Determination of Biodegradation Process of Benzene, Toluene, Ethylbenzene and Xylenes in Seabed Sediment by Purge and Trap Gas Chromatography

Benzene, toluene, ethylbenzene, and xylenes (BTEX) are commonly found in crude oil and are used in geochemical investigations as direct indicators of the presence of oil and gas. BTEX are easily volatile and can be degraded by microorganisms, which affect their precise measurement seriously. A method for determining the biodegradation process of BTEX in seabed sediment using dynamic headspace (purge and trap) gas chromatography with a photoionization detector (PID) was developed, which had a detection limit of 7.3–13.2 ng L^?1 and a recovery rate of 91.6–95.0%. The decrease in the concentration of BTEX components was monitored in seabed sediment samples, which was caused by microorganism biodegradation. The results of BTEX biodegradation process were of great significance in the collection, transportation, preservation, and measurement of seabed sediment samples in the geochemical investigations of oil and gas.     

吹扫捕集-气相色谱法测定海水中苯、甲苯、乙苯和二甲苯的生物降解

苯、甲苯、乙苯和二甲苯(简称BTEX)等单环芳烃是石油的重要组分。在油气地球化学勘查领域,BTEX是油气藏信息的直接指示物。BTEX具有挥发性,并且可以受到微生物的降解作用,直接影响到BTEX含量的准确测量。本研究建立了动态顶空(吹扫捕集)和光离子化检测器(PID)的气相色谱测量海水基样品中BTEX的生物降解方法。苯、甲苯、乙苯、对间二甲苯及邻二甲苯的检出限分别为7.3、8.1、11.4、8.3、13.2ng/L;1μg/L海水样品中BTEX回收率为92.84%~100.92%。样品无需预处理。BTEX生物降解规律对海洋油气地球化学勘探中所涉及的样品采集、运输、保存、测量及结果分析具有重要指导意义。     

Headspace–Mass Spectrometry with Alternative Chromatographic Separation Using a Column Switching System for the Screening and Determination of BTEX and Styrene in Comestible Oil

A headspace–mass spectrometry with alternative chromatographic separation using a column switching system was developed for the screening and confirmation of BTEX and styrene in comestible oils. According to the position of the switching valve, the chromatographic column can be bypassed and the volatile sample constituents are transferred directly from the headspace sampler to the mass spectrometer providing a global, non resolved, signal in less than 1 min after injection. In this way, a set of samples can be rapidly processed in order to determine if they are (or not) contaminated with BTEX and styrene. Subsequently, only the samples with positive response in the previous screening can be processed by gas chromatography–mass spectrometry in the same analytical system by switching the position of the valve, thus confirming the presence of the analytes in the sample.

The method presents good analytical features and it is applicable to the analysis of real samples. Detection limits were lower than 0.1 ng mL^?1, and recoveries were between 97 and 105% with relative standard deviations lower than 4%.

Analysis of real comestible oils showed the presence of toluene, benzene, and styrene in some samples packed in plastic bottles.     

Determination of BTEX Compounds by Dispersive Liquid–Liquid Microextraction with GC–FID

Rapid, inexpensive, and efficient sample-preparation by dispersive liquid–liquid microextraction (DLLME) then gas chromatography with flame ionization detection (GC–FID) have been used for extraction and analysis of BTEX compounds (benzene, toluene, ethylbenzene, and xylenes) in water samples. In this extraction method, a mixture of 25.0 μL carbon disulfide (extraction solvent) and 1.00 mL acetonitrile (disperser solvent) is rapidly injected, by means of a syringe, into a 5.00-mL water sample in a conical test tube. A cloudy solution is formed by dispersion of fine droplets of carbon disulfide in the sample solution. During subsequent centrifugation (5,000 rpm for 2.0 min) the fine droplets of carbon disulfide settle at the bottom of the tube. The effect of several conditions (type and volume of disperser solvent, type of extraction solvent, extraction time, etc.) on the performance of the sample-preparation step was carefully evaluated. Under the optimum conditions the enrichment factors and extraction recoveries were high, and ranged from 122–311 to 24.5–66.7%, respectively. A good linear range (0.2–100 μg L⁻¹, i.e., three orders of magnitude; r ² = 0.9991–0.9999) and good limits of detection (0.1–0.2 μg L⁻¹) were obtained for most of the analytes. Relative standard deviations (RSD, %) for analysis of 5.0 μg L⁻¹ BTEX compounds in water were in the range 0.9–6.4% (n = 5). Relative recovery from well and wastewater at spiked levels of 5.0 μg L⁻¹ was 89–101% and 76–98%, respectively. Finally, the method was successfully used for preconcentration and analysis of BTEX compounds in different real water samples.

     

Analysis of BTEX, PAHs and metals in the oilfield produced water in the State of Sergipe, Brazil

During oil and gas exploitation, large amounts of produced water are generated. This water has to be analyzed with relation to the chemical composition to deduce the environmental impact of its discharge after a treatment process. Therefore, a study was carried out to evaluate preliminarily the BTEX (benzene, toluene, ethylbenzene and xylenes), polycyclic aromatic hydrocarbons (PAHs) and metals contents in produced water samples taken from effluents of the Bonsucesso treatment plant located in the city of Carmópolis, the most important oil and gas producer in the State of Sergipe, North-east of Brazil. Three methods were optimized to determine the target compounds. Polycyclic aromatic hydrocarbons were determined by gas chromatography with mass spectrometric detection (GC/MS), volatile aromatic hydrocarbons (BTEX) by gas chromatography with photoionization detector (GC/PID) and metals were analyzed by flame atomic absorption spectrometry (FAAS). The results showed that concentrations of the target compounds in these samples ranged from 96.7 to 1397 μg L^− 1 for BTEX, from 0.9 to 10.3 μg L^− 1 for PAHs and from 0.003 to 4540 mg L^− 1 for metals.     

Biodegradation of BTEX Aromatics by a Haloduric Microbial Consortium Enriched from a Sediment of Bohai Sea,China

This study focused on a haloduric BTEX-degrading microbial consortium EC20 enriched from Bohai Sea sediment. EC20 degraded 87% of BTEX at 435 mg L^?1 initial concentration (benzene, toluene, ethylbenzene, and xylenes in equal proportions) in the presence of 3.4% NaCl. 16S rRNA gene-based PCR-DGGE profiles revealed that the dominant bacteria in EC20 were Proteobacteria, Actinobacteria, Bacteroidetes, and Firmicutes at the phylum level, and Pseudomonas, Mesorhizobium, Achromobacter, Stenotrophomonas, and Halomonas at the genus level. PCR detection of genes coding the key enzymes which participated in BTEX degradation pathways showed that the enriched consortium EC20 contained TOL pathway and TOD pathway to initiate biodegradation of BTEX.     

Large Volume Headspace Analysis Using Solid-Phase Microcolumn Extraction

A rapid and simple large volume headspace (HS) sampling technique termed headspace solid-phase microcolumn extraction (HS-SPMCE) is described. HS gas above a liquid or solid sample is aspirated by attaching a gas-tight syringe onto a glass thermal desorption tube filled with Tenax sorbent. The trapped analytes are recovered by thermal desorption for gas chromatography–mass spectrometry (GC–MS) analysis. Benzene, toluene, ethylbenzene and the xylene isomers (BTEX) are used as model compounds to demonstrate the application of the extraction procedure for water samples. The results of the tests of the effect of agitation time and aspiration rate on recovery of the analytes show a good robustness of the method. BTEX are determined in the linear range from 0.5 to 50.0 μg L^?1 with limits of detection (3 σ) ranging within 0.09–0.14 μg L^?1 (MS was in scan mode). The method provides a good repeatability (RSD < 9%) and only a negligible carryover effect was observed ( ≤0.05%) when analysing BTEX at concentration 50.0 μg L^?1.     

Ultrasensitive direct determination of BTEX in polluted soils using a simple and novel pressure-controlled solid-phase microextraction setup

A pressure-controlled headspace solid-phase microextraction (PC-HS-SPME) setup was developed, by reconsidering the strengths and weaknesses points of the similar reported systems. The new setup was coupled with gas chromatography–flame ionization detection (GC–FID) for direct analysis of benzene, toluene, ethylbenzene and xylene (BTEX) in contaminated soils, without any sample preparation step. The important experimental factors, affecting the performance of the method, including volumes of extraction and vacuum vials, type of SPME fiber, extraction time and temperature, moisture content of the sample, and sonication time were studied and optimized. Under the optimal conditions, good linearity of the calibration curves (R² > 0.997) was obtained in the concentration range of 0.1–20,000 ng g^?1. The limits of detections were found to be 0.001–0.08 ng g^?1. The relative standard deviations, for six repetitive analyses of 100 ng g^?1 BTEX, were obtained to be 5.7–12.3%. The PC-HS-SPME–GC–FID procedure was successfully applied for the extraction and determination of BTEX in the polluted soil samples.     

Effect of the Degree of Oil Biodegradation on the Crystallization of Methane Hydrate and Ice in Water-Oil Emulsions

To study the influence exerted by oxidized oil components on the nucleation and growth of gas hydrates the nucleation of methane hydrate and ice in 50 wt % emulsions of oil in native oil and two samples of the same oil subjected to biodegradation for 30 and 60 days (samples N, V30, and V60, respectively) were examined. In the course of measurements, the samples were cooled to–15°C at a constant rate of 0.14 deg min^–1 and then heated to the initial temperature. The initial methane pressure in the system was 15 MPa at 20°C. In the process, the temperatures were recorded at which heat effects corresponding to the formation of hydrate/ice and the melting of these. In the case of emulsion N, no exothermic effects were manifested in the cooling stage. In the heating stage, the endothermic effects of ice melting were found in half of the samples. No effects corresponding to the decomposition of the hydrate were observed. In experiment with V30 samples, the formation of the hydrate and ice was manifested as strong exothermic effects. Ice was formed in all the experiments, and the hydrate, only in 21% of the samples. Finally, in experiments with V60, ice and the hydrate were formed in 54 and 13% of cases, respectively. Their formation was manifested as weak exothermic effects in the cooling stage. Thus, it was demonstrated that the biodegradation level of oil samples affects the nucleation of methane hydrate and ice in emulsions formed on the basis of these samples.

     

Comparative study of direct immersion and headspace single drop microextraction techniques for BTEX determination in water samples using GC-FID

In the present work the determination of benzene, toluene, ethylbenzene and o-xylene (BTEX) in environmental sample solutions using gas chromatography with flame ionisation detection (GC-FID) combined with three different sampling techniques, such as; direct single drop microextraction (DI-SDME), headspace single drop microextraction (HS-SDME) and ultrasonic assisted HS-SDME, were compared. In all of these techniques, for the determination of BTEX, the experimental parameters such as organic solvent effect, extraction time, agitation speed and salting effect were optimised. At their optimised conditions of operation the detection limits, times of extraction and precision for the three techniques are established. A detailed comparison of the analytical performance characteristics of these techniques for final GC-FID determination of BTEX in water samples was given. The technique provided a linear range of 50–20000?ng?mL^–1 for DI-SDME and 10–20000?ng?mL^–1 for HS-SDME methods, good repeatability (RSDs <4.72–7.74% for DI-SDME and 1.80–7.05% for HS-SDME (n?=?5), good linearity (r?≥?0.9978) and limits of detection (LODs) in the range of 0.006–10?ng?mL^?1 for DI-SDME, 0.1–3?ng?mL^–1 for HS-SDME methods (S/N?=?3). Then the optimised techniques were also applied to real samples (river and waste waters) containing BTEX and similar precision (RSD?<?8.2,?n?=?3) was obtained.     

Determination of BTEX in urine samples using cooling/heating-assisted headspace solid-phase microextraction

Excessive and uncontrolled exposures of the workers to benzene, toluene, ethylbenzene and xylene (BTEX) have currently raised great concerns among industrial hygienist all over the world. Therefore, the effective monitoring of such exposures is assumed to be of prime importance. A cold fiber solid-phase microextraction device based on a cooling capsule as a cooling unit and CO₂ as a coolant was applied to quantitatively analyze BTEX in aqueous samples. A gas chromatography with flame ionization detection was recruited to analyze the target analytes, which had been identified according to their retention times. Several factors such as coating temperature, extraction time and temperature, sample volume and sodium content were optimized. Two modes of extraction, i.e., headspace (HS) and headspace cold fiber (HS-CF) in SPME, were investigated and compared under optimized conditions. The results revealed that HS-CF-SPME has the most appropriate outcome for the extraction of BTEX from aqueous samples. Under the optimized conditions, the calibration curves were linear within the range of 0.2–500 ng ml^?1 and the detection limits were between 0.02 and 0.07 ng ml^?1.The intraday relative standard deviations was lower than about 10%. The method was successfully applied to the determination of BTEX in urine samples with good recovery.     

Simultaneous determination of cyromazine,melamine and their biodegradation products by ion-pair high-performance liquid chromatography

An ion-pair high-performance liquid chromatography with ultraviolet detection method for the determination of cyromazine, melamine and its biodegradation products (ammeline, ammelide, cyanuric acid and biuret) was developed. C18 column was utilised to separate the six analytes with a mobile phase consisting of perchloric acid-ammonia solution and acetonitrile, under gradient elution and variable flow rate. The detection wavelengths were 205 nm for cyanuric acid and biuret and 222 nm for cyromazine, melamine, ammeline and ammelide. For analysis of sediment samples, the extraction solution containing acetonitrile, ammonia and water (80:10:10 by volume) was used to extract the analytes from sediment matrix. Using the extraction method for the spiked sediment sample, high linearity of matrix-matched standard curve could be obtained for the six analytes. The method detection limit was 0.1 μg g^?1 for melamine and cyromazine, 0.2 μg g^?1 for ammeline and ammelide, 1.2 μg g^?1 for cyanuric acid and 1.0 μg g^?1 for biuret in sediment matrix. The recoveries of these compounds were 70.1–98.3% and the relative standard deviations were 0.5–4.4%. Finally, the proposed method was successfully applied to the analysis of the sediment sample near the wastewater outlet of a melamine-producing factory.     

Bioremediation of Marine Sediments Impacted by Petroleum

The aim of this work was to optimize the bioremediation of crude oil-contaminated sand sediment through the biostimulation technique. The soil was obtained in the mid-tide zone of Guanabara Bay, Rio de Janeiro, Brazil and was artificially contaminated with crude oil at 14 g kg^?1. Bioremediation optimization was performed using an experimental design and statistical analysis of the following factors: supplementation with commercial biosurfactant Jeneil® IBR 425 and commercial mineral NPK fertilizer. The response variable used was the biodegradation of the heavy oil fraction, HOF. The analysis of the studied factors and their interactions was executed using contour plots, Pareto diagram and ANOVA table. Experimental design results indicated that the supplementation with fertilizer at 100:25:25 C/N/P ratio and biosurfactant at 2 g kg^?1 yielded biodegradation of HOF at about 30% during 30 days of process. Some experiments were carried out using the experimental design results, yielding 65% of biodegradation of HOF and 100% of n- alkanes between C15 and C30 during 60 process days. Intrinsic biodegradation test was carried out, yielding 85% of biodegradation of n-alkanes between C15 and C30 during 30 days of process.     

Electrodeposition of a copolymer nanocomposite for the headspace solid-phase microextraction of benzene,toluene, ethylbenzene and xylenes

In this study, polyaniline-co-poly(o-toluidine)/graphene oxide nanosheets composite was electrodeposited on the surface of a stainless steel wire as a new coating for headspace solid-phase microextraction of benzene, toluene, ethylbenzene and xylenes (BTEX) with gas chromatography–mass spectrometry. The characteristics of the new coating were evaluated by the scanning electron microscopy and Fourier transform infrared spectroscopy. To study the coating performance, the influence of various parameters such as deposition potential and time, concentration of the monomers and GONSs, desorption temperature and time, extraction temperature and time and ionic strength on BTEX extraction efficiency was investigated. At the optimum conditions, the linear ranges and detection limits (S/N?=?3) were found 0.01–50 and 0.001–0.05 ng mL^?1, respectively. The intra-day and inter-day relative standard deviations (RSDs) at 0.5 ng mL^?1 concentration level (n?=?5) using a single-fiber were from 5.4 to 8.3 and 7.5 to 10.3%, respectively. The fiber-to-fiber RSDs % (n?=?3) was between 8.4 and 12.5%. Finally, the development method was applied to the analysis of various real samples.     

Determination of BTEX Compounds in Solid–Liquid Mixing Paint Using the Combination of Solid Phase Extraction,Thermal Desorption and GC-FID

A novel method was developed and validated for determination of benzene, toluene, p-xylene, m-xylene, o-xylene (BTEX) in a solid–liquid mixing matrix. It makes use of solid phase extraction and thermal desorption (SPE-TD), followed by gas chromatographic flame ionization detector analysis (GC-FID). The trapped BTEX can be measured directly after thermal desorption onto the stainless-steel packed chromatographic column. The effect of tailing area of solvent was removed with the use of SPE-TD technique, and the result shows good reproducibility with very little matrix dependency. The study also supports that the lifetime of the Tenax adsorption tube could be extended over 150 desorption operation at 200 °C, which enables performing excellent stability and reproducibility of BTEX analysis.

     

Ordered Nanoporous Carbon-Based SPME and Determination by GC

CMK-1 (carbon mesoporous from Korea) type ordered nanoporous carbon was investigated as a novel solid-phase microextraction fiber for the first time. The microextraction process was coupled with GC-FID and used to extract benzene, toluene, ethylbenzene and xylenes (BTEX) from the head space of the solution samples. Prepared fibers featured advantages like easy and fast preparation, high thermal and mechanical stability in which a fiber could be used for more than 60 tests. Employing Taguchi method and orthogonal array design; OA₁₆ (4⁵), the HS-SPME of BTEX was optimized. Under the optimized conditions for all BTEX components, the linearity was from 3 to 800 μg L^?1, the relative standard deviation (RSD%) of the method was between 4.2 and 9.4% and limit of detections was between 0.27 and 1.1 μg L^?1. The recovery values were from 87.1 to 106.2% in water samples. Finally, the applicability of the proposed method was evaluated by the extraction and determination of BTEX in the water and petrochemical samples.     

Application of passive sampling technique in monitoring research on quality of atmospheric air in the area of Tczew,Poland

This paper presents the results of atmospheric air quality research in Tczew (adjacent to the Vistula River) on the content of BTEX compounds. procedure applied during the sampling of the analytes from the air used the passive sampling technique (diffusive passive sampler, Radiello^®). For determination of BTEX compounds in atmospheric air, two-stage thermal desorption technique combined with gas chromatography (TD-GC-FID) was applied.

Research was conducted from March to December 2011. The annual average concentration of benzene, toluene, ethylbenzene and total xylenes determined in atmospheric air for the monitoring period were: 0.87 μg m^–3, 2.9 μg m^–3, 1.3 μg m^–3 and 5.9 μg m^–3, respectively. In order to pre-identify potential sources of emissions of BTEX compounds, statistical analysis was carried out. This determined interactions between specified concentration levels of BTEX compounds in atmospheric air for the monitored area.     

Enhanced Biodegradation of Alkane Hydrocarbons and Crude Oil by Mixed Strains and Bacterial Community Analysis

In this study, two strains, Acinetobacter sp. XM-02 and Pseudomonas sp. XM-01, were isolated from soil samples polluted by crude oil at Bohai offshore. The former one could degrade alkane hydrocarbons (crude oil and diesel, 1:4 (v/v)) and crude oil efficiently; the latter one failed to grow on alkane hydrocarbons but could produce rhamnolipid (a biosurfactant) with glycerol as sole carbon source. Compared with pure culture, mixed culture of the two strains showed higher capability in degrading alkane hydrocarbons and crude oil of which degradation rate were increased from 89.35 and 74.32?±?4.09 to 97.41 and 87.29?±?2.41 %, respectively. In the mixed culture, Acinetobacter sp. XM-02 grew fast with sufficient carbon source and produced intermediates which were subsequently utilized for the growth of Pseudomonas sp. XM-01 and then, rhamnolipid was produced by Pseudomonas sp. XM-01. Till the end of the process, Acinetobacter sp. XM-02 was inhibited by the rapid growth of Pseudomonas sp. XM-01. In addition, alkane hydrocarbon degradation rate of the mixed culture increased by 8.06 to 97.41 % compared with 87.29 % of the pure culture. The surface tension of medium dropping from 73.2?×?10^?3 to 28.6?×?10^?3 N/m. Based on newly found cooperation between the degrader and the coworking strain, rational investigations and optimal strategies to alkane hydrocarbons biodegradation were utilized for enhancing crude oil biodegradation.     

Headspace Solid‐Phase Microextraction (HS‐SPME) for the Determination of Benzene,Toluene, Ethylbenzene,and Xylenes (BTEX) in Foundry Molding Sand

Abstract

The use of headspace solid‐phase microextraction (HS‐SPME) to determine benzene, toluene, ethylbenzene, and xylenes (BTEX) in foundry molding sand, specifically a “green sand” (clay‐bonded sand) was investigated. The BTEX extraction was conducted using a 75 µM Carboxen‐polydimethylsiloxane (CAR‐PDMS) fiber, which was suspended above 10 g of sample. The SPME fiber was desorbed in a gas chromatograph injector port (280°C for 1 min) and the analytes were characterized by mass spectrometry. The effects of extraction time and temperature, water content, and clay and bituminous coal percentage on HS‐SPME of BTEX were investigated. Because green sands contain bentonite clay and carbonaceous material such as crushed bituminous coal, a matrix effect was observed. The detection limits for BTEX were determined to be ≤0.18 ng g^?1 of green sand.     

A Screening Method for Polycyclic Aromatic Hydrocarbons Determination in Sediments by Headspace SPME with GC–FID

A screening method for polycyclic aromatic hydrocarbons (PAHs) determination in sediment using headspace solid phase microextraction (HS-SPME) with gas chromatography–flame ionization detection was developed. In order to obtain the convenient experimental conditions for HS-SPME extraction an experimental design with two steps was done. 0.2 g of sediment and 85 µm polyacrylate fibre, 80 °C and 120 min were the chosen extractions conditions. The limit of detection (LOD) was from 0.8 ng g⁻¹ (fluoranthene) to 8 ng g⁻¹ (chrysene). The relative standard deviation (RSD) was less than 7.0%. Determination of PAHs in NRC–CNRC–HS–3B reference marine sediment showed good agreement with the certified values. The method was applied in the analysis of ten river and estuary surface sediments from Gipuzkoa (North Spain). PAHs total concentration ranged from 400 to 5,500 ng g⁻¹.