroleum jet fuels by capillary gas chromatography and high-performance liquid chromatography

About a hundred hydrocarbon compounds have been identified as components of petroleum jet fuel by capillary gas chromatography and high-performance liquid chromatography. In gas chromatography stuides, glass capillary columns over 100 m long with polysiloxane OV-101 have been used as the stationary phase. In liquid chromatography, 150-mm-long columns with a separation ability of about 60 000 theoretical plates meter of length have been used to separate partitioned fractions of aromatic hydrocarbons from petroleum jet fuels of various origins.     

Recovery of diesel fuel from soil by supercritical fluid extraction–gas chromatography

An analytical method based on CO₂ supercritical fluid extraction (SFE) followed by gas chromatography (GC) was evaluated, compared to Soxhlet extraction, and found to determine accurately and precisely diesel fuel contamination of standard soil samples at a total petroleum hydrocarbon level of 100 μg/g in soil. While both extraction methods have the same 3% relative repeatability standard deviation for determination of total hydrocarbon contamination at this level, SFE requires much less time, uses less organic solvent and provides better recovery of the more volatile n-C₁₀ to n-C₁₂ hydrocarbons.     

Thin-layer chromatography in the heavy organic industries

The technique of thin-layer chromatography, as practised in the organic industrial laboratory, is described and its applications to the analysis of petroleum hydrocarbons, fuels, lubricants, polymers, plastics and their additives, non-ionic surfactants and explosives are reviewed. The role of thin-layer chromatography in the conservation of the environment is also considered.     

A simple and rapid method for identifying the source of spilled oil using an electronic nose: confirmation by gas chromatography with mass spectrometry

Two types of electronic nose (EN), different in operational principle, were used to identify the source of spilled oil in an accident. The suspected sources considered were petroleum oil reservoirs and pipelines located near the site of the accident. Gas chromatography/mass spectrometry (GC/MS), operated in both EI and CI modes, was employed to confirm the identified source. The advantage of multisensors in spatially resolved sensing for direct multicomponent analysis was explored to minimize tedious sample preparation procedures. Subsequent principal component analysis helped in identifying the source. The advantage of fast separation in temporally resolved sensing was explored to rapidly yield compositional information; the resulting graphical representations helped clarify the source. Traditional GC/MS not only confirms the identified spilled oil source, but also provides detailed diagnostic information such as total petroleum hydrocarbons, polycyclic aromatic hydrocarbons and their C1-C4 alkylated homologues, as well as the n-alkanes, which are essential for follow-up remedial and regulatory actions. The main use of the electronic nose was demonstrated to be as a simple and rapid screening method for identifying a spilled oil source.     

The determination of petroleum hydrocarbons in soil using a miniaturized extraction method and gas chromatography

A gas chromatographic (GC) method for the determination of petroleum hydrocarbons (PH) in the boiling range from 175°C to 525°C (C₁₀?C₄₀ alkane) in soil was evaluated. The extraction was carried out using minimal amounts of acetone and heptane, prior to a clean up with silica gel. The extraction procedure was tested by means of standard solutions of petroleum products and soil samples. The clean up procedure did not have any significant effect on the amounts of petroleum hydrocarbons present and hydrocarbons of natural origin were removed effectively. The recovery of the extraction and clean up procedure for petroleum products in soil was greater than 90%. The standard deviation for the repeatability was estimated to be less than 10% based on multiple analyses of homogenized soil samples. The detection limit for soil was determined to be 10 mg/kg dry matter. Comparing the GC method with the widely used infrared spectrometry (IR) method in combination with a Soxhlet-extraction using Freon-113, the results obtained are equivalent.     

Trace analysis of N-formylmorpholine in hydrocarbons and water by gas-liquid chromatography

Summary N-Formylmorpholine, which is a solvent used in the extraction of benzene, toluene and xylenes extraction from petroleum feedstocks, is determined in trace amounts in water and in aromatic hydrocarbons by gas-liquid chromatography using two stationary phases. Traces of N-formylmorpholine in hydrocarbons was determined on a column packed with 2.3% Bentone 34+4.6% DEGA on Chromosorb W AW treated with 1% KOH. Traces of N-formylmorpholine in water was determined on 20% SE-30 on Chromosorb W AW. The developed methods were examined and proved to give quantitative results.     

A comparative study of solvent extraction of total petroleum hydrocarbons in soil

Three non-specific methods for the extraction of total petroleum hydrocarbons (TPH) from soil into organic solvent were compared. The techniques used for sample preparation were Soxhlet extraction, closed-vessel microwave-assisted extraction, and CEN shake extraction. The total concentrations of extracted compounds in the boiling point range of C10–C40 were determined by gas chromatography with flame ionization detection. The best recovery (99%) and repeatability (±3%) from standard oil mixtures were obtained with microwave-assisted extraction. However, the different extraction methods exhibited different behaviour when spiked soil samples were extracted. The best repeatability was obtained with CEN shake extraction (±6%) but the repeatability values for Soxhlet and microwave-assisted methods were quite high (>20%). However, the larger uncertainties of the latter extraction methods does not necessarily limit the applicability of these methods to the determination of petroleum hydrocarbons in soil, as in the assessment of soil contamination the expanded uncertainty of the result is usually not limited by analytical uncertainty, but rather by the uncertainty of the primary sampling stage. However, distinctive variation found in the chromatographic profiles illustrates that discretion should be obeyed when chromatograms obtained after application of different extraction methods on petroleum contaminated samples are to be used in the fingerprinting or age dating studies. Otherwise, misleading conclusions concerning the age of spillage could be drawn.     

Identification and quantification of alkene-based drilling fluids in crude oils by comprehensive two-dimensional gas chromatography with flame ionization detection

Comprehensive two-dimensional gas chromatography with flame ionization detection (GC x GC-FID) was used to measure alkene-based drilling fluids in crude oils. Compared to one-dimensional gas chromatography, GC x GC-FID is more robust for detecting alkenes due to the increased resolution afforded by second dimension separations. Using GC x GC-FID to analyze four oil samples from one reservoir contaminated with the same drilling fluid, C(15), C(16), C(17), C(18) and C(20) alkenes were identified. The drilling fluid that contaminated these samples also differed from another commercially obtained fluid, which only contained C(16) and C(18) alkenes. These results should motivate the petroleum industry to consider GC x GC-FID for measuring drilling fluids.     

Rapid preliminary separation of petroleum hydrocarbons by solid-phase extraction cartridges

Small, prepacked columns are tested for fractionating petroleum hydrocarbons from crude oil and products oils. Both normal-phase (silica) and reversed-phase (C₁₈) stationary phases yielded fast, easy, and reproducible separations, which facilitated further analysis of the oils by gas or liquid chromatography and mass spectrometry. The different separation characteristics of the stationary phases offer great flexibility in fractionating oil, enriching special compound classes, or separating hydrocarbons from environmental matrices.     

Detection and separation of mitoxantrone and its metabolites in plasma and urine by high-performance liquid chromatography

A high-performance liquid chromatographic method using ion-pair chromatography on reversed-phase C18 material was developed. After sample clean-up on XAD columns, mitoxantrone at concentrations below 1 ng/ml in serum and 0.2 ng/ml in urine were measurable with a coefficient of variation of less than 9.3% at a wavelength of 658 nm. Four metabolites were separated in urine. The two major metabolites co-chromatographed with the synthesized mono- and dicarboxylic acid derivatives of mitoxantrone. The method allowed the measurement of mitoxantrone and its metabolites in serum up to more than one week and in urine up to four weeks after administration of the drug.     

Pressurized solvent extraction followed by gas chromatography tandem mass spectrometry for the determination of benzotriazole light stabilizers in indoor dust

A novel and sensitive method for the determination of five benzotriazole compounds (commonly used as light stabilizers) in indoor dust is presented. Pressurized liquid extraction (PLE) and gas chromatography followed by tandem in time mass spectrometry (GC–MS/MS) were used as sample preparation and determination techniques, respectively. Extraction and clean-up were integrated on-line and, after an evaporative concentration step, the extract provided by the PLE instrument was injected directly in the GC–MS/MS system. Parameters affecting the performance of the sample preparation process were evaluated using experimental factorial designs. Under optimized conditions, analytes were recovered from 0.5 g samples in 3 static extraction cycles of 10 min, using a hexane:dichloromethane (7:3) mixture, at 90 °C. Silica (1 g) was placed in the bottom of the extraction cells as clean-up sorbent. The recoveries of the method varied from 82 to 122%, with standard deviations below 13. The inter-day precision ranged from 9 to 12%, and the limits of quantification (LOQs) remained below 10 ng g⁻¹ for all species. For the first time, four of the five investigated species were found in dust from indoor environments. Their mean concentrations ranged from 71 to 780 ng g⁻¹.     

Quantitative determination of organic priority pollutants in the composts of sewage sludge with rice straw by gas chromatography coupled with mass spectrometry

In order to investigate the occurrence and distribution of organic contaminants in the compost of sewage sludge with rice straw, four different composting treatments at a low carbon/nitrogen (C/N) ratio (13:1) were conducted. Thirty semi-volatile organic compounds (SVOCs) listed as priority pollutants by both China and the US Environmental Protection Agency (EPA) were Soxhlet-extracted, separated and analyzed by gas chromatography coupled with mass spectrometry (GC-MS). The results showed that after composting (56 days) most of SVOCs were detected in the final composts. The total concentrations of polycyclic aromatic hydrocarbons (PAHs) and phthalic acid esters ranged from 1.8 to 10 mg/kg dry weight (d.w.) and from 9.8 to 18 mg/kg d.w., respectively, being significantly higher than those of chlorobenzenes and nitroaromatic compounds which were generally less than 1.0 mg/kg d.w. The concentrations and predominant compounds of organic contaminants in the different composts varied, and were affected by their physico-chemical properties and the composting processes. Concentrations of SVOCs in the static aerated composting processes especially intermittently aerated composting treatment were considerably lower than those in the manual-turned composting treatments. Concentrations of organic contaminants especially PAHs and di(2-ethylhexyl) phthalate in the final composts were in agreement with the maximum permissible limits for agricultural purposes proposed by the European Union and by the EPA.     

A new interface for coupling solid phase microextraction with liquid chromatography

A modified Rheodyne 7520 microsample injector was used as a new solid phase microextraction (SPME)–liquid chromatography (LC) interface. The modification was focused on the construction of a new sample rotor, which was built by gluing two sample rotors together. The new sample rotor was further reinforced with 3 pieces of stainless steel tubing. The enlarged central flow passage in the new sample rotor was used as a desorption chamber. SPME fiber desorption occurred in static mode. But all desorption solvent in the desorption chamber was injected into LC system with the interface. The analytical performance of the interface was evaluated by SPME–LC analysis of PAHs in water. At least 90% polycyclic aromatic hydrocarbons (PAHs) were desorbed from a polyacrylonitrile (PAN)/C18 bonded fuse silica fiber in 30 s. And injection was completed in 20 s. About 10–20% total carryovers were found on the fiber and in the interface. The carryover in the interface was eliminated by flushing the desorption chamber with acetonitrile at 1 mL min⁻¹ for 2 min. The repeatability of the method was from 2% to 8%. The limit of detection (LOD) was in the mid pg mL⁻¹ range. The linear ranges were from 0.1 to 100 ng mL⁻¹. The new SPME–LC interface was reliable for coupling SPME with LC for both qualitative and quantitative analysis.     

反相液相制备色谱法结合超临界流体制备色谱法分离纯化海风藤中的化合物

建立了基于反相液相制备色谱和超临界流体制备色谱的组合方法,用于分离纯化醇提水沉后石油醚层中的海风藤。首先以甲醇作为改性剂,采用醇提水沉法去除海风藤甲醇提取物中的叶绿素,加入硅藻土后用石油醚回流富集目标成分。选用反相C18制备色谱柱将其分为18个组分,然后将组分在SFC模式下进行制备。选用酰胺色谱柱,以甲醇为改性剂,在柱温30℃、背压15.0 MPa的条件下进行分离。基于反相色谱和超临界流体色谱不同的分离选择性,最后分离得到6个高纯度化合物。该法展示了反相制备色谱和超临界流体制备色谱在海风藤分离纯化方面的优势,特别是超临界流体色谱在天然产物的分析和制备方面的巨大潜力。     

Detailed elucidation of hydrocarbon contamination in food products by using solid-phase extraction and comprehensive gas chromatography with dual detection

The present work is focused on the development/optimization of a comprehensive two-dimensional gas chromatography method, with dual detection [flame ionization (FID) and mass spectrometric], for the simultaneous identification and quantification of mineral-oil contaminants in a variety of food products. The two main classes of contaminants, namely saturated and aromatic hydrocarbons, were previously fractionated on a manually-packed silver silica solid-phase extraction (SPE) cartridge. The quantitative results were compared with those obtained by performing a large volume injection, in a GC-FID system, after the same SPE process and by an on-line liquid–gas chromatography method, with very similar results observed. The presence of a series of unknown compounds, that appeared when using the off-line methods, was investigated using the mass spectrometric data, and were tentatively-identified as esterified fatty acids, most probably derived from vegetable oil based ink.     

全二维气相色谱用于轻质石油馏分中芳烃含量的测定

建立了采用全二维气相色谱(GC×GC)技术一次进样完成轻质石油馏分中非芳烃、一环芳烃和二环芳烃的分离、定性 和定量。通过对柱系统的选择和色谱条件的优化,实现了一次全二维气相色谱分析即完成轻质石油馏分的族组成分离以及 目标化合物的分离。方法的加标回收率为89.5%～106.1%;样品中各组分含量重复测定的相对标准偏差均不大于5.8%,能 够满足样品测定的精密度和准确性要求,且完成1次分析最多只需要30 min。     

Determination of penicillin G in bovine plasma by high-performance liquid chromatography after pre-column derivatization.

A simple, selective, and sensitive liquid chromatographic method with ultraviolet detection was developed for the analysis of penicillin G in bovine plasma. The assay utilizes a simple extraction of penicillin G from plasma (with a known amount of penicillin V added as internal standard) with water, dilute sulphuric acid and sodium tungstate solutions, followed by concentration on a conditioned C18 solid-phase extraction column. After elution with 500 microliters of elution solution, the penicillins are derivatized with 500 microliters of 1,2,4-triazole-mercuric chloride solution at 65 degrees C for 30 min. The penicillin-mercury mercaptide complexes are separated by reversed-phase liquid chromatography on a C18 column. The method, which has a detection limit of 5 ng/ml (ppb) in bovine plasma, was used to quantitatively measure the concentrations of penicillin G in plasma of steers at a series of intervals after the intramuscular administration of a commercial formulation of procaine penicillin G.