Anaerobic BTEX biodegradation linked to nitrate and sulfate reduction

Effective anaerobic BTEX biodegradation was obtained under nitrate and sulfate reducing conditions by the mixed bacterial consortium that were enriched from gasoline contaminated soil. Under the conditions of using nitrate or sulfate as reducing acceptor, the degradation rates of the six tested substrates decreased with toluene>ethylbenzene>m-xylene>o-xylene>benzene>p-xylene. The higher concentrations of BTEX were toxic to the mixed cultures and led to reduce the degradation rates of BTEX. Benzene and p-xylene were more toxic than toluene and ethylbenzene. Nitrate was a more favorable electron acceptor compared to sulfate. The measured ratios between the amount of nitrate consumed and the amount of benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene degraded were 9.47, 9.26, 11.14, 12.46, 13.36 and 13.02, respectively. The measured ratios between sulfate reduction and BTEX degradation were 3.51, 4.33, 4.89, 4.81, 4.86 and 4.76, respectively, which were nearly the same to theoretical ones, and the relative error between the measured and calculated ratios was less than 10%.     

An analysis of synergistic and antagonistic behavior during BTEX removal in batch system using response surface methodology

The removal of benzene, toluene, ethylbenzene and xylene (BTEX) as quaternary mixtures were studied in batch systems using a well-defined mixed microbial culture. The synergistic and antagonistic effects of total BTEX removal (BTEXT-RE) due to the presence of mixed substrate was evaluated through experiments designed by response surface methodology (RSM). The low and high concentrations of individual BTEX were 15 and 75 mg l(-1), respectively. The results showed that, increasing the concentration of xylene increased the cumulative BTEX removal (BTEXT-RE), however the reverse occurred when benzene concentrations were increased from low to high levels. A mixed response of increasing and decreasing trend in the BTEXT-RE value was observed when either of toluene or ethylbenzene concentration was increased. When the concentrations of individual BTEX compounds were 30 mg l(-1), the BTEXT-RE was about 58%. Complete BTEXT-RE was achieved at optimal BTEX concentrations of 48.1, 45.6, 49.3 and 56.6 mg l(-1). The RSM approach was found efficient in explaining the main, squared and interaction effects among individual BTEX concentrations on the BTEXT-RE in a more statistically meaningful way.     

CS_2萃取毛细柱气相色谱法测定焦化厂区空气中的苯

活性炭富集采样,CS2萃取,毛细柱分离,FID检测,测定焦化厂区空气中苯。在选择的色谱条件下,可以将苯系物样品中的苯、甲苯、乙苯、间、对二甲苯、邻二甲苯、苯乙烯等色谱峰分开,从而实现各组分的单独测定。实验表明,CS2对苯的萃取效果可靠。充分利用标准物质,探讨了该方法的准确度和灵敏度,在较宽的浓度范围内(0.33-50.7μg/mL),可以对焦化厂区空气中的苯进行直接测定,为管理打下基础。     

Performance of a reactor containing denitrifying immobilized biomass in removing ethanol and aromatic hydrocarbons (BTEX) in a short operating period

A horizontal-flow anaerobic immobilized biomass reactor (HAIB) containing denitrifying biomass was evaluated with respect to its ability to remove, separately and in a short operating period (30 days), organic matter, nitrate, and the hydrocarbons benzene (41.4 mg L-1), toluene (27.8 mg L-1), ethylbenzene (31.1 mg L-1), o-xylene (28.5 mg L-1), m-xylene (28.4 mg L-1) and p-xylene (32.1 mg L-1). The purified culture, which was grown in the presence of the specific hydrocarbon, was used as the source of cells to be immobilized in the polyurethane foam. After 30 days of operation, the foam was removed and a new immobilized biomass was grown in the presence of another hydrocarbon. The average hydrocarbon removal efficiency attained was 97%. The organic matter, especially ethanol, was removed with an average efficiency of 83% at a mean influent concentration of 1185.0 mg L-1. A concomitant removal of 97% of nitrate was observed for a mean influent concentration of 423.4 mg L-1. The independent removal of each hydrocarbon demonstrated that these contaminants can be biodegraded separately, without the need for a compound to be the primary substrate for the degradation of another. This study proposes the application of the system for treatment of areas contaminated with these compounds, with substitution and formation of a biofilm in a 30-day period.     

Enhancing sensitivity in headspace-mass spectrometric determination of BTEX in drinking water

A way to extract useful chemical information from the volatile profile provided by a headspace-mass spectrometer (HS-MS) is developed in order to improve sensitivity in HS-MS analysis. The methodology is based on the selection of a narrow window in the volatile profile where the signal-to-noise ratio was maximal by combining the data acquisition time and scan rate. To test this approach, benzene, toluene, ethylbenzene, and p-xylene (BTEX) as well as their mixtures were quantified in drinking waters. Individual hydrocarbons were determined between 1 and 30 microg/L (mean RSD, 4.0% for 10 microg/L) while mixtures were quantified at a microgram per liter level by using the partial least-squares multivariate algorithm with a relative standard prediction error of under 3.5%. These results indicate that the method proposed is useful as a sensitive and selective tool for the determination of BTEX and surpasses other reported HS-MS alternatives. In addition, the proposed methodology can be extended to others that insert analytes from a sample directly into a MS, such as membrane introduction mass spectrometry among others.     

The effect of surfactants on the distribution of organic compounds in the soil solid/water system

The efficiency of soil remediation by surfactant washing was evaluated via the measured distribution coefficients of a number of nonpolar compounds in several soil-water mixtures. The studied compounds (contaminants) are BTEX (benzene, toluene, ethylbenzene, and p-xylene) and three chlorinated pesticides (lindane, alpha-BHC, and heptachlor epoxide), which span several orders of magnitude in water solubility (S(w)). A peat, and two natural soils were used that comprise a wide range in soil organic matter (SOM) content. The surfactants tested included cationic, anionic and nonionic types, with concentrations up to five to six times the critical micelle concentration (CMC). The K(d)(*)/K(d), values were used to evaluate the remediation efficiency under various operation conditions. For relatively water soluble BTEX compounds, the surfactant adsorption on the soil surface is the deciding factor on contaminant desorption from soil. For the less-soluble pesticides, surfactant micelles in solution influence the contaminant desorption more. The contaminants partitioning to SOM or adsorbed surfactants lowers the desorption efficiency. Anionic surfactants are found to be a better choice on soil remediation because they do not form admicelle on soil surface that enhances the SOM content. Cationic surfactant, which adsorb onto soil surfaces, leads to poor remediation efficiency. An improper selection of surfactant would result in inefficiency in soil remediation by surfactant washing.     

Permeation of aromatic solvent mixtures through nitrile protective gloves

The permeation of binary and ternary mixtures of benzene, toluene, ethyl benzene and p-xylene through nitrile gloves were investigated using the ASTM F739 test cell. The more slowly permeating component of a mixture was accelerated to have a shorter breakthrough time than its pure form. The larger differences in solubility parameter between a solvent mixture and glove resulted in a lower permeation rate. Solubility parameter theory provides a potential approach to interpret the changes of permeation properties for BTEX mixtures through nitrile gloves. Using a one-dimensional diffusion model based on Fick's law, the permeation concentrations of ASTM F739 experiments were appropriately simulated by the estimated diffusion coefficient and solubility. This study will be a fundamental work for the risk assessment of the potential dermal exposure of workers wearing protective gloves.     

Removal of o-xylene using biofilter inoculated with Rhodococcus sp. BTO62

Rhodococcus sp. BTO62 was isolated from activated sludge from a wastewater treatment plant as an o-xylene-degrading microorganism. BOT62 degraded not only o-xylene, but also benzene, toluene, ethylbenzene, m- and p-xylenes and styrene (BTEXS). A laboratory scale biofilter packed with Biosol as packing material, which is made from foamed waste glass mixed with corrugated cardboard, was inoculated with strain BTO62 and operated to remove relatively high loading of o-xylene at different space velocities under non-sterile and sterile conditions. The o-xylene elimination capacity to maintain more than 90% removal efficiency was 41g/m3/h under sterile condition, but it enhanced to 160g/m3/h under non-sterile condition. This indicates possibilities of the role of other contaminants for degradation of o-xylene and the degradation of intermediate products of o-xylene by contaminants. Quick recovery of o-xylene degradation was observed after shutdown of o-xylene gas supply and mineral medium circulation for 10-30 days.     

Silicone sensing phase for detection of aromatic hydrocarbons in water employing near-infrared spectroscopy

The use of silicone for detection of aromatic hydrocarbons in water using near-infrared spectroscopy is proposed. A sensing phase of poly(dimethylsiloxane) (PDMS) was prepared, and a rod of this material was adapted to a transflectance probe for measurements from 850 to 1800 nm. Deionized water samples contaminated separately with known amounts of benzene, toluene, ethylbenzene, and m-xylene were used for evaluation of the PDMS sensing phase, and measurements were made in a closed reactor with constant stirring. Equilibrium states were obtained after 90, 180, 360, and 405 min for benzene, toluene, ethylbenzene, and m-xylene, respectively. The PDMS sensing phase showed a reversible response, presenting linear response ranges up to 360, 290, 100, and 80 mg L(-1), with detection limits of 8.0, 7.0, 2.6, and 3.0 mg L(-1) for benzene, toluene, ethylbenzene, and m-xylene, respectively. Reference spectra obtained with different rods showed a relative standard deviation of 0.5%, indicating repeatability in the sensing phase preparation. A relative standard deviation of 6.7% was obtained for measurements performed with six different rods, using a 52 mg L(-1) toluene aqueous solution. The sensing phase was evaluated for identification of sources of contamination of water in simulated studies, employing Brazilian gasoline type A (without ethanol), gasoline type C (with 25% of anhydrous ethanol), and diesel fuel. Principal component analysis was able to classify the water in distinct groups, contaminated by gasoline A, gasoline C, or diesel fuel.     

High-speed gas chromatography-multiplex coherent Raman analysis of BTEX

Gas chromatography-multiplex coherent Raman (GC-MCR) is a new tandem technique that can be used for the high-speed analysis of volatile mixtures. BTEX serves as a useful and challenging test sample because of the similarity in boiling point and spectroscopic properties of its constituents. The ability to spectroscopically resolve isomers (e.g., m-xylene and p-xylene) allows GC-MCR to sacrifice chromatographic resolution for speed. The result is the analysis of BTEX in less than 5 min, which is relatively fast compared with other tandem GC techniques.     

Organic compound distribution between nonionic surfactant solution and natural solids: applicability of a solution property parameter

A solution property parameter phi was defined to examine the distribution characteristics of organic compounds between the solids and four nonionic surfactant solutions. The studied compounds consisted of BTEX (benzene, toluene, ethylbenzene, and p-xylene) and chlorinated pesticides (lindane, alpha-BHC, and heptachlor epoxide), which span several orders of magnitude in terms of water solubility (Sw). The solid samples were composed of a very low organic matter clay (Ca-montmorillonite), and a high organic matter natural soil (Shamou Mountain soil). The surfactants tested included two alkyl chain surfactants and two containing aromatic group surfactants with added concentrations both below and above their critical micelle concentration (CMC). By observing the Kom or Ksf variation, the result indicates, besides the Sw of the organic compounds, the distribution coefficient is regarded as a function of the soil organic matter (SOM) constituents, and the chemical structure of the organic compounds. Also, it can be found the greater phi values represent the higher releasing ratios of the organic compounds from the contaminated soil to groundwater. For the relatively higher Sw compounds, such as BTEX, all of the phi values are close to 1. The phi values for the relatively lower Sw compounds are far greater than 1, and increase with the increasing affinity of the compounds to the surfactants.     

Headspace solvent microextraction.

A hanging microliter drop of 1-octanol is shown to be an excellent preconcentration medium for headspace analysis of volatile compounds in an aqueous matrix by gas chromatography (GC) or gas chromatography/mass spectrometry (GC/MS). Model compounds benzene, toluene, ethylbenzene, and o-xylene (BTEX) are conveniently and rapidly preconcentrated in the microdrop. An internal standard, decane, is present in the organic extracting solvent, and linear calibration curves of relative peak area versus aqueous concentration are obtained for the four model compounds. Detailed kinetic studies reveal that the overall rate of mass transfer is limited by both the aqueous-phase stirring rate and the degree of convection within the organic phase. The very low vapor pressure of 1-octanol results in minimal evaporation of the microdrop during the extraction time. This system represents an inexpensive, convenient, and precise sample cleanup and preconcentration method for the determination of volatile organic compounds at trace levels.     

Retention behavior of phenols, anilines, and alkylbenzenes in liquid chromatographic separations using subcritical water as the mobile phase

The unique characteristic of subcritical water is its widely tunable physical properties. For example, the polarity (measured by dielectric constant) of water is significantly decreased by raising water temperature. At temperatures of 200-250 °C (under moderate pressure to keep water in the liquid state), the polarity of pure water is similar to that of pure methanol or acetonitrile at ambient conditions. Therefore, pure subcritical water may be able to serve as the mobile phase for reversed-phase separations. To investigate the retention behavior in subcritical water separation, the retention factors of BTEX (benzene, toluene, ethylbenzene, and m-xylene), phenol, aniline, and their derivatives have been determined using subcritical water, methanol/water, and acetonitrile/water systems. Subcritical water separations were also performed using alumina, silica-bonded C18, and poly(styrene-divinylbenzene) columns to study the influence of the stationary phase on analyte retention under subcritical water conditions.     

HS-GC/MS法检测食品塑料包装中的挥发性有机物

采用顶空-气相色谱/质谱联用技术检测了两种食品用塑料包装袋中可能残留的挥发性有机物:苯、乙苯、邻二甲苯、间/对二甲苯、异丙醇、乙酸乙酯、乙酸丁酯.结果证明,所建立的方法分离效果理想,线性关系良好,线性相关系数均大于0.999,检出限均达到10-3数量级,能够满足实际分析的要求.     

Microfluidic device for airborne BTEX detection

We fabricated a microfluidic device for the optical detection of airborne benzene, toluene, ethylbenzene and xylenes (BTEX). The device consists of concentration and detection cells formed of 3 cm x 1 cm Pyrex plates. The concentration cell is composed of an adsorbent to concentrate the BTEX gases and a thin-film heater todesorb the concentrated gases from the adsorbent thermally. The collected gases are introduced into the detection cell, which is connected to optical fibers, to measure their absorption spectra. We optimized the device's operating conditions by studying the thermal characteristics of the concentration cell and the time profile of the gas concentration flowing in the detection cell. We used the device under optimized operating conditions to detect toluene gas as a typical example BTEX. The gas concentration amplification rate was approximately 2 orders of magnitude, and we successfully measured parts-per-million levels of toluene gas with this device.     

Influence of ethanol-gasoline blended fuel on emission characteristics from a four-stroke motorcycle engine

Emission characteristics from a four-stroke motorcycle engine using 10% (v/v) ethanol-gasoline blended fuel (E10) were investigated at different driving modes on the chassis dynamometers. The results indicate that CO and HC emissions in the engine exhaust are lower with the operation of E10 as compared to the use of unleaded gasoline, whereas the effect of ethanol on NO(X) emission is not significant. Furthermore, species of both unburned hydrocarbons and their ramifications were analyzed by the combination of gas chromatography/mass spectrometry (GC/MS) and gas chromatography/flame ionization detection (GC/FID). This analysis shows that aromatic compounds (benzene, toluene, xylene isomers (o-xylene, m-xylene and p-xylene), ethyltoluene isomers (o-ethyltoluene, m-ethyltoluene and p-ethyltoluene) and trimethylbenzene isomers (1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene)) and fatty group ones (ethylene, methane, acetaldehyde, ethanol, butene, pentane and hexane) are major compounds in motorcycle engine exhaust. It is found that the E10-fueled motorcycle engine produces more ethylene, acetaldehyde and ethanol emissions than unleaded gasoline engine does. The no significant reduction of aromatics is observed in the case of ethanol-gasoline blended fuel. The ethanol-gasoline blended fuel can somewhat improve emissions of the rest species.     

Adsorption of BTEX from aqueous solution by macroreticular resins

Theoretical and experimental investigations were conducted on the adsorption of benzene, toluene, ethylbenzene and xylene (BTEX) by macroreticular resins. A mass transfer model based on the squared-driving force principle is presented for describing the BTEX transfer between the aqueous and solid phases. Also proposed is a theoretical model for describing the BTEX breakthrough curves of the adsorption column. While the mass transfer model involves only an overall mass transfer coefficient, the column adsorption model has two model parameters. Those parameters are conveniently estimated using the observed mass transfer and breakthrough data. The predictions using the proposed models were found to compare well with the experimental data of batch and column BTEX adsorption tests.     

Calibration for on-site analysis of hydrocarbons in aqueous and gaseous samples using solid-phase microextraction

Rapid sampling and sample preparation methodology was investigated using adsorptive poly(dimethylsiloxane)/divinylbenzene and Carboxen/poly(dimethylsiloxane) solid-phase microextraction (SPME) fiber coatings and volatile aromatic hydrocarbons (BTEX: benzene, toluene, ethylbenzene, and o-xylene). A flow-through system was used to generate a standard aqueous solution of BTEX as model sample with known linear velocity. Parameters that affect the extraction process, including sampling time, concentration, water velocity, and temperature, were investigated. Very short sampling times from 10 s and sorbents with strong affinity and large capacity were used to ensure the effect of '"zero sink" and to calibrate the extraction process in the initial linear extraction region. Several different concentrations were investigated, and it was found that mass uptake changes with concentration linearly. The increase of water velocity increases mass uptake, though the increase is not linear. Temperature does not affect mass uptake significantly under typical field sampling conditions. To further accurately describe rapid SPME analysis of aqueous samples, a new model translated from heat transfer to a circular cylinder in cross-flow was used. An empirical correlation to this model was used to predict the mass-transfer coefficient. Findings indicate that predicted mass uptake compares well with experimental mass uptake. The new model was tested for rapid air sampling, and it was found that this new model also predicted rapid air sampling accurately. Findings presented in this study extend the existing fundamental knowledge related to rapid sampling/sample preparation with SPME.     

Development and application of a needle trap device for time-weighted average diffusive sampling

A simple, cost-effective analysis combining solventless extraction, thermal desorption, and determination of volatile organic compounds (VOCs) was developed and validated. A needle trap device (NTD) packed with the sorbent Carboxen1000 was used as a time-weighted average (TWA) diffusive sampler to collect target compounds by molecular diffusion and adsorption to the packed sorbent. This process can be described with derivations of Fick's first law of diffusion, which expresses the relation between the TWA concentrations to which the passive sampler is exposed and the mass of analytes adsorbed to the packed sorbent in the sampler. The effects of experimental factors such as temperature, pressure, humidity, and face velocity were taken into account in applying diffusive sampling under nonideal conditions. This study demonstrates that NTD is effective for air analysis of benzene, toluene, ethylbenzene, and o-xylene (BTEX), due to the good adsorption/desorption quality of Carboxen 1000 and to the special geometric shape of the needle with a small cross section avoiding the need for calibration. Storage tests showed good storage stability for BTEX. Verification of the theoretical model showed good agreement between theoretical and experimental sampling rates. Method validation done against NIOSH method 1501, SPME, and NTD active sampling revealed good agreement between those methods. Automated NTD sample introduction to a gas chromatograph facilitates the use of this technology for industrial hygiene applications.     

Ambient BTEX and MTBE in the neighborhoods of different industrial parks in Southern Taiwan

This study assessed the concentrations of five volatile organic compounds (VOCs), including BTEX (the acronym for benzene, toluene, ethylbenzene, and xylene) and methyl tertiary-butyl ether (MTBE), in six different industrial park neighborhoods in southern Taiwan, including the Nei-Pu, Ping-Tung, Ping-Nan, Ren-Wu, Lin-Yuan and Nan-Zi industrial parks. The concentrations of MTBE and BTEX ranged from undetectable to 145.6 microg/m3. Average MTBE-BTEX ratios of Nei-Pu, Ping-Tung, Ping-Nan, Ren-Wu, Lin-Yuan and Nan-Zi were (13.4:3.6:4.7:1.0:7.4), (2.9:1.0:1.7:1.3:2.9), (3.0:1.0:2.7:1.0:2.7), (5.2:1.0:8.6:1.7:4.9), (3.1:3.1:2.8:1.0:3.3) and (4.3:1.2:3.6:1.0:3.8), respectively. Moreover, average T/B ratios in Nei-Pu, Ping-Tung, Ping-Nan, Ren-Wu, Lin-Yuan and Nan-Zi were 1.3, 1.7, 2.6, 8.6, 0.9 and 2.9, respectively. High T/B ratio (8.6) in the neighborhood of the Ren-Wu industrial park suggested that the emission of large additional sources of toluene from this industrial park, or the existence of major differences in the auxiliary fuels used. Average X/E ratios in Nei-Pu, Ping-Tung, Ping-Nan, Ren-Wu, Lin-Yuan and Nan-Zi were 7.4, 2.2, 2.7, 2.9, 3.3 and 3.8, respectively. The lower X/E ratio (2.2) in the Ping-Tung neighborhood compared to elsewhere indicates an aged air parcel. Furthermore, principal component analysis also confirmed that the dominant influences in the six different industrial park neighborhoods were related to the emissions of MTBE, benzene and toluene.