Levels of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in sediment of bitumen deposit impacted area

Polycyclic aromatic hydrocarbons and polychlorinated biphenyls were investigated in sediment of bitumen deposit impacted area of Agbabu, Nigeria, to determine the present level of contamination with these toxic compounds prior to exploitation. Samples were collected during the dry season (March) and the wet season (August) of year 2008. Analysis was carried out with gas chromatography using mass spectrometry detector for polycyclic aromatic hydrocarbons and flame ionization detector for polychlorinated biphenyls. In the dry season sum of concentration of PAHs ranged from zero to 0.12 ± 0.06 ppm, while in the wet season the minimum was 0.18 ± 0.07 ppm and the maximum was 1.04 ± 0.16 ppm. Most of these values were higher than sum of polycyclic aromatic hydrocarbons concentrations of 1–10 μg/kg indicating that they were likely to come from anthropogenic sources. Average concentrations of PAHs such as naphthalene and benzo (a) pyrene obtained in sediment in the wet season in some of the stations were higher than recommended limits. The linear regression analysis between sum of concentrations and percentage organic carbon showed no significant correlation in sediment in the dry season (r² = 0.0025) and in the wet season (r² = 0.1345). The predominance of 4–6 ringed polycyclic aromatic hydrocarbons and the ratios between pairs of individual polycyclic aromatic hydrocarbons showed that they are likely to have come from pyrolytic sources. No polychlorinated biphenyl congener was detected in the samples.     

Survey of polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons in Jiaxing city, China

Polycyclic aromatic hydrocarbon (PAH) and nitrated PAH (NPAH) products are toxic. Thus, determination of their concentrations is of great interest to researchers of soil and water pollution control. In this work, soil samples, surface water samples, and groundwater samples were collected, and the concentrations of 16 priority PAHs and 15 NPAHs were determined using an HPLC-ultraviolet detector. Results showed that the total PAH concentrations ranged within 489.69–1,670.11 ng/g (average = 905.89 ng/g) in soil samples, 4.00–23.4 μg/l (average = 9.84 μg/l) in surface water samples, and 2.14–22.3 μg/l (average = 8.37 μg/l) in groundwater samples. The NPAH concentrations were one to two orders of magnitude lower than the PAH concentrations and ranged within 22.72–128.70 ng/g (average = 63.88 ng/g) in soil samples. 2-Nitropyrene and 6-nitrochrysene were the most abundant compounds, accounting for about 14.3 and 26.5 %, respectively. Source analysis revealed that most PAHs originated from coal combustion around the study area, whereas NPAH studies suggested that the primary emission of gasoline engines and daytime OH reactions were the dominant sources of these compounds.     

Determination of hydrocarbon distributions in oils and sediment extracts by gas chromatography—high resolution mass spectrometry

The distributions of steroid and triterpenoid hydrocarbons in crude oils and sedimentary rock extracts can be routinely determined by the direct injection of the sample into a gas chromatograph coupled to a mass spectrometer (GC-MS). The mass spectrometer is operated at a resolution of about 2500 (10% valley), and only the ion intensities at selected accurate mass values, diagnostic of the structural types of interest, are monitored throughout the analysis. The distributions, so obtained, find application in the assessment of the source and thermal maturity of crude oil accumulations in the subsurface. This technique eliminates chromatographic separation steps and combines two analyses in one. Thus, more geological samples and reference mixtures may be analyzed in a given time.     

Vertical profile of polycyclic aromatic hydrocarbons in a sediment core from a reservoir in Osaka City

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured in a dated sediment core from a reservoir at Osaka City, Southwest Japan. The sediment core consisted of deposits collected over a period of almost 70 years whose PAH content would serve as a historical record of atmospheric environment at Osaka City. Total PAH concentrations varied from 4.2 to 26 mg kg⁻¹ dry wt, and peaked in the 1940s, reflecting the occurrence of a large fire due to air attacks during World War II. The results indicated that warfare had the largest impact on atmospheric environment in Osaka City. Total PAH concentrations decreased in the post-war period except for a small peak. In the 1950s, there was a downward trend from the 1970s to the present. These trends can be ascribed to the growth of industrial activities and the regulation of atmospheric pollutant emissions, respectively.     

Identification of steranes and tritepanes in geolipid extracts by high-resolution gas chromatography and mass spectrometry

One method for the analysis of complex organic mixtures from geological sources is the use of high-resolution gas chromatographic data together with mass spectra obtained by combined gas chromatography-mass spectrometry (gc-ms). The present study involved examination of a variety of authentic triterpenoid alkanes (triterpanes) and steroid alkanes (steranes) for reference purposes, by measurement of their Kovats indices on OV-101 and Dexsil 300 liquid phases, and by the recording of their low-resolution mass spectra by gc-ms. These measurements provide reference data for analysis of the triterpenoid alkanes in geological samples and show that mass spectrometry is a valuable technique for triterpane analysis, permitting in many cases gross structural assignments which may be refined by a comparison of Kovats indices with those of authentic standards.     

吹扫捕集-气相色谱-质谱法测定土壤中挥发酚的方法研究

文章研究了吹扫捕集-气相色谱-质谱法测定土壤中挥发酚的方法,分析了吹扫捕集各参数对挥发酚测定的影响,优化了吹扫捕集条件和气相色谱-质谱条件.通过与索氏提取技术对比,证明吹扫捕集-气相色谱-质谱法在实际样品检测中具有操作简便、分析周期短、试剂用量少、干扰小等优点,适用于测定沸点较低、溶解度较小的挥发酚,推荐选择经典的索氏提取技术测定沸点较高、溶解度较大的挥发酚.     

Significance of polycyclic aromatic hydrocarbons (PAHs) in Permian/Triassic boundary sections

In this study the abundances of several polycyclic aromatic hydrocarbons (PAHs Table 1, I–XXI) have been measured throughout three Permian/Triassic (P/Tr) sections from Meishan (South China), Kap Stosch area (East Greenland) and Peace River Basin (Western Canada). Dibenzothiophene (I) and dibenzofuran (II) were found to decrease in abundance just before or shortly after the P/Tr transition in all three sections while perylene (III) was observed to increase in abundance at the onset of the main extinction horizon (bed 25) in Meishan. Perylene has been attributed to a wood degrading fungal source and, therefore, it seems possible these phenomena are related to the demise of land plants. Further, distinct patterns of various combustion-derived PAHs occurring in each section imply that forest fire events occurred within the Late Permian and Early Triassic. In the Meishan section high amounts of combustion-derived PAHs [pyrene (IV), fluoranthene (V), benzo[a]anthracene (VI), benzofluoranthenes (sum, i.e. VII), benzo[a]pyrene (VIII), benzo[e]pyrene (IX) and coronene (X)] occur within bed 25, also containing ash attributed to the fallout from massive volcanic eruptions in Siberia and/or China.     

Sample preparation and analytical techniques for determination of polyaromatic hydrocarbons in soils

Polyaromatic Hydrocarbons (PAHs) have been determined in soil samples for many years. PAHs can arise in the environment from natural sources, oil and petroleum products and combustion processes. Although oil spills influence PAHS concentrations in local areas, the major sources of PAHS are anthropogenic and derived from land based combustion sources. PAHs are globally distributed and the highest concentrations generally occur close to urban centres. Monitoring is essential during the assessment and remediation. It makes further demands on the analytical methods used, since the transformation products are often present in lower concentrations than the parent PAHs and they may be difficult to identify in the complex mixtures found in these samples. It is therefore essential to use powerful analytical tools to fractionate, separate and identify the analyses in the samples. In this paper we review those aspects relating to the analysis and monitoring of PAHs in soils. The aim is to provide an overview of current knowledge, so as to assess the need for future monitoring of PAHs and the present capability for their analysis. Further monitoring of PAHs is justified because of their ubiquity in the environment, their persistence and bioaccumulative properties and their potential for toxicity both to aquatic organisms and human consumers.     

Soil contamination by polycyclic aromatic hydrocarbons at natural recreational areas in Delaware,USA

As a US east coast state with a major income from outdoor recreation and tourism, Delaware highly values its environmental quality and natural resources. However, no results on polycyclic aromatic hydrocarbons (PAHs) contamination in soil at natural recreational areas (NRAs) in the state have been reported. In this study soil samples from seven state parks, two city parks, two state forests, and two national wildlife refuges in Delaware were analyzed for the concentrations of 12 selected PAHs. Results indicated that the median concentration of total PAHs in urban, suburban, and rural NRAs was 1,159, 138, and 130 μg/kg, respectively. Based on the classification proposed by Maliszewska-Kordybach, soil PAH contamination level at almost all sampling sites in urban NRAs was classified as contaminated or heavily contaminated, while that at sampling sites in suburban and rural NRAs was classified as not or weakly contaminated. Principal component analysis showed that all these areas share the same independent variable, which may be composed of one or more contribution sources. Pyrogenic processes were inferred to be the major source of soil PAH contamination in Delaware NRAs. Individual PAH concentration at all sampling sites were observed below the limit of Canadian Quality Guidelines except for site F3, where the concentration of benzo[b]flouranthene, benzo[k]flouranthene, and benzo[a]pyrene was found to exceed the limit by 88.3, 125, and 281 %, respectively. Further investigation on PAH contamination and possible remediation in area F are recommended.     

Toxicity and genotoxicity of industrial soils polluted by polycyclic aromatic hydrocarbons (PAHs)

Three soil samples polluted by PAH were assessed for both acute (Vibrio fischeri [Microtox® test], Daphnia magna, Thamnocephalus platyurus) and chronic (Pseudokirchneriella subcapitata) toxicity, as well as for genotoxicity (Vibrio fischeri M169, [Mutatox® test]). Bioassays were performed on soil water leachates and on soil solvent extracts to characterise not only the fraction of water soluble pollutants but also to evaluate less soluble and soil-bound pollutants. The toxicity of the water leachates was low to moderate (from 0 to 30 toxic units) whereas the toxicity of the methanol extracts was about 100 to 10,000 toxic units. Although only slightly toxic, the genotoxicity of water leachates was clearly demonstrated. This finding shows that acute and chronic toxicity assays alone may not be sufficient to characterize soil hazards. A step procedure to characterise soil ecotoxicity is therefore proposed which allows one to study the pollutant mobility, toxicity and genotoxicity. It can be used to identify the hazard, to classify soil hazards and thus map contaminated sites, to assess the success of treatment and finally to monitor rehabilitated sites.     

表层岩溶带土壤中多环芳烃分布特征及来源解析

利用气相色谱-质谱联用仪(GC-MS)对表层岩溶泉域土壤中的16种优控的多环芳烃(Polycyclic Aromatic Hydrocarbons, PAHs)含量进行了分析,并对其组成、污染水平和来源进行了探讨。结果表明,16种优控PAHs在表层岩溶泉域土壤中的检出率为100%,其含量介于439.19~3329.72ng/g之间,平均值为1392.44ng/g,7种致癌性PAHs占总量的26%。PAHs的组成特征受地形的控制,随着海拔升高,低环PAHs所占比例升高,高环PAHs比例降低。同分异构体比值分析表明,研究区土壤中的PAHs主要来自于煤、生物质和石油的燃烧排放。研究区土壤中16种PAHs的TEQcarc值介于18.65~501.13ng/g,平均值为140.57ng/g。7种致癌性PAHs占总TEQcarc的比例达到96.8%。研究区表土中,后沟泉域的污染程度最大,次之是兰花沟泉域和柏树湾泉域,水房泉泉域的污染程度最小,但由于柏树湾泉域松针落叶中BaP、PAHs含量较高,松针落叶中PAHs含量分别高达36.36ng/g和2370.1ng/g,土壤生态风险评价中应考虑松针落叶层的潜在影响。      

Preliminary assessment of trace metals and polycyclic aromatic hydrocarbons in the sediments

Total concentrations of Cd, Cr, Co, Fe, Pb, Ni, Mn and Zn were determined by atomic absorption spectrophotometry in the surface sediments of Taylor Creek, Southern Nigeria. The most concentrated trace metals, ranging from 113.2 to 5160.7 mg/g-dry weights were Fe, Pb, Mn, Ni and Zn. There was no significant variation in sediment-associated metal levels (P>0.05). The metal pollution index was highest at Agbia/Nedugo and is attributed to local contamination of the Creek. The concentrations of low molecular weight polycyclic aromatic hydrocarbons (PAHs) were also detected and quantified in the sediments by capillary gas chromatography equipped with a flame ionization detector. The concentration levels of 178.1-1266.3 mg/g-wet weights were high for the PAHs. The results indicate that the pollutants, which are bio-accumulatable, could contribute to inferior biodiversity, and shifts in community composition from sensitive to tolerant taxa.     

Vertical distribution and source identification of polycyclic aromatic hydrocarbons in anoxic sediment cores of Chini Lake, Malaysia: Perylene as indicator of land plant-derived hydrocarbons

Four anoxic sediment cores were collected from Chini Lake, Malaysia in order to investigate the variability of polycyclic aromatic hydrocarbon (PAH) and perylene concentrations. The study also determined significant differences of perylene concentrations in different sediment layers. Total PAH concentrations ranged from 248 to 8098 ng g⁻¹ in the samples. Diagnostic PAH ratios such as methylphenanthrenes/phenanthrene (MP/P), phenanthrene/anthracene (P/A) and fluoranthene/(fluoranthene + pyrene) (Fl/(Fl + Py) revealed a dominance of pyrogenic influences and partial petrogenic inputs to the top sediment layers. Perylene concentrations were high in the top layers (<12 cm) and increased with increasing depth. There is a significant positive correlation (r = 0.705, p = 0.01) between perylene concentrations and TOC. Analysis of variance (ANOVA) and LSD revealed significant differences (p < 0.05) in TOC-normalized perylene concentrations between the upper (<12 cm) and bottom layers (>12 cm). The average perylene concentrations accounted for 26–50% (0–12 cm) and 50–77% (12–36 cm) of pentacyclic-aromatic hydrocarbon isomers (PAI) present whereas it made up 10–34% (0–12 cm) and 46–66% (12–36 cm) of the total PAH. The average pyrene concentrations decreased with increasing depth and accounted for 62% (0–3 cm), 20–23% (3–12 cm) and 3–1.4% (12–36 cm) of perylene present. The results of hierarchical cluster analysis based on these ratios suggested different input sources for the top and bottom layers. It is concluded that the activity of termites on woody plants produced perylene which is supplied to the lake by run-off from the heavy and frequent rains in this Asian tropical climate. In addition, there was also in situ formation of perylene in the bottom layers due to diagenetic processes.     

Use of comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry for the characterization of biodegradation and unresolved complex mixtures in petroleum

A comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOFMS) method has been developed for separation of a series of petroleum samples using a polar/non-polar column set configuration. Groups of oils were selected to provide samples from the same oil family to assist in comparison of compositional changes during biodegradation. The groups also represented different sources and ages to allow an assessment of the application of GC × GC for the differentiation of oil source, as well as fluid history. The increased resolution and separation afforded by the GC × GC technique provides more complete compositional information on complex biodegraded oil samples than one-dimensional GC, and improves the ability to study biodegradation trends. Among the components identified, it is proposed that alkyl-decahydronaphthalenes constitute a significant contribution to the UCM.     

Biomarkers in crude oil revealed by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry: Depositional paleoenvironment proxies

Crude oil samples from two basins were analyzed using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC–TOFMS) to better understand the compositional heterogeneity of branched-cyclic hydrocarbons. GC×GC–TOFMS and conventional GC–MS results were compared. GC×GC–TOFMS revealed a wide range of compounds, including tricyclic, tetracyclic and pentacyclic terpane series, rearranged hopanes, methyl hopanes, secohopanes, onoceranes and steranes. Assignment of methyl hopane and 8,14-secohopane series other than onocerane isomers was only possible due to the high peak capacity and sensitivity of GC×GC. The oils comprised a mixture of two end members: non-biodegraded oil with abundant tricyclic terpanes and hopanes, and severely biodegraded oil with abundant 8,14-secohopane and demethylated tricyclic terpanes. A predominance of two distinct series, 3β-methylhopane and onocerane, was detected only in the lacustrine samples (classification based on biomarker parameters). In contrast, the predominance of a 2α-methylhopane series and lack of onocerane were found only for the marine oil sample. The results suggest that the distribution of 3β- and 2α-methylhopane series and the presence or absence of onocerane isomers reflect genetic differences in the source organic matter and that these compounds are new classes of biomarkers that can used as depositional paleoenvironment proxies.     

Historical records and the sources of polycyclic aromatic hydrocarbons in the East China Sea

The coastal cities are the most advanced regions in China. In the past few decades, the environment changed very significantly due to large scale human activities in the coastal regions. Polycyclic aromatic hydrocarbons (PAHs) in three dated sediment cores from the west coast of the Yellow Sea (core A01), the Yangtze River estuary (YRE; core A02) and the Oujiang River estuary (ORE; core A03) were analyzed to reconstruct the environmental evolutionary process of the east China coastal region over the past century. In the three cores, PAHs concentrations were increased rapidly. Lower concentrations of PAHs were measured in core A02 than in cores A01 and A03. The vertical variation of PAHs in the YRE was dominated by the petrogenic sources. Historical records of PAHs in the ORE were controlled by pyrolytic sources. PAHs on the west coast of the Yellow Sea were contributed by the two sources.     

Characterization of aromatic steroids and hopanoids in marine and lacustrine crude oils using comprehensive two dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-TOFMS)

The distribution of the aromatic steroids and hopanoids in six crude oils was determined using comprehensive two dimensional gas chromatography time-of-flight mass spectrometry (GCxGC-TOFMS) in order to improve their identification and application in geochemical studies. Co-elution between monoaromatic and triaromatic steroids and benzohopanes and their methylated homologues, which are commonly observed in ¹D conventional GC, were resolved, with GCxGC facilitating recognition of the compounds. One important feature was that, despite the oils showing mid-oil window maturity characteristics, the distribution of long chain aromatic steroids decreased in lacustrine samples vs. marine samples. This difference in the distribution of long chain and short chain aromatic steroids may reflect the different origins of these oils although this aspect needs further evaluation.     

Uptake, accumulation and translocation of polycyclic aromatic hydrocarbons by winter wheat cultured on oily sludge-amended soil

The purpose of this study is to comparatively investigate the plant uptake, accumulation and translocation behaviors of polycyclic aromatic hydrocarbons (PAHs) as priority pollutants in soil contaminated with oily sludge. The influence of different oily sludge application doses on the uptake of contaminants was studied together with the profile of individual PAH in roots, straws and leaves of winter wheat. Pot experiments were conducted using oily sludge application doses of 0, 5, 10, 15 and 20 percent, respectively. The total PAHs contents of control soil and oily sludge were 16.96 and 3504.66 μg/g, respectively. Analysis for the contents of the 16 PAHs was carried out with a HPLC-UV using plant tissue samples obtained at the 265th day of growth. The total PAHs contents in treated winter wheat were 9.02-334.81 ng/g for roots, 8.45-336.52 ng/g for straws and 10.70-406.32 ng/g for leaves. In addition to 5% of oily sludge dose, the total PAHs content in leaves was always highest under other doses of oily sludge application. With respect to individual PAH, the content did not show a significant plant tissue related trend. However, both the total content and individual content of PAHs in treated winter wheat tissues did increase with increasing oily sludge application dose. Another analysis for the control soil indicates that the degradation rate of PAHs was significantly enhanced by winter wheat after 265 days of growth based on the residual concentrations of PAHs in planted and unplanted soils.     

Fluxes of polycyclic aromatic hydrocarbons to marine and lacustrine sediments in the northeastern United States

Polycyclic aromatic hydrocarbons (PAH) were measured in dated sediment cores from several sites in the northeastern United States (Lake Superior, Isle Royale, Somes Sound, Hadlock Lower Pond. Coburn Mountain Pond, and outer Boston Harbor). Fluxes of ten PAH were measured for each site for the periods roughly corresponding to the present, 1950, and 1900. Remote sites consistently demonstrated present-day deliveries of individual PAH near 1 ng cm^?2 yr^?1, probably reflecting the atmospheric fallout of these combustion-derived pollutants. Sites located nearer to urban centers showed much greater current inputs (average of 35 ng cm^?2 yr^?1 for most individual PAH), presumably caused by greater fallout of PAH-laden particles nearer their urban origins, augmented by runoff delivery of PAH-contaminated sediments. Differences in the relative abundances of individual PAH at remote-versus-urban locations support suggestions of different delivery mechanisms. The sedimentary historical records of PAH inputs confirm the previous finding that anthropogenic activities began introducing large quantities of PAH into the environment about 80–100 years ago.