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1.
Lee MR  Chang CM  Dou J 《Chemosphere》2007,69(9):1381-1387
A trace analytical method of benzene, toluene, ethylbenzene and xylenes (BTEX) in water has been developed by using headspace solid-phase microextraction (HS-SPME) coupled to cryo-trap gas chromatography-mass spectrometry (GC-MS). The chromatographic peak shape for BTEX was improved by using cryo-trap equipment. The HS-SPME experimental procedures to extract BTEX from water were optimized with a 75 microm carboxen/polydimethylsiloxane (CAR/PDMS)-coated fiber at a sodium chloride concentration of 267 g l(-1), extraction for 15 min at 25 degrees C and desorption at 290 degrees C for 2 min. Good linearity was verified in a range of 0.0001-50 microg l(-1) for each analyte (r(2)=0.996-0.999). The limits of detection (LODs) of BTEX in water reached at sub-ng l(-1) levels. LODs of benzene, toluene, ethylbenzene, m/p-xylene and o-xylene were 0.04, 0.02, 0.05, 0.01 and 0.02 ng l(-1), respectively. The proposed analytical method was successfully used for the quantification of trace BTEX in ground water. The results indicate that HS-SPME coupled to cryo-trap GC-MS is an effective tool for analysis of BTEX in water samples at the sub-ng l(-1) level.  相似文献   

2.
Burke ER  Holden AJ  Shaw IC 《Chemosphere》2003,50(4):529-535
A method has been developed for the analysis of organochlorine pesticides in human milk using solvent extraction, Florisil solid phase extraction clean-up and analysis by gas chromatography with an electron capture detector. The recovery of analytes from spiked milk samples was in the range 53 +/- 1% to 109 +/- 7% (n = 9). A small number of samples were obtained from women in a rural and an urban area of Indonesia and analysed using the developed method. The results are reported on a milk fat basis. All samples contained detectable residues of p,p'-DDT (urban mean 0.11 +/- 0.18 mgkg(-1) (n = 5), rural mean 0.07 +/- 0.03 mg kg(-1) (n = 5)) and p,p'-DDE (urban mean 0.05 +/- 0.04 m kg(-1) (n = 5), rural mean 0.76 +/- 1.46 mg kg(-1) (n = 5)). Residues of HCB, betaHCH, alpha-endosulfan and dieldrin were also detected in some samples. There was no significant difference (at the 95% confidence level) in levels of pesticides between urban and rural areas. The levels of organochlorine pesticides in milk from Indonesian women were lower than those reported from Indonesian women exposed to DDT through malaria eradication schemes and were similar to levels reported from UK and Japan.  相似文献   

3.
Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta13C is associated with increased delta15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.  相似文献   

4.
This study evaluates the performance of Model 3300 Ogawa Passive Nitrogen Dioxide (NO2) Samplers and 3M 3520 Organic Vapor Monitors (OVMs) by comparing integrated passive sampling concentrations to averaged hourly NO2 and volatile organic compound (VOC) measurements at two sites in El Paso, TX. Sampling periods were three time intervals (3-day weekend, 4-day weekday, and 7-day weekly) for three consecutive weeks. OVM concentrations were corrected for ambient pressure to account for higher elevation. Precise results (< 5% relative standard deviation, RSD) were found for NO2 measurements from collocated Ogawa samplers. Reproducibility was lower from duplicate OVMs for BTEX (benzene, toluene, ethylbenzene, and xylene isomers) VOCs (> or = 77% RSD for 2-day samples) with better precision for longer sampling periods. Comparison of Ogawa NO2 samplers with chemiluminescence measurements averaged over the same time period suggested potential calibration problems with the chemiluminescence analyzer. For BTEX species, generally good agreement was obtained between OVMs and automated-gas chromatograph (auto-GC) measurements. The OVMs successfully tracked increasing levels of VOCs recorded by the auto-GCs. However, except for toluene, OVM BTEX measurements generally exceeded their continuous counterparts with a mean bias of 5-10%. Although interpretation of the study results was limited due to small sample sizes, diffusion barrier influences caused by shelters that housed OVMs and differences in sampling heights between OVMs and auto-GC inlet may explain the overestimation.  相似文献   

5.
Modified pressurised hot water is used for the development of a high pressure liquid-liquid extraction method for the decontamination of used industrial oils from inorganic non-metal species (chlorine, fluorine and sulphur). The oils were subjected to dynamic extraction with water modified with 5% v/v HNO3 at 200 degrees C as extractant. Under these working conditions the analytes were transferred to the aqueous phase. Spontaneous separation of the two immiscible liquid phases (the used oil and extract) takes place in the collection flask after extraction. The treated and untreated oil samples were oxidised and the chloride, fluoride and sulphate thus formed were determined by ion-chromatography. The method was applied to four oil samples from different locations in Spain. A residence time of approximately =10 min provided oil samples from which 88.3%, 89.4% and 89.4% of chloride, fluoride and sulphate, respectively, have been removed with respect to the initial concentration of each analyte in the oil. The repeatability, expressed as relative standard deviation (RSD), was of 11.9%, 13.7% and 7.2% for Cl(-), F(-) and SO4(2-), respectively; whilst the within-laboratory reproducibility yielded RSDs of 6.2%, 7.9% and 6.2% for the same analytes. The proposed approach has proved to be efficient, simple, easily transferable to industrial scale, cheap, fast and environmentally friendly.  相似文献   

6.
In this paper, the treatment of real groundwater samples contaminated with gasoline components, such as benzene, toluene, ethylbenzene, and xylene (BTEX), methyl tert-butyl ether (MTBE), tert-butyl alcohol (TBA), and other gasoline constituents in terms of total petroleum hydrocarbons as gasoline (TPHg) by an ozone/UV process was investigated. The treatment was conducted in a semi-batch reactor under different experimental conditions by varying ozone gas dosage and incident UV light intensity. The groundwater samples contained BTEX compounds, MTBE, TBA, and TPHg in the ranges of 5-10000, 3000-5500, 80-1400, and 2400-20000mugl(-1), respectively. The ozone/UV process was very effective compared to ozonation in the removal of the gasoline components from the groundwater samples. For the various gasoline constituents, more than 99% removal efficiency was achieved for the ozone/UV process and the removal efficiency for ozonation was as low as 27%. The net ozone consumed per mol of organic carbon (from BTEX, MTBE, and TBA) oxidized varied in the range of 5-60 for different types of groundwater samples treated by the ozone/UV process. In ozonation experiments, it was observed that the presence of sufficient amount of iron in groundwater samples improved the removal of BTEX, MTBE, TBA, and TPHg.  相似文献   

7.
In this study, a version of the "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method was modified to use ethyl acetate (EtOAc) rather than acetonitrile (MeCN) for extraction in the determination of multiple pesticide residues in fruits and vegetables. EtOAc is better suited than MeCN for gas chromatographic (GC) analysis with electron capture detection (ECD) and nitrogen-phosphorus detection (NPD). The method entailed extraction of 30 g chopped sample plus 5 g NaHCO(3) and 30 g anhydrous Na(2)SO(4) with 60 mL EtOAc using a probe blender. After a centrifugation step, removal of residual water and cleanup were performed using dispersive solid-phase extraction (dispersive-SPE) with MgSO(4) and primary secondary amine (PSA) sorbent. (14)C-labeled chlorpyrifos with liquid scintillation counting was used to assist in optimizing and characterizing the method, and GC-ECD and GC-NPD were used for analysis of 24 selected pesticides. The method was validated using tomato, apple and frozen green bean matrices spiked at 0.05, 0.5, and 5 mg/kg. For 22 of the analytes, recoveries averaged 93% for all three commodities over the validation range with a relative standard deviation of 10% (n = 1182). Lower recoveries of dichlorvos were obtained with the method and iprodione determination was compromised in the green beans by an interfering peak. Typical limits of detection were 0.005-0.01 mg/kg with the method.  相似文献   

8.
Chen HC  Kuo HW  Ding WH 《Chemosphere》2009,74(4):508-514
Two complementary LC-MS ionization methods, electrospray (ESI) and atmospheric pressure photoionization (APPI), have been optimized to determine three natural estrogenic compounds (estrone, 17beta-estradiol and estriol) and two synthetic estrogenic compounds (17alpha-ethynylestradiol and diethylstilbestrol) in the influent and effluent of wastewater treatment plants (WWTPs). The wastewater samples were first subjected to solid-phase extraction coupled with desalting extraction to remove matrix interference. The analytes were then detected using liquid chromatography-tandem mass spectrometry (LC-MS-MS) with ESI and dopant-assisted (DA) APPI to evaluate the ion suppression effect and to complement the detection and quantification of estrogenic compounds in complex wastewater samples. The average ion suppression factors for the extracts of the WWTP influent analyzed using ESI and APPI were 52+/-5% and 27+/-7%, respectively. The sensitivity and ionization efficiency of the LC-ESI-MS-MS system decreased dramatically when a complex matrix was present in the WWTP influent sample. Estrogenic compounds could be detected in the WWTP influent and effluent samples at concentrations below the parts-per-billion level. The lower detection limits obtained when using ESI and the higher matrix tolerance of the APPI method allowed the complete quantification of estrogenic compounds in very complex samples in a complementary manner.  相似文献   

9.
A pilot study was conducted to determine the feasibility of using constructed treatment wetlands to remediate recovered groundwater from the subsurface of a former refinery site. The pilot system consisted of four subsurface flow treatment cells operated in an upward vertical flow mode and equipped with subsurface aeration lines. The treatment system showed minimal capability for methyl-tert-butyl ether removal, but did effectively remove total petroleum hydrocarbons-deisel range organics and total benzene, toluene, ethylbenzene, and o-, m-, and p-xylenes (total BTEX). Effluent benzene concentrations were less than 0.05 mg/L in 70% of the samples from a treatment cell using subsurface aeration and a wetland sod amendment. Based on 1 year of operating data, cumulative mass removal approached 80% for benzene and 88% for total BTEX.  相似文献   

10.
Bossio JP  Harry J  Kinney CA 《Chemosphere》2008,70(5):858-864
The objective of this research was the development, optimization, and demonstration of an ultrasonic assisted extraction (UAE) based method for organic anthropogenic waste indicators (AWIs) with a range of physicochemical properties from soil and sediment samples. The optimized method was designed to be cost effective compared to existing extraction methods, which may require large quantities of consumables, produce substantial volumes of organic waste, or require costly instrumentation or equipment. Reagent grade sand, soil collected from the native grassland in proximity to Eastern Washington University (EWU), and sediment samples collected from the Spokane river were used as sample matrices during method development. These matrices were fortified with eight AWIs of varying chemical properties that are representative of a variety of household, industrial, and agricultural sources. The recoveries of the AWIs spiked onto these matrices were determined in the extracts using gas chromatography/mass spectrometry (GC/MS). These values reflect the efficiency of the method for extraction of these analytes from representative environmental matrices. Recoveries ranged from 46.1% to 110% in the fortified soil and from 49.2% to 118.6% in the fortified sediment samples, which is comparable with existing methods for the study analytes. The optimized method was then used to quantify AWIs in a biosolid-amended soil. Indole and p-cresol were detected in the biosolid-amended soil.  相似文献   

11.
A method has been developed and validated in order to assess the occurrence of the alkylphenols tert-octylphenol and the isomers of technical nonylphenol as well as bisphenol A in gasphase and aerosol samples of a remote area. Gasphase samples were adsorbed to XAD2 resin, aerosol samples were taken on glass fiber filters. After ultrasonic extraction, clean-up by column chromatography and silylation of the analytes, ten nonylphenol peaks were quantified separately using a GC-MSD-SIM method. The absolute limits of detection and determination are in the range of a few pg per compound, which is a prerequisite for the quantification of the analytes in relatively unpolluted air. The precision of the whole analytical method is in the range of 1-17% and the recoveries range from 57% to 80%. Problems were encountered during method development due to the tendency of the analytes to sorb to glass surfaces. Silanisation of glassware was crucial to achieve acceptable recoveries. The widespread use of the analytes in plastic resins resulted in sample contamination. For this reason a careful choice of sampling material was necessary. Measured concentrations in gasphase samples (lower nanogram per m3 range) and aerosol samples (upper picogram per m3 range) are one to three orders of magnitude below already published concentrations.  相似文献   

12.
The rate and extent of biodegradation of benzene, toluene, ethylbenzene and xylenes (BTEX) in ground-water was studied in samples from a contaminated site which contained total BTEX concentrations of up to 20 000 microg litre(-1). All compounds were rapidly degraded under natural aerobic conditions. Elevation of incubation temperature, supply of organic nutrients or addition of inorganic fertiliser did not increase the rate or extent of biodegradation and it appeared that oxygen supply was the factor limiting BTEX degradation at this site. Attempts to increase the dissolved oxygen concentration in the ground-water by the addition of hydrogen peroxide to give a final concentration of 200 mg litre(-1) resulted in the complete inhibition of biodegradation. No biodegradation occurred under anaerobic conditions except when nitrate was provided as a terminal electron acceptor for microbial respiration. Under denitrifying conditions there was apparent biodegradation of benzene, toluene, ethyl-benzene, m-xylene and p-xylene but o-xylene was not degraded. Degradation under denitrifying conditions occurred at a much slower rate than under oxygenated conditions.  相似文献   

13.
In this study, gaseous benzene, toluene, ethylbenzene, and o-xylene (BTEX) were extracted by passive needle trap samplers (NTS) using divinylbenzene (DVB) particles (mesh sizes 60–80, 80–100, and 100–120, respectively) as packed sorbents. An aspirating pump measured sampling flow rates of NTS, and the relations between BTEX mass and sampling flow rates were sufficient to maintain the extraction performance of these self-designed DVB-NTS. Furthermore, this investigation compared the extraction efficiency of NTS with that of the 100-µm polydimethylsiloxane solid-phase microextration (PDMS SPME) fiber when applied to sample heating products from electric-vaporization anti-mosquito mats, and the experimental results indicated that NTS effectiveness increased with decreasing adsorbent particle diameter. Substantially less mass of gaseous BTEX was extracted using 100-µm PDMS SPME fiber than with NTS of 100–120 mesh DVB for 60-min TWA sampling of anti-mosquito mats. The 100–120 mesh DVB-NTS primarily adsorbed 4.2 ng acetone, 13.3 ng dichloromethane, and 4.5–25.3 ng C10–C12 alkanes.
Implications: The needle trap sampler (NTS) has been evaluated to be a device for sampling heating products from electric-vaporization anti-mosquito mats. Based on the experimental results, this investigation assessed NTS as suitable for occupational and environmental health applications.  相似文献   

14.
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.  相似文献   

15.
The effect of dissolved organic matter (DOM) and oil on the removal of the water-soluble compounds benzene, toluene, ethylbenzene, and xylene isomers (BTEX) by two low-cost biosorbents Macrocystis pyrifera and Ulva expansa) was evaluated. DOM decreased the adsorption capacity of toluene, ethylbenzene, and xylenes of the two biosorbents. In contrast, the removal of benzene increased under the same conditions in single and multi-solute systems: this effect was dominant in U. expansa biomass treatments. In the presence of DOM and oil in solutions, the removal of BTEX notoriously increased, being oil that contributed the most. Solubility and hydrophobicity of pollutants played a key role in the adsorption process. The attractions between BTEX molecules and biosorbents were governed by π–π and hydrophobic interactions. Affinities of biosorbents for BTEX were mainly in the order of X > E > T > B. The Langmuir and Sips equations adjusted the adsorption isotherms for BTEX biosorption in deionized and natural water samples, but in the case of oily systems, the Freundlich equation seemed to have a better fit. The biosorption processes followed a pseudo-second-order rate in all the cases.  相似文献   

16.
Okuda T  Naoi D  Tenmoku M  Tanaka S  He K  Ma Y  Yang F  Lei Y  Jia Y  Zhang D 《Chemosphere》2006,65(3):427-435
We developed a useful analytical method for the determination of polycyclic aromatic hydrocarbons (PAH) concentrations in the aerosol of China. We used an accelerated solvent extraction (ASE) method for the extraction of PAHs from the aerosol samples, in order to reduce the extraction time and the solvent volume used. The optimum purification method was developed, with aminopropylsilane chemically-bonded stationary-phase column chromatography, in order to remove many co-extractives which cannot be removed by conventional purification methods using silica-gel column chromatography. HPLC/fluorescence detection (FLD) was adopted as the analytical method, because it has very high sensitivity to PAH and it is easy to install, operate, and maintain as compared with GC/MS. With the analytical method developed in this study, the recovery and precision (RSD) for most of the PAHs ranged from 75% to 129% and from 2.8% to 22.7%, respectively. The concentrations of PAHs in the aerosol samples collected from October 2003 to April 2005 in Beijing, China were determined using the newly developed method. SigmaPAHs, which is the sum of the concentrations of all detected PAHs, was 177.8 +/- 239.9 ng m(-3) (n = 64). The SigmaPAHs concentration in the heating season (305.1 +/- 279.0 ng m(-3), n = 33) was 7.2 times higher than that in the non-heating season (42.3 +/- 32.0 ng m(-3), n = 31). These strong seasonal variations in atmospheric PAH concentration are possibly due to coal combustion for residential heating in winter.  相似文献   

17.
A two-phase partitioning bioreactor (TPPB) consisting of an aqueous phase containing a bacterial consortium and a polymeric phase of silicone rubber pellets (solid volume fraction 0.1) was used to treat a gaseous waste stream containing benzene, toluene, ethylbenzene and o-xylene (BTEX). The function of the solid polymer phase was to absorb/desorb the gaseous volatile organic compounds providing a buffering effect to protect the cells from high transient loadings and to sequester the BTEX for subsequent degradation. The TPPB was subjected to high and fluctuating inlet loadings of BTEX in the form of 4h step changes of 2, 4, 6 and 10 times the nominal inlet loading of 60 gm(-3) h(-1) total BTEX in approximately equal amounts, and removal efficiencies and elimination capacities were determined. It was found that overall removal efficiencies of greater than 95% can be achieved while obtaining overall elimination capacities of up to 282 gm(-3) h(-1) during transient operation and TPPB operation succumbs to toxic substrate levels between step changes of 6 and 10 times the nominal loading value (360-600 gm(-3) h(-1)). BTEX concentrations in the aqueous phase and the polymer phase of the TPPB were monitored throughout the imposed step changes to determine the extent to which the sequestering phase can buffer the aqueous phase from BTEX. With the polymer phase comprising only 10% of the total working volume of the reactor, the polymer beads accounted for up to 93%, 91% and 70% of the total BTEX present in the working volume for step changes of 2, 4 and 6 times the nominal loading, respectively.  相似文献   

18.
Urban roadside levels of benzene, toluene, ethylbenzene and xylenes (BTEX) were investigated in three typical cities (Guangzhou, Macau and Nanhai) in the Pearl River Delta Region of south China. Air samples were collected at typical ground level microenvironments by multi-bed adsorbent tubes. The BTEX concentrations were determined by thermal desorption–gas chromatography–mass selective detector (TD–GC–MSD) technique. The mean concentrations of benzene, toluene, ethylbenzene and xylenes were, respectively, 51.5, 77.3, 17.8 and 81.6 μg/m3 in Guangzhou, 34.9, 85.9, 24.1, 95.6 μg/m3 in Macau, and 20.0, 39.1, 3.0 and 14.2 μg/m3 in Nanhai. The relative concentration distribution pattern and mutual correlation analysis indicated that in Macau BTEX were predominantly traffic-related while in Guangzhou benzene had sources other than vehicle emission. In Nanhai, both benzene and toluene had different sources other than vehicle emission. The samples collected from Guangzhou showed that BTEX had significant higher concentrations in November than those in July.  相似文献   

19.
The system performance of a trickle bed biofilter for treating single and mixed benzene, toluene, ethylbenzene, and o-xylene (BTEX) vapors from waste gases was investigated under different gas flow rates and influent BTEX concentrations. When a single substrate was fed, removal efficiencies of greater than 90% could be achieved for the loads below 64 g benzene/m3/hr, 110 g toluene/m3/hr, 53 g ethylbenzene/m3/hr, and 55 g o-xylene/m3/hr. When a mixed substrate was fed, removal efficiencies of each compound could be above 90% at BTEX loads below 96 g/m3/hr. The trickle bed biofilter appears to be an effective treatment process for removing both single and mixed BTEX vapors with low to high loads. Under similar substrate loads, BTEX vapors were preferentially biodegraded in the order of toluene, benzene, o-xylene, and ethylbenzene. The volumetric removal rates (elimination capacities) of BTEX vapors for a single-substrate feed were higher than those for a mixed-substrate feed under similar substrate loads; these differences were enhanced at higher substrate loads and less significant for a preferred substrate.  相似文献   

20.
A novel nanocomposite based on incorporation of multiwalled carbon nanotubes (MWCNTs) in polyvinyl chloride (PVC) was prepared. Proposed nanocomposite was coated on stainless steel wire by deep coating. Composition of nanocomposite was optimized based on results of morphological studies using scanning electron microscopy. The best composition (83% MWCNTs:17% PVC) was applied as a solid phase microextraction fiber. Complex mixture of aromatic (BTEX) and aliphatic hydrocarbons (C5–C34) were selected as model analytes, and performance of proposed fiber in extraction of the studied compounds from water and soil samples was evaluated. Analytical merits of the method for water samples (LODs = 0.10–1.10 ng L−1, r2 = 0.9940–0.9994) and for soil samples (LODs = 0.10–0.77 ng kg−1, r2 = 0.9946–0.9994) showed excellent characteristics of it in ultra trace determination of petroleum type environmental pollutants. Finally, the method was used for determination of target analytes in river water, industrial effluent and soil samples.  相似文献   

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