Polycyclic aromatic hydrocarbons in surface water and soil in the vicinity of fuel-oil spillage from a tank farm distribution facility, Esuk Utan, Calabar Municipality, Nigeria

The concentrations of total polycyclic aromatic hydrocarbons (??PAHs) and 16 individual PAH compounds in 6 surface water and 44 soil samples collected from the vicinity of spilled fuel from a pipeline which carries fuel from a jetty to the tank farm were analyzed. The ??PAHs concentrations in surface water ranged from 0.37 to 99.30?mg/l with a mean concentration of 57.83?mg/l. The ??PAHs concentrations in water are of several orders of magnitude higher than in unpolluted water and some national and international standards including in some surface water in other parts of the world. This suggests that the surface water of the area were heavily polluted by anthropogenic PAHs possibly from the spills. The total PAH concentrations in soil ranged from 16.06 to 25,547.75???g/kg with a mean concentration of 2,906.36???g/kg. ??PAH concentrations of the seven carcinogenic PAH compounds in soil varied between 0.02 and 97,954???g/kg. In terms of composition of patterns in surface water and soil, the PAHs were dominated by four and three rings. The distribution pattern showed marked predominance by low molecular weight compounds. In comparison with ??PAHs concentrations in other part of the world, the total PAH concentrations of this area were higher than those reported for some urban soils in some regions of the world. The ratios of Phe/Ant, Flu/Pyr, Flu/(Flu?+?Pyr), and BaA/(BaA?+?Chyr) in both water and soil indicated various sources of PAH in the area. These sources include fuel spills, burning of motor tyres and vegetation, vehicle repairs and washing, motor exhaust and fire wood burning from cooking.     

Sources and bioavailability of polynuclear aromatic hydrocarbons in Galveston Bay, Texas

Oyster and sediment samples collected from six sites in Galveston Bay from 1986 to 1998 were analyzed for polynuclear aromatic hydrocarbons (PAHs). Total concentrations of parent PAHs in oysters ranged from 20 ng g⁻¹ at one site to 9,242 ng g⁻¹ at another and varied randomly with no clear trend over the 13 year period at any site. Concentrations of alkylated PAHs, which are indications of petroleum contamination, varied from 20 to 80,000 ng g⁻¹ in oysters and were in higher abundance than the parent PAHs, indicating that one source of the PAH contaminants in Galveston Bay was petroleum and petroleum products. Four to six ring parent PAHs, which are indicative of combustion source , were higher than those of 2–3 ring parent PAHs, suggesting incomplete combustion generated PAHs was another source of PAHs into Galveston Bay. Concentrations of parent PAHs in sediments ranged from 57 to 670 ng g⁻¹ and were much lower than those in oysters. Sediments from one site had a high PAH concentration of 5,800 ng g⁻¹. Comparison of the compositions and concentrations of PAHs between sediment and oysters suggests that oysters preferentially bioaccumulate four to six ring PAHs. PAH composition in sediments suggests that the sources of PAH pollution in Galveston Bay were predominantly pyrogenic, while petroleum related PAHs were secondary contributions into the Bay.     

The role of zooplankton fecal pellets in the sedimentation of polycyclic aromatic hydrocarbons in Dabob Bay,Washington

Polycyclic aromatic hydrocarbon (PAH) compositions were determined in plankton, sediment-trap-collected particulate material and sediment cores from Dabob Bay using a high performance liquid Chromatographie (HPLC)/fluorescence technique. The annual flux of individual PAH measured in a series of sediment traps was compared with the flux of corresponding compounds determined from ²¹⁰Pb dated bottom sediments. Systematic seasonal variations in the fluxes and concentrations of PAH, Al and organic carbon in the trap-collected particulates and seasonally collected plankton were also investigated to determine whether or not PAH are associated with either terrestrial or marine-derived materials.Concentrations of all PAH studied increased tenfold within the last 80–100 yr of sediment deposition, except for perylene which displayed a reasonably constant concentration profile. This suggests at least two sources contribute to the observed sedimentary PAH compositions in Dabob Bay, i.e., anthropogenic combustion and a natural source. Plankton and sediment trap-collected particulates contained PAH mixtures qualitatively similar to underlying surface sediments. Microscopic examination indicated fecal pellets were the major form of particulate material in the sediment traps. The fecal pellets collected in the sediment trap time series quantitatively account for essentially 100% of the PAH fluxes measured in the ²¹⁰Pb dated sediments, implying Zooplankton fecal pellets control the removal of PAH to Dabob Bay sediments. These measurements provide clear evidence that the PAH studied are not produced after sediment deposition. The observed seasonal covariations of PAH and Al in both sediment trap and plankton samples further indicate that PAH originate from terrestrially-based sources, are introduced into the marine environment by runoff and erosion or atmospheric deposition and are not produced by marine plankton.     

The global distribution of polycyclic aromatic hydrocarbons in recent sediments

Polycyclic aromatic hydrocarbons (PAH) and their alkyl homologs are distributed in sediments throughout the world. The qualitative PAH pattern is remarkably constant for most of the locations studied, and the quantitative PAH abundance increases with proximity to urban centers. These findings are consistent with anthropogenic combustion's being the major source of these compounds. Two non-combustion sources of PAH have also been noted: retene coming from abietic acid and perylene probably coming from various extended quinone pigments.     

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.     

Weathering of fuel oil spill on the east Mediterranean coast, Ashdod, Israel

Residual fuel oil spilled into the sea from the Eshkol power station on 8 February, 1998 contaminated about 9 km of the foreshore north of the Ashdod harbour. A study of the aliphatic, polycyclic alkane and polyaromatic hydrocarbon (PAH) composition of the spilled oil shows rapid weathering in the early stages followed by gradual slowdown after about three months. Weathering of isoprenoids and PAH compounds and variation in Pr/Ph ratio appear to occur almost contemporaneously with that of n-alkanes, at a relatively moderate level of degradation, when much of the >C₂₀ n-alkane envelope is still well preserved. Depletion of various compounds in accordance with molecular size rather than molecular structure appears to imply that physical weathering processes, i.e. evaporation and perhaps flushing due to wave energy, might have played an important role in the degradation of the spilled residual fuel oil in this study case.     

Distribution of hydrocarbons in the estuarine area of the Northern Dvina River during seasonal flood

Heavy contaminant load released into the Northern Dvina River during flooding increased the concentrations of aliphatic (AHC) and polcyclic aromatic (PAH) hydrocarbons in water and bottom sediments. The composition of hydrocarbons was different from that of the summer low flow season. The concentrations of dissolved and particulate AHC ranged from 12 to 106 and from 192 to 599 μg/l, respectively, and bottom sediments contained from 26.2 to 329 μg/g AHC and 4 to 1785 ng/g PAH. As the transformation of AHC occurred at low spring temperatures, the alkane composition was shown to be dominated by terrigenous compounds, whereas more stable PAH showed elevated contents of petrogenic and pyrogenic compounds. It was also shown that the Northern Dvina-Dvina Bay geochemical barrier prevents contaminant input into the White Sea, i.e., acts as a marginal filter.     

Source Apportionment of PAHs Using Two Mathematical Models for Mangrove Sediments in Shantou Coastal Zone,China

Thirty-five surface sediment samples collected from three mangroves in Shantou coastal zone, China in 2007 were analyzed for a suite of polycyclic aromatic hydrocarbons (PAHs). Two mathematical models were used to determine the profiles and relative contributions of PAH sources to the mangroves. The two models are principal component analyses (PCA) with multiple linear regression analysis (MLR) and positive matrix factorization (PMF). Both models identified five factors and gave excellent correlation coefficients between predicted and measured levels of 16 PAH compounds, but the results had some differences. The PAH contribution rate attributed to vehicular emission sources identified by PCA-MLR was 37.20%, but the rate identified by PMF was only 12.37%. The main sources identified by PCA-MLR were combination of biomass/coal combustion and vehicular emissions, whereas the main source identified by PMF was only biomass/coal combustion. The PMF analysis was the preferred model for the paper data set.     

Urban and suburban storm water runoff as a source of polycyclic aromatic hydrocarbons (PAHs) to Massachusetts estuarine and coastal environments

Urban and suburban storm water runoff from ten locations in eastern Massachusetts was analyzed for 39 polycyclic aromatic hydrocarbons (PAHs) compounds. Similar profiles in PAH composition were observed for groups of samples and appear to reflect land use. The largest group includes, urban storm water from areas with a mix of industrial, commercial, and residential use. Fluoranthene, phenanthrene, pyrene, chrysene, and benzo (b) fluoranthene were the predominant compounds in this group, but lighter molecular weight PAHs were also present. Sources of PAHs to storm water include a combination of petroleum and combustion. The profile of PAH compounds in local atmospheric deposition was similar to urban storm water, but differed in several of the predominant compounds. PAHs in storm water could increase the levels of these compounds in nearshore sediments and may be the most important source of high molecular weight PAHs to these environments.     

Polycyclic aromatic hydrocarbons as an indicator of contamination of medicinal waters in the spas in the Sudetes mountains of Southwestern Poland

Thirteen polycyclic aromatic hydrocarbons (PAH) compounds have been identified in spa waters of 10 different health sources in the Sudetes region. In some of the waters the amount of PAH exceed the standard limits set up by the World Health Organization (WHO). The results obtained show that PAH can be a sensitive indicator of pollution of underground water.     

PAH refractory index as a source discriminant of hydrocarbon input from crude oil and coal in Prince William Sound,Alaska

Geochemical correlation and differentiation of hydrocarbons from crude oils and coals is difficult. The complex mixture of the hydrocarbon constituents and the dynamic nature of these constituents in the environment as they weather contribute to this difficulty. A new parameter, the polycyclic aromatic hydrocarbon (PAH) refractory index, is defined here to help in this correlation. The PAH refractory index is a ratio of two of the most refractory constituents of most crude oils, namely triaromatic steranes and monomethylchrysenes. These are among the most persistent compounds in oil after deposition in the environment and thus retain reliably the signature of the original petroleum input. This index is utilized in Prince William Sound (PWS) to differentiate three different oils, as well as to provide evidence that coal, not oil, is the dominant source of the PAHs which are prominent constituents of marine sediments from PWS and the Gulf of Alaska.     

Atmospheric sources and soil filtering of PAH content in karst seepage waters

The analysis of PAHs (polycyclic aromatic hydrocarbons) in karst environments has provided an assessment of the vulnerability of karst water and the study of PAH records in stalagmites. The major source of PAHs has generally been considered to be the soil. In this study, we report the quantification of PAHs in the ecosystem compartments of a mountain karst system over a snow-melting period and the spring to summer dry period. PAH profiles in karst seepage waters were consistently similar to those in wet deposits, following the change in PAH profiles between winter and summer periods. However, PAH signatures of atmospheric wet deposits were modulated by a loss of the high molecular weight PAHs, which appear to accumulate in soils. A PAH mass balance was calculated during a summer storm event. This mass balance suggests that dry deposits and canopy throughfall could account for the PAH abundance in karst seepage waters. This study demonstrates the ability of organic hydrophobic compounds to be directly transferred from the atmosphere or canopy into seepage waters, giving new emphasis to the study of PAHs recorded in stalagmites.     

大气干湿沉降: 地下河多环芳烃的重要来源——以广西清水泉地下河为例

为证实大气干湿沉降物是岩溶地下河中多环芳烃(PAHs)的来源,研究选择了某城市典型的岩溶地下河水源地作为研究地点,采用大气干湿采样器、聚氨酯泡沫(PUF)大气被动采样器分别采集大气及其干湿沉降物样品,同时采集地下河水样和分层采集流域土壤,利用气相色谱-质谱联用仪(GC-MS)测定了16种PAHs优先控制污染物。结果表明,地下河流域大气干湿沉降中PAHs的干湿沉降通量为147.26 ng·(m2·d)-1,流域PAHs沉降量为1943.8 g;大气中的PAHs浓度为45.33 ng·m-3;地下河水中PAHs浓度平均值为220.98 ng·L-1;土壤中PAHs浓度为38.72 ng·g-1;大气、降雨和土壤中PAHs组成以2~3环的萘、芴、菲、荧蒽、芘5种为主,地下河水中以芴、菲、荧蒽、芘、苯并[a]蒽、苯并[a]芘6种为主。利用地下河多介质中的16种PAHs成分谱、特征比值结合它们的物理化学性质进行PAHs的源解析,研究显示大气干湿沉降是岩溶地下河水中多环芳烃的主要污染源之一,这归因于岩溶地区防污性能的脆弱性。     

High molecular weight polycyclic aromatic hydrocarbons in hydrothermal petroleums from the Gulf of California and Northeast Pacific Ocean

Hydrothermal petroleums and heavy tars have been analyzed for polycyclic aromatic hydrocarbons (PAH) with molecular weights greater than that of coronene (300 da). Samples from the hydrothermal systems in the Guaymas Basin (Gulf of California) and in the Escanaba Trough and Middle Valley (Northeastern Pacific) were analyzed by gas chromatography-mass spectrometry and high pressure liquid chromatography with diode-array absorbance detection. Mass spectra and fluorescence spectra were used to characterize the compounds. Several large PAHs with six and more rings were identified among the heavy PAH. Production routes via one-ring build-up and Scholl-condensation are proposed to explain the observed structures. The variations in PAH concentrations and distributions between samples from different locales are a consequence of the hydrothermal conditions of generation, migration, and post-depositional alteration.     

The polycyclic aromatic hydrocarbon concentrations in soils in the Region of Valasske Mezirici, the Czech Republic

The polycyclic aromatic hydrocarbon (PAH) contamination of urban, agricultural and forest soil samples was investigated from samples obtained in the surroundings of Valasske Mezirici. Valasske Mezirici is a town located in the north-east mountainous part of the Czech Republic, where a coal tar refinery is situated. 16 PAHs listed in the US EPA were investigated. Organic oxidizable carbon was also observed in the forest soils. The PAH concentrations ranged from 0.86-10.84 (with one anomalous value of 35.14) and 7.66-79.39 mg/kg dm in the urban/agricultural and forest soils, respectively. While the PAH levels in the urban/agricultural soils are within the range typically found in industrialized areas, the forest soils showed elevated PAH concentrations compared to other forest soils in Western and Northern Europe. The PAH concentrations and their molecular distribution ratios were studied as functions of the sample location and the meteorological history. The soils from localities at higher altitudes above sea level have the highest PAH concentrations, and the PAH concentrations decrease with increasing distance from the town.     

Historical record of polycyclic aromatic hydrocarbons (PAH) and heavy metals in floodplain sediments from the Rhine River (Hessisches Ried, Germany)

The depth-related content of polycyclic aromatic hydrocarbons (PAH) and heavy metals was determined for two soil profiles (i.e. one Fluvisol and one Gleyic Cambisol) which developed in sediments from floodplains located at an old meander of the Rhine river. The meander had been cut off from the main river in 1829. The separation of the meander from the main river caused a change in sediment deposition (i.e. from sand to silt) which is clearly visible in the soil-profiles. Since that time, approximately 100 cm of sediments have accumulated due to temporary flooding of the area. Each soil profile was separated into 18 samples. The samples were analysed for their content of PAH after solvent extraction. Additionally, several trace elements (Co, Ni, Cd, Pb, Zn, Cr and Cu) were determined in the same sample set, and depth-related concentration profiles for both PAH and trace elements were developed. The distribution patterns of PAH with more than 3 condensed rings did not provide any evidence for PAH biodegradation or vertical transport after deposition of the sediments. Thus, in the case of PAH, the historical record can be derived not only from subhydric sediments but also from floodplain sediments. It was not possible to distinguish between atmospheric and fluvial input of PAH into the sediments from the observed distribution patterns due to the same origin of PAH from pyrolytic processes. A source determination of the PAH was not possible except for perylene, for which biogenic formation can be assumed. A comparison of the results shows that the depth-related PAH and trace element concentrations display similar trends over most of the total profiles. In the uppermost section of the profiles, the concentration of most trace elements declines whereas the PAH concentration remains high. This indicates the presence of different sources for PAH and trace elements in the last decades.     

Polycyclic aromatic hydrocarbons in an anoxic sediment core from the Pettaquamscutt River (Rhode Island,U.S.A.)

Fifteen sections from an anoxic sediment core were analyzed for polycyclic aromatic hydrocarbons (PAH). Two types of PAH were observed: (a) those from combustion sources such as pyrene and chrysene and (b) those from natural sources such as retene and perylene. The combustion PAH levels in core sections dated between 1900 and 1970 were much higher than in earlier sections; this indicated an anthropogenic origin of these PAH at this location. The perylene and retene core profiles show significant anomalies during the period 1850–1880. Organic carbon does not fluctuate markedly but δC-13 of organic carbon shows several unexplained excursions; one of which correlates with the perylene and retene anomalies.     

Using GC-MS/Combustion/IRMS to determine the C/C ratios of individual hydrocarbons produced from the combustion of biomass materials--application to biomass burning

Simultaneous mass spectral detection and stable carbon isotope analysis was performed on individual indigenous n-alkanes isolated from single C₄ and C³ plant species and on a series of aliphatic and polycyclic aromatic hydrocarbons (PAH) produced from the combustion of these same biomass materials. The analysis technique used a combined gas chromatograph-mass spectrometer/combustion/isotope ratio mass spectrometer (GC-MS/C/IRMS). Precision (2σ) for replicate measurements of individual compounds in standard solutions using this novel configuration ranged between 0.2 and 0.5‰ for n-alkanes and 0.3 and 0.8‰ for PAH. Accuracy of the n-alkane measurements ranged between 0.1 and 0.4‰ and that of the PAH measurements ranged between 0.2 and 0.9‰. Replicate GC-MS/C/IRMS measurements on the combustion-derived n-alkene/alkane pairs were performed to within a precision of between 0.1 and 1.1‰ and the precision for the combustion PAH was similar to the standard PAH solution. No notable isotopic effects were observed when altering the temperature of the combustion process from 900 to 700°C, or as a result of the individual n-alkenes/alkanes partitioning between the gaseous and condensate fractions. Combustion-derived n-alkenes/alkanes ranged from C₁₁ to C₃₁, and the C₄-derived n-alkenes/alkanes were approx. 8‰ more enriched in ¹³C than the C₃-derived compounds. Both the C₄ and C₃-derived n-alkenes/alkanes (C₂₀-C₃₀) were isotopically similar to the indigenous n-alkanes and were 2-3‰ more depleted in ¹³C than the lower mol. wt (C₁₁₁₁-C₁₉) n-alkenes/alkanes, suggesting an independent origin for the lower mol. wt compounds. Combustion-generated C₄ and C₃-derived 2-, 3-, and 4-ring PAH were also isotopically distinct (Δδ = 10‰). Unlike the n-alkenes/alkanes, no compound-to-compound variations were observed between the low and high mol. wt PAH. This study demonstrates that the isotopic composition of original plant biomass material is mainly preserved in the aliphatic hydrocarbons and PAH generated by its combustion. Consequently, analyses of these compounds in sediments impacted by fire occurrences may provide useful information about paleo-fire activity that may help elucidate the impact biomass burning may have had and could have on climate-biosphere interactions.     

贡嘎山海螺沟降雪中多环芳烃的短周期分布特征及来源分析

2013年1月在贡嘎山海螺沟3个不同采样点共收集了多个雪样,利用GC-MS分析了雪样中16种优控多环芳烃的含量,探讨了多环芳烃的短周期分布特征与来源,估算了采样点与排放源的直线距离。结果显示,海螺沟各采样点雪样中多环芳烃的总含量在163.7 ng/L~281.4 ng/L之间,其中菲的含量最高。雪样中2~4环多环芳烃占多环芳烃总量的百分比为92.0%~93.7%,表明污染来自较远距离传输,但主要排放源离海螺沟的直线距离不超过357 km。将雪层与气象资料的降雪期对应,结果表明从2012年11月到2013年1月这个短周期内,海螺沟雪样受多环芳烃污染的程度没有太大变化。对海螺沟雪样中的多环芳烃进行了来源分析,结果表明海螺沟雪样中的多环芳烃主要来自煤燃烧,不排除少部分木材燃烧,这一源解析结果与海螺沟及其周边地区主要以煤炭作为燃料的能源特征相吻合。