首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
Horizontal and vertical distributions of organic compounds extractable with n-hexane were investigated at five sampling stations (Ross Sea) during the Italian Antarctic Expedition 1997/98. Samples were collected from seven depths under pack ice and from two or three depths at the other stations located at different distances from the coast. The lowest concentrations of biogenic and anthropogenic compounds were found at station Y3, the furthest from the coast, while the highest concentrations were observed under pack ice (B2-2 station) or in the Polynya zone (Y1 station). The levels of organic compounds in the particulate phase were higher than those in the dissolved phase for all the investigated samples. Concentrations of biogenic organic compounds (long-chain aldehydes and alcohols, fatty acid esters and n-alkanes) were well related to fluorescence intensity, which is usually reported as a biological activity index. The odd-to-even carbon-number ratio for n-alkanes was lower than 1 at stations B2-2, Y1, Y5 and Y6 (located less than 150?km far from the coast) with the predominance of n-C16, n-C24 and n-C28, indicative of autochthonous pelagic species. An odd-to-even ratio higher than unity and a different n-alkane profile were observed at station Y3 (about 300?km from the Ross Ice Shelf and 600?km from Terra Nova Bay). Low levels of pollutants (i.e. phthalates) were found, mainly in the particulate phase up to a depth of 50?m, confirming a local source of the phthalates found at significant concentrations during previous expeditions.  相似文献   

2.
Nonpolar organic compounds (NPOCs) in ambient particulate matter (PM) commonly include n-alkanes, branched alkanes, hopanes and steranes, and polycyclic aromatic hydrocarbons (PAHs). The recent development of thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) has greatly reduced time and labor in their quantification by eliminating the laborious solvent extraction and sample concentration steps in the traditional approach that relies on solvent extraction. The simplicity of the TD-GCMS methods has afforded us concentration data of NPOCs in more than 90 aerosol samples in two aerosol field studies and 20 vehicular emissions-dominated source samples in Hong Kong over the past few years. In this work, we examine the interspecies relationships between select NPOCs and their concentration ratios to elemental carbon (EC) among the ambient samples and among the source samples. Our analysis indicates that hopanes were mainly from vehicular emissions and they were significantly oxidized in ambient PM. The hopane/EC ratio in ambient samples was on average less than half of the ratio in vehicular emissions-dominated source samples. This highlights the necessity in considering oxidation loss in applying organic tracer data in source apportionment studies. Select PAH/EC ratio–ratio plots reveal that PAHs had diverse sources and vehicular emissions were unlikely a dominant source for PAHs in Hong Kong. Biomass burning and other regional sources likely dominated ambient PAHs in Hong Kong.  相似文献   

3.
Pressurised microwave-assisted extraction was used to extract a complex mixture containing polycyclic aromatic hydrocarbons (PAHs), nitrated PAHs and heavy n-alkanes from a particularly refractory carbonaceous material resulting from the combustion in a diesel engine. A second-order central composite design was used to determine the optimal conditions of extraction in terms of time, temperature, volume and nature of extracting solvent from spiked diesel soots. To begin, methylene chloride, tetrahydrofuran and chloroform were tested for extracting the spiked diesel particulates; however, the nature of these solvents was not really an influential factor. Volume was the most influential factor and was kept at a medium level to enhance the extraction of heavy PAHs without introducing an important dilution factor. Temperature and time were not influential as main factors but interacted with the other factors. Finally, high temperature and duration associated with a medium volume of methylene chloride were better for the extractions. After this optimisation, five-ring and six-ring PAHs were nevertheless not satisfactorily desorbed. Other solvents were therefore tested. Only aromatic ones, and particularly heterocyclic aromatic solvents, managed to desorb the heaviest PAHs. Pyridine, with its both aromatic and its basic character, was the most successful solvent. Desorption was even complete with an addition of 17% of diethylamine into pyridine. So, using MAE, we succeeded in extracting quantitatively, from the spiked refractory diesel soot surface, two-ring to six-ring PAHs, heavy n-alkanes and short nitrated PAHs. However, heavy nitrated PAHs were better extracted with a small addition of acetic acid (1%) into pyridine instead of a basic cosolvent.  相似文献   

4.
Chiu KH  Yak HK  Wai CM  Lang Q 《Talanta》2005,65(1):149-154
Packed in a high-pressure vessel and under calculated conditions, dry ice can be used as a source of carbon dioxide for supercritical CO2 extraction or liquid CO2 of organic compounds from environmental samples. Coupled with a fluid modifier such as toluene, dry ice-originated supercritical CO2 (Sc CO2) achieves quantitative extraction of many volatile organic compounds (VOCs) and semivolatile organic compounds (SOCs) including polycyclic aromatic hydrocarbons (PAHs), n-alkanes, and polychlorinated biphenyls (PCBs) from solid matrices. Compared to contemporary manual or automated supercritical fluid extraction (SFE) technologies, this novel technique simplifies SFE to a minimum requirement by eliminating the need of a high-pressure pump and any electrical peripherals associated with it. This technique is highly suitable to analytical areas where sample preservation is essential but difficult in the sampling field, or where sample collection, sample preparation, and analysis are to be done in the field.  相似文献   

5.
Supercritical fluid extraction (SFE) was performed to extract complex mixtures of polycyclic aromatic hydrocarbons (PAHs), nitrated derivatives (nitroPAHs) and heavy n-alkanes from spiked soot particulates that resulted from the incomplete combustion of diesel oils. This polluted material, resulting from combustion in a light diesel engine and collected at high temperature inside the particulate filter placed just after the engine, was particularly resistant to conventional extraction techniques, such as soxhlet extraction, and had an extraction behaviour that differed markedly from certified reference materials (SRM 1650). A factorial experimental design was performed, simultaneously modelling the influence of four SFE experimental factors on the recovery yields, i.e.: the temperature and the pressure of the supercritical fluid, the nature and the percentage of the organic modifier added to CO2 (chloroform, tetrahydrofuran, methylene chloride), as a means to reach the optimal extraction yields for all the studied target pollutants. The results of modelling showed that the supercritical fluid pressure had to be kept at its maximum level (30 MPa) and the temperature had to be kept relatively low (75 °C). Under these operating conditions, adding 15% of methylene chloride to the CO2 permitted quantitative extraction of not only light PAHs and their nitrated derivatives, but also heavy n-alkanes from the spiked soots. However, heavy polyaromatics were not quantitatively extracted from the refractory carbonaceous solid surface. As such, original organic modifiers were tested, including pyridine, which, as a strong electron donor cosolvent (15% into CO2), was the most successful. The addition of diethylamine to pyridine, which enhanced the electron donor character of the cosolvent, even increased the extraction yields of the heaviest PAHs, leading to a quantitative extraction of all PAHs (more than 79%) from the diesel particulate matter, with detection limits ranging from 0.5 to 7.8 ng for 100 mg of spiked material. Concerning the nitrated PAHs, a small addition of acetic acid into pyridine, as cosolvents, gave the best results, leading to fair extraction yields (approximately 60%), with detection limits ranging from 18 to 420 ng.  相似文献   

6.
Typical analytical features of petroleum products in environmental samples were considered. Among them are typical shapes of chromatograms; peaks of n-alkanes; the ratio between n-alkanes with even and odd numbers of carbon atoms; peaks of biomarkers (isoprenanes, steranes, triterpanes, etc.); the predominance of methyl- and alkyl-substituted mono-, bi-, and polynuclear aromatic hydrocarbons over unsubstituted aromatic hydrocarbons; and other features. These features altogether enable reliable conclusions about the petroleum origin of the identified pollutants to be made.  相似文献   

7.
Abstract

Oil hydrocarbons represent a great proportion of organic compounds in the atmosphere. Information about these compounds in the atmosphere of the Eastern Province of Saudi Arabia is lacking. In this study, n-alkanes and polynuclear aromatic hydrocarbons in air particulates were determined. The highest median concentration levels of n-alkanes in three urban areas and three areas near oil production centers were 121 ng/m3 and 42.9 ng/m3, respectively. Polynuclear aromatic hydrocarbons were also detected, although they are present in too low concentration for reliable quantitative measurement by GC and GC/MS techniques. A positive correlation was found between the concentration levels of n-alkanes in air particulates and the total suspended particulates measured at most locations. The carbon preference index (CPI) and the presence of the unresolved complex envelope suggested an anthropogenic origin for the n-alkanes.  相似文献   

8.
We examined an applicability of an improved urea adduction technique for the determination of hydrogen isotopic composition (δD) of homologous series of n-alkanes present in polluted urban aerosols using GC/TC/IRMS. Unresolved complex mixture (UCM) of hydrocarbons that interferes with accurate isotope measurements of n-alkanes was removed from n-alkane fraction by a urea adduction method. Recoveries of C20 to C30 n-alkanes during the urea adduction procedure were greater than 90% when the concentrations of total n-alkanes exceed 6.1?µg?mL?1. Our compound-specific D/H ratios confirm the absence of significant hydrogen isotope fractionation in n-alkanes during urea adduction and recovery of the purified n-alkane fraction. We applied this technique to the urban aerosols that contain a large quantity of UCM to measure δD of C20 to C35 n-alkanes in urban aerosols from Tokyo and Sapporo with an accuracy less than 10‰. We found that the δD values widely ranged from ?38 to ?179‰. Based on the δD values of individual n-alkanes in aerosol samples, we can obtain further information on the sources of aerosol n-alkanes and their source regions, and the atmospheric processes such as long-range transport and atmospheric mixing of air masses of different origin.  相似文献   

9.
In recent years there has been much progress in the miniaturization of sample treatment approaches for the analysis of organic contaminants. Whilst much focus has been given to analysis of liquid matrices (e.g., water, biological fluids), equivalent approaches for lipid rich biota samples have seen significantly less progress. This is especially the case for samples of very small organisms commonly employed as standard test species in ecotoxicity studies. Typically, the extractable biotic sample size available for body residue analysis is very small and the total pollutant accumulation can vary significantly between species types according to factors such as organism size, lipid content and exposure conditions. Depending on the physical and chemical characteristics of the analyte(s) in question, extraction and purification, especially from more complex matrices, appears to be one of the main bottlenecks in achieving their quantification. The current article presents a review of the available micro-extraction methods for small marine biota samples, focusing on environmentally important organic pollutants such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and pesticides.  相似文献   

10.
A fast and simple fractionation method was optimized to selectively separate oxy-PAH from polycyclic aromatic hydrocarbons (PAH) and n-alkanes contained in solvent extracted organic matter (SEOM) from atmospheric particles with an aerodynamic diameter ≤2.5 μm (PM2.5). Samples were collected in Mexico City. Multivariate parameters were adjusted on a standard mixture, and on SEOM spiked with pure standard mixture solutions: type and amount of phase; packing densities; type, proportion and amount of solvents, and elution flow rates were tested under several elution schemes. Cyanopropylsilyl-bonded phase material was the selected stationary phase. The separation method was applied to real samples of SEOM (2.6, 5.6 and 8.5 mg) spiked with n-alkanes, PAH and oxy-PAH. n-Alkanes overlapped with PAH due to an excess of n-alkanes in real samples overloading the capacity of the stationary phase. Oxy-PAH was separated totally from n-alkanes and PAH. Mean recoveries ± confidence intervals (95%) for n-alkanes ranged from 53 ± 17% (n-tetracontane) to 101 ± 11% (n-hexacosane); for PAH from 58 ± 5% (phenanthrene) to 85 ± 9% (benzo[k]fluoranthene); and for oxy-PAH from 68 ± 12% (9,10-dihydrobenzo[a]pyren-7(8H)one) to 108 ± 9% (1,2-benzopyrone). This method is an efficient fractionation procedure to be applied to oxy-PAH, PAH and n-alkanes in complex organic mixtures extracted from PM2.5.  相似文献   

11.
Abstract

The lipidic fraction compositions of both concentrated vinasses, a by-product of the sugar industry, and a compost made basically from olive oil vegetation waters (alpechin) were studied. The alpechin lipids are composed mainly by series of n-alkanes and lineal and branched fatty acids, whereas the major lipids in vinasses were n-alkanes, n-alkanols and acetals. Concentrations and composition of lipids in both materials do not seem of concern.

Preliminary results on the effects of the application of both materials over two years on the organic status of an agricultural soil are also reported. No significant changes were observed in total organic carbon and contents in humic fractions and lipids before and after the applications. However, analysis by GC-MS of the lipid compounds present in bound forms in the subsoil layer revealed that some hydrophobic components were accumulated in the soil following the waste applications.  相似文献   

12.
The partial molar free energy, enthalpy, and entropy of sorption of C11−C23 n-alkanes were calculated on the basis of the GC data obtained on the glass capillary column coated with fullerene C60 (Ful-60) as stationary phase. The thermodynamic parameters ofn-alkane sorption on a column with Ful-60 and a fused silica capillary column with polydimethylsiloxane OV-1 were determined and compared. The enthalpy-entropy compensation effect for the sorption ofn-alkanes on Ful-60 and OV-1 was found. A linear dependence of the partial molar free energy ofn-alkane sorption on the temperature of analysis and carbon chain length was found. The free energy contributions of the methylene groups were calculated, and their temperature dependences were studied. The differences in the temperature dependences of the energy contributions of methylene groups ofn-alkanes on Ful-60 and OV-1 were revealed. The entropy contribution is 68–82% of the enthalpy contribution which indicates a substantial role of the number of contacts with Ful-60 in retention ofn-alkanes. The ability of Ful-60 for dispersive interactions is similar to those of nonpolar liquid phases and substantially differs from that for carbon adsorbents. Fullerene columns were shown to be convenient for analysis of highly boiling organic substances in aqueous and organic solutions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1490–1495, August, 1999.  相似文献   

13.
Polycyclic aromatic hydrocarbons (PAHs), organic compounds formed by at least two condensed aromatic rings, are ubiquitous environmental pollutants that are produced by incomplete combustion of organic materials. PAHs have been classified as carcinogenIC to humans by the International Agency for Research on Cancer, because they can bind to DNA, causing mutations. Therefore, the levels of PAHs in human urine can be used as an indicator for potential carcinogenesis and cell mutation. An analytical method was developed for the accurate measurement of PAHs in urine using high‐resolution gas chromatography–mass spectrometry. Urine samples were extracted by an Oasis HLB extraction cartridge after enzymatic hydrolysis with a β‐glucuronidase/arylsulfatase cocktail. The 18 PAHs were separated using an Agilent DB‐5 MS capillary column (30 m × 0.25 mm, 0.25 μm) and monitored by time‐of‐flight mass spectrometry. Under the optimized method, the linearity of calibration curves was >0.994. The limits of detection at a signal‐to‐noise ratio of 3 were 10–100 ng/L. The coefficients of variation were in the range of 0.4–9.0%. The present method was highly accurate for simultaneous determination of 18 PAHs in human urine and could be applied to monitoring and biomedical investigations to check exposure of PAHs.  相似文献   

14.
Counter‐current chromatography (CCC) was investigated as a new sample pretreatment method for the determination of trace polycyclic aromatic hydrocarbons (PAHs) in water environmental samples. The experiment was performed with a non‐aqueous binary two‐phase solvent system composed of n‐heptane and acetonitrile. The CCC column was first filled with the upper stationary phase, and then a large volume of water sample was pumped into the column while the CCC column was rotated at 1600 rpm. Finally, the trace amounts of PAHs extracted and enriched in the stationary phase were eluted out by the lower mobile phase and determined by gas chromatography–flame ionization detector (GC‐FID) or gas chromatography–mass spectrometry (GC‐MS). The enrichment and cleanup of PAHs can be fulfilled online by this method with high recoveries (84.1–103.2%) and good reproducibility (RSDs: 4.9–12.2%) for 16 EPA PAHs under the optimized CCC pretreatment conditions. This method has been successfully applied to determine PAHs in lake water where 8 PAHs were detected in the concentration of 40.9–89.9 ng/L. The present method is extremely suitable for the preparation of large volume of environmental water sample for the determination of trace amounts of organic pollutants including PAHs as studied in this paper.  相似文献   

15.
Whereas common fluorescence and phosphorescence spectra of organic molecules in solutions show little details, Shpol'skii spectra exhibit completely resolved vibronic transitions, enabling the analytical distinction between isomeric compounds. In a simplified qualification, the Shpol'skii technique combines the sensitivity inherent to luminescence spectroscopy with the selectivity of infrared spectra. There are however two main limitations as far as its applicability is concerned: (i) cryogenic temperature conditions are required and (ii) the analytes should be compatible with the solvent matrix, typically an-alkane.The present paper is focused on the potential and achievements of Shpol'skii spectrometry in environmental analysis. After a discussion of the fundamental aspects of spectral line-broadenings and the approaches to accomplish high-resolution, special attention is paid to experimental and instrumental aspects. Recent instrumental developments have made Shpol'skii spectroscopy not only attractive for qualitative but also for quantitative purposes.The main part of the review is devoted to recent applications, for instance the determination of parent polycyclic aromatic hydrocarbons (PAHs) in complex environmental samples as crude oils, sediments, soils and biota. The special features of large PAHs, i.e. PAHs with seven or more hexagonal aromatic rings are considered separately. The analysis of PAH-metabolites in samples like fish bile and human urine is extensively discussed. Subsequently the applicability of Shpol'skii spectroscopy to both in-ring and atring substituted polycyclic aromatics is concerned, including amino- and nitro-substituted PAHs and nitrogen-, oxygen- and sulphur-heterocyclic compounds. The review ends with an interesting new development i.e. the Shpol'skii spectra of fullerenes, the soccerball and rugbyball shaped molecules C60 and C70, compounds receiving wide attention in physics and chemistry.  相似文献   

16.
Abstract

The atmospheric transport of organic pollutants over long distances and their effect on the biological cycles of the sea are two major questions of concern in environmental chemistry. These processes are of particular importance in the Mediterranean Sea because of its semi-enclosed characteristics, which determine the accumulation of the pollutants entering into the system.

In order to get some insight into these processes a project (PHYCEMED), was developed for the evaluation of the atmospheric budget of organic and inorganic substances in the Western Mediterranean and for the investigation of the exchange mechanisms of these materials across the air/sea interface.

A high volume air sampling system including a cascade impactor was placed on board of the R/V le Suroit for collecting the acrosols along several transects parallel to the French, Spanish and North-African coasts, facing areas of different population densities and industrial activities. The cruise was realised on October 1983 and the particulate material was fractionated into the following sizes: 7.2, 3.0, 1.5, 0.96, and 0.03 μm. Quantitative and qualitative analyses of the aliphatic and the aromatic hydrocarbons present in these fractions were performed by high resolution gas chromatography and gas chromatography-mass spectrometry.

Total non-aromatic hydrocarbon concentrations are in the range 30-57 ng/m3 (10-14ng/m3 for n-alkanes). The distribution of n-alkanes indicates that most of the aerosol mass is associated with small particles < 1 μm.Polycyclic aromatic hydrocarbons are identified from phenanthrene to benzo(ghi)perylene with fluoranthene and pyrene as dominant compounds. Concentrations for individual PAH vary in the range 4.1 pg/m3 for benzo(a)anthracene up to 100 pg/m3 for fluoranthene. The evaluation of different contributions such as land plant waxes or soil sources and various anthropogenic sources is discussed from n-alkanes and PAH distribution patterns.  相似文献   

17.
18.
Solid-phase microextraction (SPME) has been successfully used for extracting polycyclic aromatic hydrocarbons (PAHs) from porewater samples from the Mersey Estuary, UK. The majority of the PAHs in porewater samples are associated with colloids due to the high DOC concentrations. The truly dissolved PAH concentrations varied from 66 to 1050?ng?L?1 in core 2 and from 95 to 740?ng?L?1 in core 3, and were dominated by naphthalene, fluoranthene, and pyrene. Although absent in the dissolved phase, the high-molecular-mass compounds were found in the colloid-associated fraction of porewater. PAHs in sediments arose from a range of compounds with 4- and 5-ring PAHs dominating. The partitioning of PAHs between sediment and porewater shows that PAHs are enriched in the sediment phase. When the soot carbon content was considered, predictions of the partition behaviour were found to agree more closely with the observed distribution. The results reiterate the importance of evaluating the speciation of organic pollutants in both porewater and sediments in order to accurately predict their environmental fate and potential toxicity.  相似文献   

19.
Solid-state urea clathrate formation (SSUCF) as a chemical separation method prior to stable carbon isotope fingerprinting of diesel fuel contaminations was studied. The stable carbon isotope ratios (δ13C) of n-alkanes in diesel fuel can be used to trace the origin of a contamination. The accurate measurement of the stable isotopic composition of individual compounds requires baseline separation from any other co-eluting compounds. For this purpose silica gel column chromatography (SGCC) and SSUCF were applied. Detailed optimisation of SSUCF was performed: different activators, clathrate formation temperatures, activator volumes, clathrate formation times and sample capacity were investigated. The main benefits of the developed method are reduced clathrate formation time and increased recoveries for lower molecular weight n-alkanes. The recoveries of the developed SSUCF method ranged between 63 and 100% for C10–C24 n-alkanes with relative standard deviation no more than 7%. The precision of the gas chromatography-isotope ratio mass spectrometry measurement was acceptable with a standard deviation of the δ13C values ranging between 0.08 and 0.15‰. The absence of isotopic fractionation was also investigated.

The robustness of the method was tested within a model experiment. Nine different water samples including distilled water, tap water, river water, industrial wastewaters and groundwater samples were spiked with the same diesel fuel. The water samples were extracted with n-hexane and after purification with both SGCC and SSUCF n-alkanes were measured. The δ13C values of n-alkanes were found to be similar for all samples. The importance of sample purification prior to compound-specific isotope analysis (CSIA) was also demonstrated within this model experiment by analysing samples from different stages of the sample preparation.

Our results show that the proposed method can remarkably improve the precision of compound-specific stable carbon isotope analysis of n-alkanes originating from diesel contamination of the aquatic environment.  相似文献   


20.
Several methods of extraction were optimized to extract polycyclic aromatic hydrocarbons (PAHs), their nitrated derivatives and heavy n-alkanes from a highly adsorptive particulate matter resulting from the combustion of diesel fuel in a diesel engine. This particular carbonaceous particulate matter, collected at high temperatures in cordierite diesel particulate filters (DPF), which are optimized for removing diesel particles from diesel engine exhaust emissions, appeared extremely refractory to extractions using the classical extracting conditions for these pollutants. In particular, the method of accelerated solvent extraction (ASE) is described in detail here. Optimization was performed through experimental design to understand the impact of each factor studied and the factors’ possible interactions on the recovery yields. The conventional extraction technique, i.e., Soxhlet extraction, was also carried out, but the lack of quantitative extractions led us to use a more effective approach: hot Soxhlet. It appeared that the extraction of the heaviest PAHs and nitroPAHs by either the optimized ASE or hot Soxhlet processes was far from complete. To enhance recovery yields, we tested original solvent mixtures of aromatic and heteroaromatic solvents. Thereafter, these two extraction techniques were compared to microwave-assisted extraction (MAE) and supercritical fluid extraction (SFE). In every case, the only solvent mixture that permitted quantitative extraction of the heaviest PAHs from the diesel soot was composed of pyridine and diethylamine, which has a strong electron-donor character. Conversely, the extraction of the nitrated PAHs was significantly improved by the use of an electron-acceptor solvent or by introducing a small amount of acetic acid into the pyridine. It was demonstrated that, for many desirable features, no single extraction technique stound out as the best: ASE, MAE or SFE could all challenge hot Soxhlet for favourable extractions. Consequently, the four optimized extraction techniques were performed to extract the naturally polluted diesel soot collected inside the DPF. Comparisons with the NIST standard reference material SRM 1650b showed that the soot collected from the DPF contained 50% fewer n-alkanes, and also markedly lower levels of PAHs (44 less concentrated) than SRM 1650b, and that the ratio of nitroPAHs to PAHs was increased. These results were attributed to the high temperatures reached inside the particulate filter during sampling runs and to the contribution of the catalytic DPF to aromatic and aliphatic hydrocarbons abatement.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号