Origin of perylene in ancient sediments and its geological significance

The distributions of polycyclic aromatic hydrocarbons (PAHs) in sediments of three Upper Triassic to Middle Jurassic sedimentary sequences from the Northern Carnarvon Basin, Australia have been investigated. Perylene was found to be a major PAH component in the top Lower to base Middle Jurassic sediments that are immature or at low maturity. Its depth/age profiles are not related to the combustion-derived PAHs that have been believed to be produced during ancient vegetation fires before deposition. This suggests a diagenetic origin for perylene. The concentration of perylene in the sediments is proportional to the amount of terrestrial input, decreasing with distance from the source of land sediments. Its carbon isotope composition is slightly heavier than higher-plant derived PAHs, but still in the range of the terrestrially sourced PAHs including higher-plant PAHs and combustion-derived PAHs as suggested previously. Fungi are proposed to be the major precursor carriers for perylene in sediments based on the facts that (1) perylenequinone structures have been previously suggested to be the natural precursors for perylene; (2) perylenequinone pigments exist in many fungal bodies; (3) fungi have played an important role during geological processes.     

Perylene dominance in sediments from a subtropical high mountain lake

Perylene formation in sediments of water bodies has been a topic of continual discussion and debate. We report the concentration and age (ca. 660 yr) profiles of perylene and other polycyclic aromatic hydrocarbons (PAHs) in a sediment core from Emerald Peak Lake, the largest high mountain lake in Taiwan. Perylene is dominant at all depths of the sediment (ranging from 60% to 98% of total PAHs), a feature not commonly found in other sediments. The concentration profile of perylene with sediment age fits a first order kinetic model, which might be an indication of a steady sedimentary environment.     

Distribution and transport of hydrocarbons in surface sediments of the alaskan outer continental shelf

Surface sediments from the Outer Continental Shelf of Alaska were analyzed for hydrocarbons as part of an environmental survey sponsored by NOAA/BLM. Sediments were collected from the proposed oil lease areas of Beaufort Sea, southeastern Bering Sea, Norton Sound, Navarin Basin, Gulf of Alaska, Kodiak Shelf and lower Cook Inlet. Data on normal and branched alkanes and di- and triterpenoids from capillary gas chromatography (GC) and gas chromatography-mass spectrometry (GC/ MS) indicate that the area displays little evidence of petroleum hydrocarbons (i.e., seeps) except at a few isolated stations. Beaufort Sea sediments have the highest hydrocarbon budget, whereas Kodiak Shelf sediments have the lowest. The molecular markers of the hydrocarbons are of a mixed marine autochthonous and terrestrial allochthonous origin. Norton Sound and Cook Inlet sediments contain the highest levels of terrigenous lipids and Kodiak Shelf the lowest. The abundance of alkenes implies that relatively low oxidizing conditions exist in some of the depositional areas studied, suggesting that extraneous petroleum hydrocarbons introduced into these sediments would be expected to have a relatively long residence time. The distribution of polynuclear aromatic hydrocarbons (PAH) is complex and shows a pyrolytic origin. The data on perylene strongly favor the hypothesis that it is “performed” from terrigenous precursors and transported into the marine environment with no apparent in situ generation. Polynuclear aromatic hydrocarbons of diagenetic origin are probably dominant in Gulf of Alaska and Kodiak Shelf sediments.Two stations, north of Kalgin Island, in lower Cook Inlet and one in southeastern Bering Sea show typical weathered petroleum distribution of n-alkanes and triterpenoids. Probable pathways of transport and fate of petroleum hydrocarbons in case of an oil spill are also briefly discussed.     

三维全扫描荧光法探讨长江口邻近陆架有机沉积物来源

近年发展起来的三维全扫描荧光光谱主要由硬件PE650-40荧光分光计,PE-3600数据站和PE-660打印画图机和专用“SCANR”软件组成.激发和发射波长分别在220-600nm范围内进行全自动,交替,连续地扫描,以发射/激发波长和荧光强度的三维全扫描荧光光谱图,以及它们的等高线图来描述测量结果,用该项新技术研究东海长江口海域表层沉积物中多环芳炷浓度和它们的环数分布特征,还讨论了具有典型陆源高等植物特征的苝的浓度分布特征,结果表明沉积物中有机质主要来自长江入海陆源物随远离河口递减,在东经123°以西附近出现最高浓度值.     

Polycyclic aromatic hydrocarbons in sediments from the Pearl river and estuary,China: spatial and temporal distribution and sources

Polycyclic aromatic hydrocarbons (PAHs) were measured in surface sediments and dated core sediments from the Pearl river and estuary, China, to investigate the spatial and temporal variability of anthropogenic pollutants. The sediments from the sampling stations at the Guangzhou channel have the highest concentrations of PAHs, owing to contributions from the large amount of urban/industrial discharges from the city of Guangzhou. The significant decrease of PAHs concentrations in sediments from the Shiziyang channel is mainly attributed to the increasing degradation and desorption of low molecular weight PAHs and alkyl PAHs, and the dilution by less contaminated water and particles from the East river. The PAH contaminants were concentrated on the western side in the Lingding bay of the Pearl river estuary because of the hydrodynamic and sedimentation conditions. Based on the characteristics of the parent compound distributions (PCDs) and the alkyl homologue distributions (AHDs) of PAHs, the potential source of PAHs in sediments from each sampling station was identified. Results indicated that the pyrogenic (combustion) source, characterized by the abundance of parent PAHs, were predominant in the heavily contaminated station (ZB01) near the aging industrial area, and the petrogenic (petroleum- derived) PAHs were more abundant in the stations (ZB02, ZB03) adjacent to the petrochemical plant and shipping harbor. Sediments from Lingding bay show variable distributions of PAH composition and variety in the proportion of combustion and petrogenic sources for the PAHs in different stations. Perylene, a naturally derived PAH, was found to be highly abundant in less contaminated stations. Analysis of the dated sediments (²¹⁰Pb) indicates that higher PAH concentrations occurred in the sediments deposited after 1980, and higher fluxes of PAHs discharged to the Pearl river are found after 1990.     

NOAA gulf of Mexico status and trends program: Trace organic contaminant distribution in sediments and oysters

Polynuclear aromatic hydrocarbons (PAH), chlorinated pesticides, and polychlorinated biphenyls (PCB) concentrations were determined in sediment and oysters to provide information on the current status of the concentration of these contaminants in Gulf of Mexico coastal areas removed from point sources of input. Coprostanol analyses of sediments showed that anthropogenic materials are associated with the sediments at all 153 stations sampled. The levels of contaminants encountered are low compared with areas of known contamination. Average PAH concentrations are nearly the same in oysters and sediments, although the molecular weight distribution is different. Average DDT and PCB concentrations are higher by a factor of 10 to 130 in oysters as compared to sediments. Continued sampling and analyses will allow for long-term trends in the concentrations of these contaminants to be determined.     

Hydrocarbons in western North Atlantic surface sediments

High concentrations of hydrocarbons (500–3000 μg/g dry weight) together with a complex and wide molecular weight range of composition, and low ¹⁴C activity of δ¹⁴C = ?833 ± 50%. strongly indicate that fossil fuel hydrocarbons make up the bulk of hydrocarbons in and near the New York Bight dump site areas. The composition and concentrations of hydrocarbons in Hudson Channel sediments suggest some transport of dump site hydrocarbons to areas in the channel midway to the edge of the continental shelf. Sediments at 16 stations in other areas of the continental shelf, continental slope and abyssal plain have hydrocarbon concentrations and compositions indicating that no more than 1 μg/g dry weight of fossil fuel hydrocarbons are present.N-alkanes from land sources were among the most predominant hydrocarbons in all samples except those in the New York Bight region. Their presence in abyssal plain surface sediments documents transport of some land derived organic matter to these deep ocean areas. Two 25-carbon cycloalkenes are among the more predominant hydrocarbons in continental shelf surface sediments except for the dump site areas. These two compounds are present in lower concentrations in slope sediments and are not detected in abyssal plain sediments.     

Polycyclic aromatic hydrocarbons in the sediments of Xiangjiang River in south-central China: occurrence and sources

The Xiangjiang River (XR), located in Hunan province in south-central China, is the second largest tributary of the Yangtze River. The occurrence, and sources of the polycyclic aromatic hydrocarbons (PAHs) in the 20 surface sediment samples from XR were analyzed, and the biological risks of the PAHs on the benthic organisms were assessed using sediment quality guidelines. The results showed that the occurrence level of the 16 USEPA priority PAHs in the surface sediments ranged from 190 to 983 ng/g (dry weight) with a mean concentration of 452 ± 215 ng/g. The concentration of phenanthrene was the highest with a mean concentration of 104 ± 44 ng/g. The compositions and principal components analysis indicated that the PAHs in the sediments in XR were mainly from pyrogenic sources which could be attributed to the open burning of rice straws and coal combustion of the local industries in the XR basin. The PAH contamination in the sediments was considered to be moderate, and has posed a small adverse biological effect on the benthic organisms.     

Hydrocarbons in the water and bottom sediments of a region with continuous petroleum contamination

The abundances and compositions of aliphatic hydrocarbons (AHC) and polyaromatic hydrocarbons (PAH) were investigated in the water and bottom sediments of the southwestern Amur Bay in the Sea of Japan. The water contained from 0 to 129 μg/1AHC (averaging 42.2 μg/l) and from 5 to 85 ng/l PAH (averaging 18 ng/l). The bottom sediments contained 168–2098 μg/g AHC and 7.2–1100 ng/g dry mass PAH. It was shown that the input of anthropogenic HC is better recorded by molecular markers than the distribution of AHC and PAH concentrations. The discovery of elevated HC concentrations in the bottom water layer suggests that the bottom sediments induced secondary contamination of the water body.     

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.     

New insights into the origin of perylene in geological samples

The origin of the polycyclic aromatic hydrocarbon (PAH) perylene in sediments and petroleum has been a matter of continued debate. Reported to occur in Phanerozoic organic matter (OM), fossil crinoids and tropical termite mounds, its mechanism of formation remains unclear. While a combustion source can be excluded, structural similarities to perylene quinone-like components present in e.g. fungi, plants, crinoids and insects, potentially suggest a product-precursor relationship. Here, we report perylene concentrations, ¹³C/¹²C, and D/H ratios from a Holocene sediment profile from the Qingpu trench, Yangtze Delta region, China. Perylene concentrations differ from those of pyrogenic PAHs, and rise to prominence in a stratigraphic interval that was dominated by woody vegetation as determined by palynology including fungal spores. In this zone, perylene concentrations exhibit an inverse relationship to the lignin marker guaiacol, D/H ratios between −284‰ and −317‰, similar to the methoxy groups in lignin, as well as co-variation with spores from wood-degrading fungi. ¹³C/¹²C of perylene differs from that of land plant wax alkanes and falls in the fractionation range expected for saprophytic fungi that utilise lignin, which is isotopically lighter than cellulose and whole wood. During progressive lignin degradation, the relative carbon isotopic ratio of the perylene decreases. We therefore hypothesise a relationship of perylene to the activity of wood-degrading fungi. To support our hypothesis, we analysed a wide range of Phanerozoic sediments and oils, and found perylene to generally be present in subordinate amounts before the evolutionary rise of vascular plants, and to be generally absent from marine-sourced oils, few exceptions being attributed perhaps to a contribution of marine and/or terrestrial-derived fungi, anoxia (especially under marine conditions) and/or contamination of core material by fungi. A series of low-molecular-weight aromatic quinones bearing the perylene-backbone were detected in Devonian and Cretaceous sediments, potentially representing precursor components to perylene.     

Distribution and ecological risks of polycyclic aromatic hydrocarbons (PAHs) in sediments of different tropical water ecosystems in Niger Delta,Nigeria

Sediments are considered as suitable matrices to study the contamination levels of aquatic environment since they represent a sink for multiple contaminant sources. In this study, the influence of sediment characteristics on the distribution of polycyclic aromatic hydrocarbons (PAHs) and its potential risk in euryhaline, freshwater and humic aquatic bodies of Douglas/Stubbs creek, Ikpa River and Eniong River, respectively, were investigated. The level of PAHs in sediment was quantified using GC–MS, while sediment properties including total organic carbon (TOC) content and grain size were determined by the wet oxidation and hydrometer methods, respectively. The results revealed that the total levels of PAHs in sediment varied significantly between the euryhaline, freshwater and humic freshwater ecosystems. In Ikpa River freshwater ecosystem, a total PAHs load of 1055.2 ng/g was recorded with the suites concentration ranging from 13.0 ng/g (for acenaphthylene) to 161 ng/g (for pyrene). The humic ecosystem of Eniong River had a total PAH load of 11.06 ng/g, while the suites level recorded ranged from 0.04 ng/g for acenaphthene to 2.65 ng/g for chrysene. The total level of PAHs detected in the euryhaline Douglas/Stubbs creek was 14.47 ng/g, and suite concentrations varied between 4.27 ng/g for naphthalene and 5.13 ng/g for acenaphthylene. This shows variation in quantity and quality of PAH contaminants with the nature of ecosystems. It implies complex and diverse contamination sources as well as different capabilities to recover from PAH contamination. Correlation analysis has shown that sediment particle and TOC content influenced PAHs burden in bottom sediments, but the effects varied with the molecular weight of PAHs and the nature of the ecosystems. The TOC was the most significant determinant of PAHs load and distribution in sediment of the freshwater Ikpa River and euryhaline Douglas/Stubbs but had little or no influence in the humic sediment of Eniong River, while the influence of particle size was generally indefinite but slightly associated with PAHs accumulation in the euryhaline sediment. Generally, the total PAH levels (11.0–1055.2 ng/g) recorded were low and below the allowable limit for aquatic sediments. The ecological risk assessment revealed that these levels were lower than the effects range low and effects range medium values. This indicates no acute adverse biological effect although the accumulation of PAHs in freshwater ecosystem of Ikpa River may pose ecological risks as most of the carcinogenic PAH suites had relatively high pollution indices compared to other ecosystem types studied.     

Biogenic and abiogenic polynuclear aromatic hydrocarbons in sediments from two remote Adirondack lakes

Sediment cores from Sagamore Lake and Woods Lake in New York State's Adirondack Park, an area remote from industrial activities, were analyzed for polynuclear aromatic hydrocarbons (PAH) by high resolution gas chromatography/mass spectrometry (GC/MS). Their composition and distribution with depth in the sediment indicate that the parental PAH in the surface sediments are primarily produced by anthropogenic combustion of fossil fuels. Perylene in deep sediments is apparently transformed from natural precursors in the reducing environment, however, the exact precursors remain unknown. The rather even sediment distributions of the non-parental PAH differ from the parental, suggesting biogenic origins. Based on their chemical structures, retene and alkylated and partially hydrogenated phenanthrenes are believed to be biogenically converted from abietic acid; hydrochrysenes and hydropicenes, from pentacyclic triterpenes.     

Perylene occurrence,alkylation and possible sources in deep-ocean sediments

81 deep-ocean sediment samples obtained from the DSDP/IPOD program Legs 63–66, and six gravity-cores from DSDP/IPOD Leg 64 Guaymas Basin, Gulf of California, site survey cruise (SIO) were analyzed for perylene(s). Perylene was found to be most abundant in anoxic diatomaceous sediments containing moderate amounts of silts and/or clays. Elevated perylene yields, normalized to organic carbon contents, coincided with enhanced preservation of autochthonous tetraterpenoid and tetrapyrrole pigments, indicating a requirement of anoxia in the formation of perylene. Strongly euxinic conditions correlate with decreased perylene yields but not its total absence, as found for strongly aerobic deposition and/or redeposition. Perylene alkylation occurs in response to increasing in situ temperatures (alt. sub-bottom depth). This alkylation was found to begin with the generation of methyl (C-1) perylene and to eventually yield a perylene-alkyl perylene homologous series, in decreasing abundance, through the equivalent of C-3 (trimethyl, methyl-ethyl, propyl?) perylene. The realm of most intense perylene alkylation for Quaternary or Pliocene/ Miocene sediments corresponds with present in situ temperatures of 40–50°C or 30–35°C, respectively. Thus, the degree of perylene alkylation may represent an organic indicator for the thermal history of immature sediments. Geological phenomena, such as reworking and igneous intrusions, were found to complicate downhole perylene alkylation patterns. A substituted (-C₄H₇O₂) perylene was isolated from several anoxically deposited diatomaceous oozes and may represent one of the many possible perylene precursors. The possible source compounds and biota for sedimentary perylene are discussed in light of the present study and review of past reports.     

Predictive environmental impact assessment of total petroleum hydrocarbons in petrochemical wastewater effluent and surface sediment

The contamination level of total petroleum hydrocarbons (TPH) in wastewater and surface sediment samples from the Petrochemical Special Economic Zone (PETZONE) and adjacent coastal area in Musa Bay (in Northwest of Persian Gulf) was examined. Concentrations of TPH in the Musa Bay sediments ranged from 16.48 to 97.15 µg/g dry weight (dw) with average value of 48.98 ± 30.36 µg/g dw. The highest concentrations were estimated in stations close to the coastline, locations affected by intensive petrochemical discharges and shipping activities. The average TPH concentration in the PETZONE wastewater effluent samples was 5.22 mg/L, with a range of 0.06–35.33 mg/L. Regarding environmental impact assessment, the concentration of TPH was lower than the wastewater effluent discharge standard at most of the monitoring stations inside PETZONE companies, with the exception of stations 15, 16 (Imam Khomeini petrochemical company 1, 2) and 17 (Razi petrochemical company). These stations were considered as moderate environmental aspects, suggesting that concentration of TPH in the wastewater effluents of these petrochemical companies could be considered as contaminants of concern in the PETZONE area.     

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.     

Stability and hydrogenation of polycyclic aromatic hydrocarbons during hydropyrolysis (HyPy) – Relevance for high maturity organic matter

A series of hydropyrolysis (HyPy) experiments have been conducted on a small suite of authentic polycyclic aromatic hydrocarbons (PAHs: coronene, pyrene and perylene) to investigate the HyPy behaviour of these PAHs. This information may help in the interpretation of the structural significance of aromatic HyPy products, often detected in high abundance, from high maturity kerogens. The PAHs were separately treated by HyPy and were all susceptible to some extent of hydrogenation. Perylene also decomposed into low molecular weight aromatics (e.g. methylbiphenyls). Structurally, perylene is much less stable than the more condensed PAHs coronene and pyrene. The total product concentrations (wt% of starting PAH) from all HyPy experiments were consistently less than 100 wt%, probably due to either the condensation of semi-volatile products on walls of the transfer line prior to reaching the HyPy trap or the inefficient cold trapping of highly volatile products. Hydrogenation of PAHs was prevalent and was found to be significantly influenced by the addition of a Mo-S based catalyst and potentially the C/Mo ratio, but largely independent of the two final temperatures used (520 °C and 550 °C). The fully aromatised and hydrogenated products for any stable ring system may provide a general indication of the size distribution of aromatic units within the kerogen structure.     

Concentrations and possible sources of PAHs in sediments from Bohai Bay and adjacent shelf

Concentrations, spatial distribution and sources of 16 polycyclic aromatic hydrocarbons (PAHs) listed by the United States Environmental Protection Agency as priority pollutants were investigated in surface sediments of Bohai Bay, North China. Total concentrations of PAHs were in the range of 140.6–300.7 ng/g (dry wt), with an average of 188.0 ng/g. The three predominant PAHs were phenanthrene, acenaphthene and naphthalene. Sedimentary PAH concentrations of the north and central Bohai Bay were higher than those of the southern side of this bay. PAHs source analysis suggested that PAHs in most of the sediments were mainly from grass, wood and coal incomplete combustion. At other stations near the estuaries (Luanhe River Estuary and Chaohe River Estuary) or the oil drilling platform, both petrogenic and pyrogenic inputs were significant. The pyrogenic PAHs close to the oil drilling platform were mainly from petroleum combustion.     

Polycyclic aromatic hydrocarbon fingerprints in the Pichavaram mangrove–estuarine sediments,southeastern India

The sources and historical deposition of 16 polycyclic aromatic hydrocarbons (PAHs) were investigated in dated sediment cores from the Pichavaram mangrove–estuarine complex. The ΣPAH flux in mangrove and estuarine sediments was 0.064 ± 0.031 μg/cm²/yr and 0.043 ± 0.020 μg/cm²/yr, respectively. The PAH flux in sediments increased up-core, coinciding with rapid urbanization since the 1970s. The flux showed a decrease in recent years (since 1990), coinciding with less riverine discharge, and perhaps more effective implementation of environmental regulations. The sediments were dominated by low molecular weight PAHs, suggesting anthropogenic input. Ratios of specific PAH isomer pairs suggested a greater input of petrogenic vs. pyrogenic derived PAHs. Notably, the deposition of high molecular weight PAHs increase in mangrove surface sediments was due to lignite and firewood combustion. Because of their overall low concentration in sediments it is unlikely these PAHs pose an immediate ecological hazard.     

Polycyclic aromatic hydrocarbons in Niger Delta soil: contamination sources and profiles

The distribution and sources of PAHs in soil as well as PAHs profiles have been investigated in areas with anthropogenic pollution in the Niger Delta (Nigeria) such as Warri and Ughelli. PAHs were identified in 21 soil samples (0–10cm upper layer) collected in May, 2003. The typical total PAHs level in Niger Delta soil ranged from 182 ± 112 - to - 433 ±256 íg/kg dw. PAH concentrations in soil samples from Warri Refinery, Tanker Loading point and Ugboko via Rapele oil field were quite high ( the mean ÓPAH concentrations were 433, 402 and 384 íg/kg dry weight respectively). The dominant PAHs in soil samples were pyrene, naphthalene and benzo[k]fluoranthene. The soil total PAHs (PAH_tot.) concentration, normalized to organic carbon content (OC), ranged from 11.4 to 47.2 mg PAH_tot. /kg OC; and showed that organic matter of the soil samples from Quality Control Centre, Ugelli West is highly contaminated with PAHs and had a value of 47.2 ± 31.2 mg PAH_tot./kg OC. Two and three ring aromatic hydrocarbons predominated in soil samples from Ughelli West, Tanker Loading point and Delta Steel Company, which is indicative of petrogenic origin.