Toward the accurate analysis of C1-C4 polycyclic aromatic sulfur heterocycles

Polycyclic aromatic sulfur heterocycles (PASH) are sulfur analogues of polycyclic aromatic hydrocarbons (PAH). Alkylated PAH attract much attention as carcinogens, mutagens, and as diagnostics for environmental forensics. PASH, in contrast, are mostly ignored in the same studies due to the conspicuous absence of gas chromatography/mass spectrometry (GC/MS) retention times and fragmentation patterns. To obtain these data, eight coal tar and crude oils were analyzed by automated sequential GC-GC. Sample components separated based on their interactions with two different stationary phases. Newly developed algorithms deconvolved combinatorially selected ions to identify and quantify PASH in these samples. Simultaneous detection by MS and pulsed flame photometric detectors (PFPD) provided additional selectivity to differentiate PASH from PAH when coelution occurred. A comprehensive library of spectra and retention indices is reported for the C(1)-C(4) two-, three-, and four-ring PASH. Results demonstrate the importance of using multiple fragmentation patterns per homologue (MFPPH) compared to selected ion monitoring (SIM) or extraction (SIE) to identify isomers. Since SIM/SIE analyses dramatically overestimate homologue concentrations, MFPPH should be used to correctly quantify PASH for bioavailability, weathering, and liability studies.     

Determination of polycyclic aromatic hydrocarbons in drinking water samples by solid-phase nanoextraction and high-performance liquid chromatography

A novel alternative is presented for the extraction and preconcentration of polycyclic aromatic hydrocarbons (PAH) from water samples. The new approachwhich we have named solid-phase nanoextraction (SPNE)takes advantage of the strong affinity that exists between PAH and gold nanoparticles. Carefully optimization of experimental parameters has led to a high-performance liquid chromatography method with excellent analytical figures of merit. Its most striking feature correlates to the small volume of water sample (500 microL) for complete PAH analyses. The limits of detection ranged from 0.9 (anthracene) to 58 ng.L (-1) (fluorene). The relative standard deviations at medium calibration concentrations vary from 3.2 (acenaphthene) to 9.1% (naphthalene). The analytical recoveries from tap water samples of the six regulated PAH varied from 83.3 +/- 2.4 (benzo[ k]fluoranthene) to 95.7 +/- 4.1% (benzo[ g,h,i]perylene). The entire extraction procedure consumes less than 100 microL of organic solvents per sample, which makes it environmentally friendly. The small volume of extracting solution makes SPNE a relatively inexpensive extraction approach.     

Quantitative analysis of fuel-related hydrocarbons in surface water and wastewater samples by solid-phase microextraction

Solid-phase microextraction (SPME) parameters were examined on water contaminated with hydrocarbons including benzene and alkylbenzenes, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs). Absorption equilibration times ranged from several minutes for low molecular weight compounds such as benzene to 5 h for high molecular weight compounds such as benzo[a]pyrene. Under equilibrium conditions, SPME analysis with GC/FID was linear over 3-6 orders of magnitude, with linear correlation coefficients (r(2)) greater than 0.96. Experimentally determined FID detection limits ranged from ～30 ppt (w/w hydrocarbon/sample water) for high molecular weight PAHs (e.g., MW > 202) to ～1 ppb for low molecular weight aromatic hydrocarbons. Experimental distribution constants (K) were different with 100- and 7-μm poly(dimethylsiloxane) fibers, and poor correlations with previously published values suggest that K depends on the fiber coating thickness and the sorbent preparation method. The sensitivity of SPME analysis is not significantly enhanced by larger sample volumes, since increasing the water volume (e.g., from 1 to 100 mL) has little effect on the number of analyte molecules absorbed by the fiber, especially for compounds with K < 500. Water sample storage should utilize silanized glassware, since hydrocarbon losses up to 70% could be attributed to unsilanized glassware walls when samples were stored for 48 h. Hydrocarbon losses at part-per-billion concentrations also occurred with surface waters due to partitioning onto part-per-thousand concentrations of suspended solids. Quantitative determinations of aromatic and aliphatic hydrocarbons (e.g., in gasoline-contaminated water) can be performed using GC/MS with deuterated internal standard or standard addition calibration as long as the target components or standards had unique ions for quantitation or sufficient chromatographic resolution from interferences. SPME analysis gave good quantitative performance with surface waters having high suspended sediment contents, as well as with coal gasification wastewater which contained matrix organics at 10(6)-fold higher concentrations than the target aromatic hydrocarbons. Good agreement was obtained between a 45-min SPME and methylene chloride extraction for the determination of PAH concentrations in creosote-contaminated water, demonstrating that SPME is a useful technique for the rapid determination of hydrocarbons in complex water matrices.     

气相色谱-质谱法测定电子电气产品材料中多环芳烃

本文建立了采用气相色谱-质谱联用检测电子电气产品材料中多环芳烃的方法。以丙酮-正己烷(1+1)为提取溶剂,利用自动索氏提取仪提取电子电气产品材料中多环芳烃,正己烷-二氯甲烷(3+2)混合液淋洗硅胶小柱净化,气相色谱-质谱联用仪检测,该方法检测限在0.2mg/kg,加标回收率在59%～99%之间,相对标准偏差(RSD)小于5%,线性范围在0.1mg/L～100mg/L,相关系数(r)大于0.999。实验结果表明,该方法简便、可靠,能满足电子电气产品材料中多环芳烃的检测要求。     

HPLC测定鄱阳湖湿地土壤中15种多环芳烃

测定鄱阳湖湿地土壤中多环芳烃的含量,采用丙酮+正己烷(1∶1)为提取溶剂,超声提取40 min,总溶剂量为70 m L(10 g样品),色谱条件为进样量为20μL、流量为1 m L/min、柱温30℃,采用适当的流动相梯度淋洗程序与荧光检测器波长变换程序,高效液相色谱法测定鄱阳湖湿地土壤中15种多环芳烃的含量。结果表明:鄱阳湖湿地土壤中15种多环芳烃的含量为(ng/g):萘,92.45;苊,未检出;芴,9.90;菲,91.75;蒽,119.67;荧蒽,未检出;芘,81.51;苯并(a)蒽,13.26;,6.79;苯并(b)荧蒽,4.53;苯并(k)荧蒽,7.76;苯并(a)芘,未检出;二苯并(a,h)蒽,7.74;苯并(g,h,i)苝,未检出;茚苯(123-cd)芘,未检出。该方法的加标回收率在76.8%~115.1%之间,相对标准偏差在1.3%~5.8%之间,具有良好的准确度和精密度。说明该文建立的方法可测定鄱阳湖湿地土壤中多环芳烃的含量,为进一步研究鄱阳湖湿地土壤中多环芳烃的污染特征与来源解析提供依据。     

Determination of distribution coefficients of priority polycyclic aromatic hydrocarbons using solid-phase microextraction

The determination of distribution coefficients is important for prediction of the chemical pathways of organic compounds in the environment. Solid-phase microextraction (SPME) is a convenient and effective method to measure the distribution of chemicals in a two-phase system. In the present study, the SPME distribution coefficient (K(spme)) of 16 priority aromatic hydrocarbons (PAHs) was determined with 100-microm poly(dimethylsiloxane) (PDMS) and 85-microm polyacrylate (PA) fibers. The partition coefficients and LeBas molar volumes were used to describe the linearity of the log K(spme) values of PAHs. Also, the validation of the distribution coefficient was examined using different sample volumes. The extraction time was dependent on the types of PAHs, and 20 min to 60 h was needed to reach equilibrium. The determined log K(spme) values ranged from 3.02 to 5.69 and from 3.37 to 5.62 for 100-microm PDMS and 85-microm PA fibers, respectively. Higher K(spme) values of low-ring PAHs were observed using 85-microm PA fiber. Good linear relationships between log K(ow) and log K(spme) for PAHs from naphthalene to benzo[alpha]pyrene and from naphthalene to chrysene for 100-microm PDMS and 85-microm PA fibers, respectively, were obtained. The correlation coefficients were 0.969 and 0.967, respectively. The linear relationship between log K(spme) and the LeBas molar volume was only up to benz[alpha]anthracene for 85-microm PA fiber and up to chrysene for 100-microm PDMS fiber. Moreover, the effect of sample volume can be predicted using the partition coefficient theory and excellent agreement was obtained between the experimental and theoretical absorbed amounts of low-ring PAHs. This result shows that the determined log K(spme) is more accurate than the previous method for estimating analytes with log K(ow) < 6 as well as for predicting the partitioning behaviors between SPME fiber and water.     

Assessment of colloid formation and physical state distribution of trace polycyclic aromatic hydrocarbons in aqueous samples.

A tandem-cartridge system was established for studying colloid formation and physical state distribution of trace polycycic aromatic hydrocarbons (PAHs) in water. The effectiveness of the method for measuring the trace PAH colloids was demonstrated. With aqueous samples prepared by adding the PAH solutes with a small amount of organic solvent carrier, the potential of colloid formation increased with the hydrophobicity and concentration of the solute, but the incipient concentration for the colloid formation may be far lower than the aqueous solubility of the solute. After formation in water, the colloids showed remarkable stability at room temperature, and the stability was greatly reduced by elevated temperature and the presence of a small amount of inorganic electrolytes. The possible mechanism of destabilization of the colloids was discussed, and the mechanism might be of utility in providing insights into the physical state distribution of the solutes in various water samples. However, further effort to investigate the mechanism through fluorescence spectrophotometry was unsuccessful. The significance of the colloid formation in methods of preparation of aqueous samples and for measuring aqueous solubilities of PAHs and other hydrophobic compounds was illustrated. The results of this work demonstrate that it is undesirable to prepare aqueous solutions of PAHs or similarly hydrophobic compounds by vigorous mixing or the use of cosolvents, methods that are widely used in many studies for which aqueous solutions of such analytes are required.     

Three-way multivariate calibration procedures applied to high-performance liquid chromatography coupled with fast-scanning fluorescence spectrometry detection. Determination of polycyclic aromatic hydrocarbons in water samples

Three-way partial least-squares and n factor parallel factor analysis have been compared for the analysis of polycyclic aromatic hydrocarbons in water samples. Data were obtained with a chromatographic system set to record short-time chromatograms containing several unresolved peaks. The detection system consisted of a fast-scanning fluorescence spectra detector, which allows one to obtain three-dimensional data, where retention time, emission wavelengths, and fluorescence intensity are represented. The combined use of a multivariate calibration method and the three-dimensional data obtained from the HPLC-FSFS system allows resolution of closely eluting compounds, thus making a complete separation unnecessary. The procedure has been applied to tap water samples (spiked at 0.10 and 0.20 μg L(-)(1) levels) with good results, similar to those obtained with a HPLC system with a conventional fluorescence detector.     

Summarizing the effectiveness of supercritical fluid extraction of polycyclic aromatic hydrocarbons from natural matrix environmental samples

A summary of the supercritical fluid extraction (SFE) of polycyclic aromatic hydrocarbons (PAHs) from four natural matrix Standard Reference Materials (SRMs) is presented. The work involved the investigation of the effects of extraction fluid [carbon dioxide (CO(2)), chlorodifluoromethane (R22), and 1,1,1,2-tetrafluoroethane (HFC134a)], fluid modifier (dichloromethane and aniline), temperature (60, 150, and 200 °C) and added water on the SFE recoveries of PAHs compared to certified results from Soxhlet extractions. For SRM 1649a (Urban Dust/Organics), R22 yielded excellent recoveries (>90% of certified concentrations) of all PAHs measured, while results for the same SRM using HFC134a as the fluid were typically <80% of the certified concentrations for most of the PAHs measured. For SRM 1941a and 1944, both aquatic sediments with similar physical and chemical compositions, extractions of the wet materials with dichloromethane-modified CO(2) (10%, v/v) yielded quantitative recoveries of all PAHs for SRM 1944 but an obvious trend of lower recoveries for higher molecular weight PAHs (≥228 amu) for SRM 1941a. Results of SFEs of SRM 1650 (Diesel Particulate Matter) showed that this material is the most refractory of the SRMs investigated in this study, with recoveries of indeno[1,2,3-cd]pyrene and benzo[ghi]perylene at <20% of the Soxhlet results.     

Soluble polycyclic aromatic hydrocarbons in raw coals

Polycyclic aromatic hydrocarbons (PAHs) are considered to be a group of compounds that pose potential health hazards since some PAHs are known carcinogens. During coal utilization processes, such as coal combustion and pyrolysis, PAHs released may be divided into two categories according to their formation pathways. One category is derived from complex chemical reactions and the other is from free PAHs transferred from the original coals. PAHs released from complex chemical reactions during combustion and pyrolysis have received considerable attention in recent years. However, free PAHs contained in raw coals have not been seriously considered as a source of these materials to be released during the utilization of coal. The goal of this study was to observe the relation between the content of PAHs in different coals and the elemental composition of the coals. In this study, eight bituminous coals with dry, ash-free carbon values varying from 65% to 90% were selected. Each coal was extracted with dichloromethane in a Soxhlet extractor for 6 h. The extracts were quantitatively analyzed with a gas chromatograph/mass spectrometer (GC-MS). More than 20 kinds of PAHs were identified. The total amount of PAHs determined varied from 1.2 to 28.3 mg/kg from the various coal types. The maximum total PAHs extracted was reached when the carbon content exceeded 84% by weight.     

Determination of aqueous solubility and surface adsorption of polycyclic aromatic hydrocarbons by laser multiphoton ionization

Polycyclic aromatic hydrocarbons (PAHs) are of considerable analytical interest due to their environmental effects. On-line monitoring of these compounds based on microdroplet sampling requires accurate characterization of their solubilities and surface adsorption. A new method to determine aqueous solubility and surface adsorption of PAHs is suggested, using a combination of microdroplet sampling and multiphoton ionization-based fast-conductivity (MPI-FC) techniques. Controlled droplet contamination by PAHs was performed by external deposition upon direct contact with renewable water droplets (?10 μL). Our approach relies on the finding that, at the onset of aqueous equilibrium solubility, X(E), a sharp increase in the detected photocharges is recorded. We show that this is directly related to enhanced surface adsorption of a particular PAH material. This behavior manifests itself in slope variation of the respective calibration curves. The PAH materials used, which have provided about four decades variation in X(E) figures, were anthracene, perylene, pyrene, and phenanthrene. Applicability of the method for studying the surface excess and adsorption is specified. The MPI-FC technique provides an easy analytical tool for measuring low aqueous solubility of organic compounds and characterization of their adsorption, with no need for laborious sample preparation routines.     

Ex-situ bioremediation of polycyclic aromatic hydrocarbons in sewage sludge

Polycyclic aromatic hydrocarbons (PAH) are regarded as environmental pollutants. A promising approach to reduce PAH pollution is based on the implementation of the natural potential of some microorganisms to utilize hydrocarbons. In this study Proteiniphilum acetatigenes was used for bioaugmentation of sewage sludge to improve the PAH removal. Bioaugmentation experiments were performed in parallel semi-continuously fed reactors started up with digested primary and secondary sludge. Three bioaugmentation approaches were investigated: A1, addition of bacteria once during starting up; A2, addition of bacteria at the beginning and then every 2nd day and A3, addition of encapsulated bacteria once during starting up. Removal of PAH was found to be both biotic and abiotic. All three approaches had a positive effect of the biological removal of PAH. Highest biological removal of individual PAH (up to 80%) was observed using continuous addition (approach A2) of the bacteria to the reactors. In general, the effect of bioaugmentation was higher in the reactors fed with primary sludge compared to the reactors fed with mixed sludge. Bioaugmentation resulted in biological removal of low molecular weight PAH in the reactors fed with primary sludge using all three approaches while clear biological removal of the medium- and high molecular weight PAH only was observed if the bacteria were added continuously (approach A2).     

Pollution patterns of polycyclic aromatic hydrocarbons in tobacco smoke

Concentrations of polycyclic aromatic hydrocarbons (PAHs) in tobacco smoke of 12 commercial brand cigarettes were determined in a simulated chamber of 20.25 m3 in size. The total concentrations of 17 PAHs (summation operatorPAHs) in the chamber were 3500 and 1152 ng/m3 in vapor phase and particulate phase, respectively. In vapor phase, the yield of naphthalene (NA) appeared to be the most abundant (2462 ng/cig) followed by fluorene (FLUOR) and acenaphthylene (ACY), while the yield of benzo[ghi]perylene (BP) was the most abundant (259.7 ng/cig) in particulate phase followed by phenanthrene (PHEN) and FLUOR. The proportion of PAHs in particulate phase increased with increasing molecular weight. PAHs with two to six rings accounted for 40.2%, 35.3%, 11.7%, 7.6%, 5.2% of summation operatorPAHs, respectively. There was no obvious correlation between PAHs, benzo[a]pyrene (BaP) concentrations in tobacco smoke and smoking tar contents, nicotine contents. With the source fingerprint of PAHs in tobacco smoke, NA could be regarded as the marker of tobacco smoke source because of its largest contribution to summation operatorPAHs (40.2%), followed by FLUOR (12.7%) and ACY (9.8%). Further study indicated that more than 80% of BaP in indoor air of resident homes in Hangzhou was from tobacco smoke.     

Direct photolysis of polycyclic aromatic hydrocarbons in drinking water sources

The widely used low pressure lamps were tested in terms of their efficiency to degrade polycyclic aromatic hydrocarbons listed as priority pollutants by the European Water Framework Directive and the U.S. Environmental Protection Agency, in water matrices with very different compositions (laboratory grade water, groundwater, and surface water). Using a UV fluence of 1500 mJ/cm², anthracene and benzo(a)pyrene were efficiently degraded, with much higher percent removals obtained when present in groundwater (83-93%) compared to surface water (36-48%). The removal percentages obtained for fluoranthene were lower and ranged from 13 to 54% in the different water matrices tested. Several parameters that influence the direct photolysis of polycyclic aromatic hydrocarbons were determined and their photolysis by-products were identified by mass spectrometry. The formation of photolysis by-products was found to be highly dependent on the source waters tested.     

Characterization and biodegradation of polycyclic aromatic hydrocarbons in radioactive wastewater

PAH degrading Pseudomonad and Alcaligenes species were isolated from landfill soil and mine drainage in South Africa. The isolated organisms were mildly radiation tolerant and were able to degrade PAHs in simulated nuclear wastewater. The radiation in the simulated wastewater, at 0.677 Bq/μL, was compatible to measured values in wastewater from a local radioisotope manufacturing facility, and was enough to inhibit metabolic activity of known PAH degraders from soil such as Pseudomonas putida GMP-1. The organic constituents in the original radioactive waste stream consisted of the full range of PAHs except fluoranthene. Among the observed PAHs in the nuclear wastewater from the radioisotope manufacturing facility, acenaphthene and chrysene predominated—measured at 25.1 and 14.2 mg/L, respectively. Up to sixteen U.S.EPA priority PAHs were detected at levels higher than allowable limits in drinking water. The biodegradation of the PAHs was limited by the solubility of the compounds. This contributed to the observed faster degradation rates in low molecular weight (LMW) compounds than in high molecular weight compounds.     

Determination of phosphorous and sulfur in environmental samples by electrothermal vaporization inductively coupled plasma atomic emission spectrometry

From the viewpoint of selective introduction of the analyte from its solvent and matrices, electrothermal vaporization (ETV) is useful for the sample introduction into the inductively coupled plasma (ICP). By using a tungsten boat furnace (TBF) vaporizer system, the loss of analyte phosphorus, which normally occurs during the drying and ashing stages, is suppressed. The phosphate ion is reacted with the tungsten supplied from the surface of the TBF to form stable tungsten phosphate species. Regarding the determination of sulfur, additional chemical modifiers such as copper(II), lead(II), etc., are necessary to retain the analyte on the TBF. The furnace-fusion (FF) method or wet-digestion technique on the TBF is applied to unify the chemical forms of the analytes. Various oxidative and reductive inorganic compounds as well as organic compounds of phosphorus and sulfur show the same sensitivities after the FF digestion with hydrogen peroxide. The detection limits are 1.5 ng and 0.12 ng for phosphorous and sulfur, respectively. The repeatabilities in terms of the relative standard deviations of 10 replicate measurements of phosphorus and sulfur are 4.2% and 2.0%, respectively. Finally, the established method is applied to the determination of several environmental waters.