Study of traffic-emitted lead pollution of soil and plants using different fuzzy clustering algorithms

We discuss the clustering of 234 environmental samples resulting from an extensive monitoring program concerning soil lead content, plant lead content, traffic density, and distance from the road at different sampling locations in former East Germany. Considering the structure of data and the unsatisfactory results obtained applying classical clustering and principal component analysis, it appeared evident that fuzzy clustering could be one of the best solutions. In the following order we used different fuzzy clustering algorithms, namely, the fuzzy c-means (FCM) algorithm, the Gustafson–Kessel (GK) algorithm, which may detect clusters of ellipsoidal shapes in data by introducing an adaptive distance norm for each cluster, and the fuzzy c-varieties (FCV) algorithm, which was developed for recognition of r-dimensional linear varieties in high-dimensional data (lines, planes or hyperplanes). Fuzzy clustering with convex combination of point prototypes and different multidimensional linear prototypes is also discussed and applied for the first time in analytical chemistry (environmetrics). The results obtained in this study show the advantages of the FCV and GK algorithms over the FCM algorithm. The performance of each algorithm is illustrated by graphs and evaluated by the values of some conventional cluster validity indices. The values of the validity indices are in very good agreement with the quality of the clustering results. Figure Projection of all samples on the plane defined by the membership degrees to cluster A₂, and A₄ obtained using Fuzzy c-varieties (FCV) algorithm (expression of objective function and distance enclosed)     

Characterisation of particulate matter from the Kara Sea using electron probe X-ray micro analysis

Automated electron probe X-ray micro-analysis (EPXMA) was used to characterise 17 600 individual particles collected in the Kara Sea and in the estuary of the Yenisey River. Samples were obtained by filtering and centrifugation of particles in suspension and from bottom sediments. Multivariate techniques were used to reduce the enormous data sets. By testing hierarchical, non-hierarchical and fuzzy clustering on the centrifuged suspension samples, it was shown that hierarchical clustering is most suitable. The two other clustering techniques are very time consuming and in most cases do not add any additional information. This hierarchical clustering of the data matrix results in different particle types which can be apportioned to their possible sources. The aluminosilicate particle types dominate in all samples and suppress the relative abundances of other interesting groups like metal-rich particles. However, Fe-rich and Ti-rich particles are still frequently found. Since the nearest industry is 200 km from the sampling site, it is especially surprising to find high contributions for Ti-rich particles which, because of their small diameter (i.e. between 0.6 μm and 1.1 μm), are most likely of anthropogenic origin. To complete this study the homogeneity and morphology of 100 particles from water suspension samples were analysed using manual EPXMA.     

Application of direct thermal desorption gas chromatography time-of-flight mass spectrometry for determination of nonpolar organics in low-volume samples from ambient particulate matter and personal samplers

Direct thermal desorption and in-situ derivatization thermal desorption methods in conjunction with gas chromatography time-of-flight mass spectrometry have been characterized and evaluated for analysis of trace components from filters loaded with ambient particulate matter (PM). The limits of quantification were in the range of 7–24 pg for n-alkanes, 20 pg for hopanes, and 4–22 pg for polycyclic aromatic hydrocarbons (PAH). The limit of quantification was defined as the minimum amount of substance that conforms to the minimum distinguishable signal plus 9 times the standard deviation of this background signal from PM-loaded filters. The method has been successfully applied to low-volume samples from ambient PM collected with stationary and personal samplers. Stationary samples were collected in winter 2008 and 2010 in Augsburg, Germany. Sample aliquots of 0.2-0.3 m3 from stationary sampling were analyzed. High diurnal variation in concentration and source contribution was found especially during periods with low wind speed and low mixing layer height. High contributions of solid fuel combustion (wood and coal) were found in evening and nighttime samples, leading to peak PAH concentrations at midnight more than 10 times higher than at noon. Finally, the method was applied to samples collected by means of a personal sampler, i.e. a micro aethalometer, in Xi’an, China. Quantitative data on n-alkanes, hopanes, and PAH were obtained from sample volumes of 17 and 24 l. The impact of different sources such as vehicular and biogenic emissions could be distinguished.     

Characteristics of wintertime polycyclic aromatic hydrocarbon assemblage in aerosol of the Southern Adriatic

Features of polycyclic aromatic hydrocarbon (PAH) assemblage in aerosol samples collected from the atmosphere of Herceg Novi during the winter months of two successive years were studied. The results showed almost the same concentration profiles of identified PAHs for samples from the two periods analyzed, generally suggesting a similar origin. Diagnostic ratios indicated combustion of wood and coal, emissions from petrol and diesel engines, and dust resuspension as sources that predominantly contributed to the atmospheric PAH concentrations. Statistical analysis, principal component analysis (PCA) in particular, allowed us to identify the impact of meteorological parameters on PAH abundance. The text was submitted by the authors in English.     

Source apportionment of polycyclic aromatic hydrocarbons in surface sediments of Izmit Bay (Turkey)

Thirty-five surface sediment samples were collected from the northeastern coast of the Izmit Bay to apportion the sources of polycyclic aromatic hydrocarbons (PAH) entering the Bay. Samples were collected in February and June, 2002 and they were analyzed for 16 PAH compounds using HPLC-UV. Total PAHs ranged from 1.1 to 68.4?μg?g^?1-dry wt. Both the factor analysis and the factor analysis-absolute factor score multiple linear regression analysis were applied to the results of 11 PAH compounds which were observed in more than 80% of the samples. From the factor analysis, two factors explaining 91.3% of the total variance were identified. The first factor was petrogenic and explained 76% of the variance. Except for the Anthracene, 57 to 85% of the lower molecular mass PAH compounds (from Fluorene to Chrysene) were contributed by this factor.     

多环芳烃指纹用于渤海采油平台原油的鉴别

采用气相色谱/质谱方法,对渤海海上4个不同区块、5个平台的6口油井原油进行了烷基化多环芳烃系列化合物和美国环保署（EPA）优先控制多环芳烃系列化合物的准确定性定量分析。通过多环芳烃原始指纹谱图、多环芳烃组分分布模式和特征比值的比较对上述原油进行鉴别。结果证明不同区块的原油中多环芳烃指纹信息不尽相同,即使在同一平台不同油井中所产的原油其指纹也存在一定差异。为确保原油鉴别的准确性,分析过程中必须在仪器的稳定性和样品前处理方面实施严格的质量控制措施。     

Residential wood combustion: A source of atmospheric polycyclic aromatic hydrocarbons

Samples were taken of the atmospheric particulate matter over Fairbanks Alaska in the winter of 1985, and from wood stoves burning the major wood types locally available. These samples were then analyzed for polycyclic aromatic hydrocarbon (PAH). A PAH emission profile was determined from the wood stove samples and applied to the atmospheric samples to determine the residential wood combustion contribution to the local atmospheric particulate burden. Emission profiles for coal burning and automobile emissions for PAH were also used to estimate their relative contributions.     

Source Apportionment for the Zinc—Containing Component of Air Particulate Matter using Automated Electron Probe Micro Analysis of Individual Particles

Abstract

A methodology is described for the apportionment of zinc-containing particulate matter sampled in the vicinity of a zinc smelter to their corresponding sources in the factory. Bulk samples of particulate matter from six potential emission sources were analysed by automated electron probe microanalysis (EPMA) in order to characterize the individual particles. Based on a data set of relative peak intensities and with the aid of a binary clustering method, the most important particle classes were identified. They were used as a basis for the development of a set of disjunct identification rules (decision rules), which were able to describe the classes in a unique manner. Applying these rules upon ambient particulate data enabled the estimation of relative contributions of different types of zinc-containing particles. Evidence was found that a large number of particles was modified by a soil component or by gas phase reactions.     

An evaluation of analytical quality for selected PAH measurements in a fuel-contaminated soil

The measurements of polycyclic aromatic hydrocarbons (PAHs) in soil require optimized analytical methods that assess reliable mass fraction results. This is particularly important for analysing very complex matrix such as contaminated soils with crude fuels. The main objectives of this work were focused to minimize analytical effort and assess result reliability in analysis of PAH by high-performance liquid chromatography with fluorescence detection (HPLC/FD). First, analysis of soil samples with/without fuel contamination was well established by sonication (US) and pressurized fluid extraction (ASE) using minimal amount of sample and minimal treatment of sample. On the other hand, an extensive study with spiked and field soil samples was performed by checking proportional and constant bias for analytical validation. The major components for estimating uncertainty contributions were evaluated on the basis of intermediate precision with two fuel matrix, PAH mass fraction and dates of analyses.     

Ultrasound-assisted extraction and on-line LC–GC–MS for determination of polycyclic aromatic hydrocarbons (PAH) in urban dust and diesel particulate matter

A method has been developed for determination of polycyclic aromatic hydrocarbons (PAH) in particulate matter from ambient air and diesel exhaust emissions. It is reproducible and accurate and, compared with similar methods for analysis of individual PAH components in complex matrices, it is relatively fast and simple. Single PAH components can be determined in samples of particulate matter from ambient air and diesel exhaust emissions with LOD of approximately 1 pg/sample. Further, sample throughput is high, because more than 20 samples can be extracted and prepared for analysis in one working (8-h) day. The particulate matter is subjected to ultrasound-assisted extraction, a technique that is shown to extract PAH from particulate material with efficiencies fully comparable with those of Soxhlet extraction. An aliphatic/PAH-enriched fraction is obtained by solid-phase extraction before isolation, separation, and identification/quantification of PAH by on-line liquid chromatography–gas chromatography–mass spectrometry. The method was validated by analysis of US National Institute of Standards and Technology (NIST) Standard Reference Materials (SRM) 1649a, Urban Dust, and 2975, Diesel Particulate Matter. Results from the method are in good agreement with the NIST-certified PAH concentrations and with NIST reference PAH concentrations.     

Polycyclic aromatic hydrocarbons in Ya-Er Lake (Hubei, China): sources and distribution

Sources and distribution of polycyclic aromatic hydrocarbons (PAH) in the Ya-Er Lake area (Hubei, China) sediment cores of 3 ponds in the shallow Ya-Er Lake were investigated for 16 PAH. Analytical procedure included extraction by ultrasonication, clean-up by gel-permeation and quantification by HPLC with fluorescence detection. The total PAH amount in sediment samples of the Ya-Er Lake ranged from 68 to 2242 μg/kg. Concentrations decreased from pond 1 to pond 3 and from upper to lower sediment layers. In addition a soil sample from Ya-Er Lake area showed a total PAH amount of 58 μg/kg. The PAH pattern in lower sediment layers were similar to that of the soil sample which indicates an atmospheric deposition into the sediments prior to 1970 only. The PAH profile of upper sediment samples, which differs completely from that of lower layers, may be explained by a gradually increasing input of mixed combustion and raw fuel sources since 1970. Therefore the origin of increased PAH contamination in Ya-Er Lake during the last 3 decades has been probably an industrial waste effluent in pond 1.     

Characterisation of Sugar Cane Combustion Particles in the Araraquara Region, Southeast Brazil

Biomass burning is an important primary and secondary source of aerosol particles. The presence of carbonaceous particles in the respirable size range makes the study of this fraction important in view of possible health and climatic effects. The annual burning of sugar cane plantations causes emission of huge amounts of pyrogenic particles. Aerosol samples were collected in Araraquara city, São Paulo state, Brazil, during the harvest season for fine and coarse particles and bulk; they were analysed by electron-probe microanalysis, including facilities for low-Z element determination (low-Z EPMA) and by energy-dispersive X-ray fluorescence (EDXRF), in order to investigate the elemental composition of individual particles and bulk samples, respectively. Numerical analysis of the EPMA results by hierarchical clustering shows high contributions of carbonaceous particles that can be distinguished mainly in two different types: biogenic and carbon-rich. Additionally, two significant contributions of aluminosilicate particles were identified: as rather pure aluminosilicates or mixed with carbonaceous species. The EDXRF results are compatible with those of aerosol particles in Amazon, which is nowadays one of the main sources of biogenic particles in the world.     

Analytical Determination of Polycyclic Aromatic Hydrocarbons in Gases from Coal Conversion by Synchronous Fluorescence Spectrometry.

Abstract

A method to analyze the most hazardous Polyclyclic Aromatic Hydrocarbons (PAH) (acenaphtene, anthracene, benzo(a) anthracene, benzo(a)pyrene, biphenyl, coronene, chrysene, dibenzo (a,h) anthracene, phenantrene, fluoranthene, fluorene, naphtalene and pyrene), by using excitation and energy constant synchronic fluorescence has been researched in depth in this study.

Spectral studies carried out allow characteristic peaks to be obtained for the qualitative identification of 8 from 11 PAH tested. From the quantitative and interference studies, the most important analytical characteristics (linear range, detection limit and reproduciblity) for the determination of ten of these compounds have been obtained.

The method was applied to the PAH determination in two different samples: 1) air filter samples for urban pollution control and 2) air samples from a laboratory scale coal carbonization oven. Fluorene (in the first type) and benzo (a) pyrene (in the second type), were identified and quantified.     

Interfacing ASE and HPLC for the Determination of PAH in Soil

A method is developed to couple an accelerated solvent extraction system (ASE) with high performance liquid chromatography (HPLC) for the analysis of PAH in soil samples. The resolution of HPLC is well maintained while the advantages of ASE, fast extraction, less solvent consumption and ease of operation,are well expressed. The precision and accuracy of this method are verified by a series of analysis of reference material and the precision of retention from multiple injection indicates minimum loss of chromatographic resolution by the interface of this technique. Detection limits for the studied PAH range from 0.07 ng/Kg to 0.21 ng/Kg with fluorescence detector.     

Closed-shell polycyclic aromatic hydrocarbon cations: a new category of interstellar polycyclic aromatic hydrocarbons

Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of polycyclic aromatic hydrocarbon (PAH) cations that explore both size and electronic structure effects on the infrared spectroscopic properties of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms (C(odd) PAHs); and (2) protonated PAH cations (HPAH+). Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a 'closed'-shell electronic configuration. The calculated spectra of circumcoronene, C54H18, in both neutral and (radical) cationic form are also reported and compared with those of the other species. Overall, the C(odd) PAHs spectra are dominated by strong CC stretching modes near 1600 cm(-1) and display spectra that are remarkably insensitive to molecular size. The HPAH+ species evince a more complex spectrum consistent with the added contributions of aliphatic modes and their generally lower symmetry. Finally, for both classes of closed-shell cations, the intensity of the aromatic CH stretching modes is found to increase with molecular size far out of proportion with the number of CH groups, approaching a value more typical of neutral PAHs for the largest species studied.     

Determination of trace PAHs in seawater and sediment pore-water by solid-phase microextraction (SPME) coupled with GC/MS

A fast and reliable method for the determination of trace PAHs (polynuclear aromatic hydrocarbons) in seawater by solid-phase microextraction (SPME) followed by gas chromatographic (GC) analysis has been developed. The SPME operational parameters have been optimized, and the effects of salinity and dissolved organic matter (DOM) on PAHs recoveries have been investigated. SPME measures only the portion of PAHs which are water soluble, and can be used to quantify PAH partition coefficient between water and DOM phases. The detection limits of the overall method for the measurement of sixteen PAHs range from 0.1 to 3.5 ng/g, and the precisions of individual PAH measurements range from 4% to 23% RSD. The average recovery for PAHs is 88.2±20.4%. The method has been applied to the determination of PAHs in seawater and sediment porewater samples collected in Jiaozhou Bay and Laizhou Bay in Shandong Peninsula, China. The overall levels of PAHs in these samples reflect moderate pollution compared to seawater samples reported elsewhere. The PAH distribution pattern shows that the soluble PAHs in seawater and porewater samples are dominated by naphthalenes and 3 ring PAHs. This is in direct contrast to those of the sediment samples reported earlier, in which both light and heavy PAHs are present at comparable concentrations. The absence of heavy PAHs in soluble forms (<0.1-3.5 ng/L) is indicative of the strong binding of these PAHs to the dissolved or solid matters and their low seawater solubility.     

Comparison of immunoassay and gas chromatography-mass spectrometry for measurement of polycyclic aromatic hydrocarbons in contaminated soil

Polycyclic aromatic hydrocarbons (PAHs) are frequently encountered in the environment and may pose health concerns due to their carcinogenicity. A commercial enzyme-linked immunosorbent assay (ELISA), was evaluated as a screening method for monitoring PAHs at contaminated sites. The ELISA was a carcinogenic PAH (C-PAH) RaPID assay testing kit that cross-reacts with several PAHs and utilizes benzo[a]pyrene (BaP) as a calibrator. Soil samples were extracted with 50% acetone in dichloromethane (DCM) for analysis by ELISA and gas chromatography-mass spectrometry (GC-MS). The overall method precision was within ±30% for ELISA and within ±20% for GC-MS. Recovery data for spiked soils ranged from 46 to 140% for BaP as determined by ELISA. Recoveries data of the GC-MS surrogate standards, 2-fluorobiphenyl and chrysene, were greater than 70%. The GC-MS procedure detected a total of 19 priority PAHs (2-6-ring PAHs) including seven probable human carcinogens (4-6-ring B2-PAHs). The ELISA results were compared to GC-MS summation results for the total 19 target PAHs as well as for the subset of the seven B2-PAH compounds. For all soil samples, the PAH concentrations derived from ELISA were greater than the sum of B2-PAH concentrations obtained by GC-MS. ELISA determinations were also frequently greater than the results obtained by GC-MS for the total 19 PAH compounds. This discrepancy can be expected, since the ELISA is a screening assay for the detection of several related PAHs while the GC-MS procedure detects priority PAH compounds. Thus, only a subset of PAHs (e.g. 19 PAHs) in the soil samples were measured by GC-MS while additional PAHs, including alkylated PAHs, and PAH derivatives have been demonstrated to be cross-reactive in the C-PAH ELISA. Results of paired tests show that the PAH data from ELISA and GC-MS methods are significantly different (P<0.001), but highly correlated. The ELISA data had a strong positive relationship with the GC-MS summation data for the B2-PAHs as well as for the 19 PAHs targeted by the GC-MS method. Results indicate that the ELISA may be useful as a broad screen for monitoring PAHs in environmental samples.     

钯(Ⅱ)-泛昔洛韦螯合物与铬天青S相互作用的共振瑞利散射光谱及其分析应用

在pH值为2.5～3.5的Britton-Robinson缓冲溶液中,泛昔洛韦与钯(Ⅱ)相互作用形成1∶1的螯合阳离子,并进一步与铬天青S反应形成1∶1的离子缔合物。该反应可引起共振瑞利散射(RRS)光谱的显著增强并产生新的RRS光谱,最大RRS波长位于367 nm。在一定范围内,共振瑞利散射增强(ΔIRRS)与泛昔洛韦的质量浓度成正比,其线性范围为0.02～2.4 mg/L。该方法的灵敏度高,对泛昔洛韦的检出限为3.6μg/L。实验考察了适宜的反应条件以及共存物质的影响。应用计算化学软件Gaussview3.07和Gaussian03W,采用密度泛函法,在B3LYP/6-31G基组水平上计算了泛昔洛韦的电荷分布,对反应机理和RRS增强的原因进行了讨论。基于Pd(Ⅱ)-泛昔洛韦-铬天青S体系三元离子缔合物的RRS光谱,发展了一种简便、快速、灵敏测定泛昔洛韦的新方法。此方法用于胶囊和尿样中泛昔洛韦的测定,结果满意。     

Miniaturisated method for the analysis of polycyclic aromatic hydrocarbons in leaf samples

A new methodology is proposed for monitoring 16 priority polycyclic aromatic hydrocarbons, using tree leaves as passive samplers, by means of a mini-ultrasonic probe coupled with reversed-phase liquid chromatography (RP-LC) and fluorescence (FL) detection. Separation and detection of the 16 PAHs were completed in 19 min, using a 3 μm (particle size) C₁₈ column RP-LC with acetonitrile–water gradient elution. The ultrasonic probe device used was equipped with a 2 mm titanium tip, and sample and solvent amounts used were just 50 mg and 1 mL, respectively. Multivariate optimisation of the variables affecting extraction was conducted by means of full factorial analysis to determine which of the variables were significant. A central composite design was applied to define surface responses and to calculate optimal values for the variables. The accuracy of the method was determined by both analysis of a Certified Reference Material with a similar matrix (IAEA-140 OC, seaweed) and by comparison of the results obtained with those from a previously developed method. The proposed analytical method avoids some of the main problems encountered in the determination of PAH in complex matrices; no clean-up step is necessary, consequently sample preparation time and costs can be significantly reduced. The developed method was applied to determine PAH in leaf samples from medlar and red and white mangrove trees, situated near PAH pollution sources.