Polycyclic aromatic hydrocarbons as evidence of hydrocarbon migration in marine and lagoon sediments of a recent rift zone (Skjálfandi and Öxarfjörður), Iceland

Polycyclic aromatic hydrocarbons (PAHs) content and distribution was studied in the northern part of modern rift zone. All samples analysed represent slightly altered clastic deposits and hot water discharging in springs and from wells. To study PAH in present-day gas emission traps with diatomite absorbent were installed in the Skógalón geothermal field. All samples were analysed by the method of Shpol'sky spectroscopy. Hydrothermally altered deposits show the highest amount of PAH. Data obtained allow to believe that the distribution of PAH is closely associated with the dynamics of the hydrothermal environment. The fissure formation and temperature fluctuation in hydrothermal systems can govern both the processes of PAH synthesis and sorption. The evidences of PAH migration up through the Skjálfandi and Öxarfjörður sedimentary basins show that hydrocarbons associate mainly with hydrothermal minerals and deep ground waters. Studying PAH associations can be used as an indicator of hydrocarbons distribution, ways of migration and possible zones of accumulation in the land and marine sedimentary basins in active and ancient rift zones of Iceland.     

Environmental status of the metropolitan river (Kifissos) of Athens,Greece

Surficial and sub-surficial sediments obtained from the lower course of the Kifissos River, which drains the Athens Basin, have been analyzed for heavy metals and aliphatic and polycyclic hydrocarbons. Oddly, the calculated enrichment factors for the identified heavy metals, with the baseline taken from a pristine area in the adjacent Saronikos Gulf, are very low excluding only those related to Cu and Zn. In contrast, the enrichment factors for the measured hydrocarbons are particularly high. However, physicochemical water conditions and annual flushing episodes of the Kifissos River may have reduced significantly the sediment chemical fingerprint found out by the present study. Moreover, an evaluation of the fluvial sediment quality based on the enriched Cu and Zn amounts and concentration of PAH fraction with a consideration of the biological thresholds proposed by the National Oceanic and Atmospheric Administration (USA) reveals little probability for serious biological impairments. Additionally, sediment toxicity due to the sediment PAH load may be considered as minimum.     

Effect of organic matter and selected heavy metals on sorption of acenaphthene,fluorene and fluoranthene onto various clays and clay minerals

The effects of organic matter (80% humic and 15% fulvic acid) and coexistence of heavy metals (Ni, Pb and Zn) on sorption of three polycyclic aromatic hydrocarbons (PAHs)—acenaphthene, fluorene and fluoranthene—were examined for kaolinite, 60% kaolinite?+?40% sand, and 43% kaolinite?+?42% sand?+?15% bentonite. In total 108 batch sorption tests of PAHs were conducted for three types of clay mineral mixtures in six possible combinations of soil organic matter and heavy metal contents from no heavy metals and organic matter added to maximum organic matter added with spiked heavy metals. Results showed that the existence of metals increased the sorption of PAHs onto kaolinite from 4.7% for acenaphthene to 17.9% for fluoranthene. Organic matter in a kaolinite-sand-bentonite matrix could increase PAH sorption by up to 140% for fluoranthene. In all cases, increases were greater for fluoranthene, a larger PAH molecule. Heavy metals coexisting with organic matter led to enhanced sorption of PAHs compared to clay minerals without organic matter. Synergistic effects of organic matter and heavy metals on PAH sorption increments in the mixtures studied were such that the overall sorption could be 10–41% higher than that based on summation of the separate effects of metals and organics.     

The rare earth element geochemistry of hydrothermal sediments from the East Pacific Rise: Examination of a seawater scavenging mechanism

The sediments recovered during DSDP Leg 92 (Site 598) include a complete 16 m.y. record of hydrothermal sedimentation along the western flank of the East Pacific Rise at 19°S. Fifty samples from this sediment column were analyzed to test the hypothesis that the REE composition of the hydrothermal component is primarily acquired via scavenging from seawater. Site 598 provides an ideal sample suite for this purpose: the sediments are lithologically “simple,” primarily consisting of a mixture of hydrothermal materials and biogenous carbonates; the composition of the hydrothermal component is essentially constant through space and time; and the sediments have undergone minimal diagenetic alteration.The following observations suggest the above-stated hypothesis is true. The Ce anomaly as well as key indices of light and heavy REE behavior all show that the REE pattern of hydrothermal sediments approaches that of seawater with increasing paleodistance from the rise crest. Moreover, shale-normalized REE patterns are similar to that of seawater, varying only in absolute REE content: the REE content increases with distance from the paleo-rise crest and exhibits a pronounced increase in sediments deposited below the paleolysocline. Based on significant correlative relationships between paleodistance from the rise crest and both the concentration and mass accumulation rates (MARs) of REEs and Fe, we conclude the REEs in the hydrothermal component are derived from the interaction of seawater and Fe in the hydrothermal plume.     

萤石矿自然重砂矿物组合规律及其找矿意义

为探究不同类型的萤石矿所反映的自然重砂矿物组合所携带的对各类型萤石矿的指示特征,统计了浙江、湖南、湖北、青海、广西、福建、安徽、新疆、甘肃、河北共计10个地区23个典型萤石矿床的自然重砂矿物报出情况,计算各重砂矿物报出率,分析得出热液型矿、后期热液型及热液充填型3种类型萤石矿床各自对应的自然重砂矿物组合和标型矿物组合。结果显示,各类型矿床自然重砂矿物组合既有相同之处也有显示各自的特点。因此,按照矿床类型建立的自然重砂矿物组合及其含量变化,对于新一轮的矿产资源勘查具有重要的意义。     

Hydrothermal bitumen generated from sedimentary organic matter of rift lakes – Lake Chapala, Citala Rift, western Mexico

Lake Chapala is in the Citala Rift of western Mexico, which in association with the Tepic-Zacoalco and Colima Rifts, form the well-known neotectonic Jalisco continental triple junction. The rifts are characterized by evidence for both paleo- and active hydrothermal activity. At the south shore of the lake, near the Los Gorgos sublacustrine hydrothermal field, there are two tar emanations that appear as small islands composed of solid, viscous and black bitumen. Aliquots of tar were analyzed by GC-MS and the mixtures are comprised of geologically mature biomarkers and an UCM. PAH and n-alkanes are not detectable. The biomarkers consist mainly of hopanes, gammacerane, tricyclic terpanes, carotane and its cracking products, steranes, and drimanes. The biomarker composition and bulk C isotope composition (δ¹³C = −21.4%) indicate an organic matter source from bacteria and algae, typical of lacustrine ecosystems. The overall composition of these tars indicates that they are hydrothermal petroleum formed from lacustrine organic matter in the deeper sediments of Lake Chapala exceeding 40 ka (¹⁴C) in age and then forced to the lakebed by tectonic activity. The absence of alkanes and the presence of an UCM with mature biomarkers are consistent with rapid hydrothermal oil generation and expulsion at temperatures of 200–250 °C. The occurrence of hydrothermal petroleum in continental rift systems is now well known and should be considered in future energy resource exploration in such regions.     

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.     

Effect of Deepwater Horizon Oil on Growth Rates of Juvenile Penaeid Shrimps

Marsh shoreline, an important habitat for juvenile penaeid shrimps, was extensively oiled in coastal Louisiana by the Deepwater Horizon oil spill of 2010. The effect of this spill on growth was examined for brown shrimp Farfantepenaeus aztecus and white shrimp Litopenaeus setiferus held for 7 days in field mesocosms in Barataria Bay during May and August 2011, respectively. The experiments each had 10 treatment combinations, five apparent oil levels, each one with and without added food. Mesocosms were placed in northern Barataria Bay along shorelines that varied in oiling (designated as heavy, moderate, light, very light, or none based on NOAA surveys), and shrimp in half the mesocosms received additional food. Polycyclic aromatic hydrocarbon (PAH) concentrations determined from sediment cores collected at each mesocosm were significantly higher at heavy and moderate than very light shorelines and also higher at moderate than light and none shorelines. Brown shrimp grew more slowly at heavy than very light or none shorelines, and a statistically significant negative relationship was detected between brown shrimp growth rates and sediment PAH concentrations. In August, PAH sediment concentrations had decreased significantly from the values measured in May, no significant difference in white shrimp growth rates was detected among oiling levels, and no relationship was detected between white shrimp growth and sediment PAH concentrations. Both brown shrimp and white shrimp grew more rapidly in mesocosms where food was added. Our study shows that exposure to nonlethal concentrations of petroleum hydrocarbons can reduce growth rates of juvenile penaeid shrimps.     

Hydrothermal petroleum in the sediments of the Andaman Backarc Basin,Indian Ocean

Recent sediments of the Andaman Backarc Basin, Indian Ocean, between the Andaman Nicobar islands and the Malay Peninsula have been analyzed for biomarker lipids. Three cores were selected: one each from the fault zone in a deep basin (a graben between two fault systems), another from a location adjacent to the fault, and the third from the topographic high in the rift valley. The molecular composition of the lipid classes (n-alkanes, isoprenoids, alkylbenzenes, alkylcyclohexanes, hopanoids, polycyclic aromatic hydrocarbons, steranes, alcohols, sterols and fatty acids) was examined by gas chromatography (GC) and GC/mass spectrometry to understand the nature and source of the hydrocarbons present and the processes of maturation of organic matter. The data show that the hydrocarbons are of hydrothermal origin, derived from thermal alteration of sedimentary organic matter, consisting of a mixture predominantly of marine-derived components with some terrestrial inputs. Normal alcohols and fatty acids also corroborate the distribution of n-alkanes. The distribution profiles and various parameters computed from the concentration of the target compounds suggest that oxidative reactions and microbial degradation in this environment are insignificant. Triterpane and PAH compositions indicate that the thermal maturity of the bitumen in the samples is comparable to or lower than that found at other hydrothermal regions such as the Northern Juan de Fuca Ridge, Guaymas Basin and Escanaba Trough.     

The concentration function of the bottom fauna at the deep sea hydrothermal vent fields

Specific features of the concentration of a group of chemical elements in the dominant bottom organisms are analyzed. The studied organisms inhabit geochemically different hydrothermal fields: Menez-Gwen, Broken-Spur, and Rainbow on the Mid Atlantic Ridge (MAR), as well as 9°50′N and Guyamas on the East Pacific Rise (EPR). It was revealed for the first time that bottom organisms accumulate 10² to 10⁵ times less the macro-ions of marine water Na and K from the water of biotopes than heavy metals. The intensive concentration of chemical elements, especially of heavy metals, and the high biomasses of bottom organisms associated with hydrothermal vents suggest that this fauna serves as a powerful deepwater biofilter. The absence of pronounced differences between values of coefficients of accumulation for the same metals in the benthos of various MAR and EPR fields evidences the uniformity of the concentration function of the hydrothermal fauna.     

云龙锡矿锡石的振动光谱和电子顺磁共振谱研究

本文用振动光谱和电子顺磁共振谱研究了云龙锡矿锡石的谱学特征。根据红外光谱的谱形、吸收频率和吸收峰强度特征,将云龙锡矿锡石的红外光谱划分成两种类型:A型谱和B型谱。红外光谱特征的研究结合宏观地质特征的研究表明:氧化物阶段锡石的红外光谱为A型谱,硫化物阶段锡石的红外光谱为B型谱。随着锡石成分和结构的变化,锡石的拉曼光谱的谱型、振动频率也发生变化,反映了锡石的成矿条件的差异。云龙锡矿锡石的EPR谱研究表明,云龙锡石中含有呈类质同象进入锡石晶格的V~(4+),根据V~(4+)的稳定场研究,云龙锡石主要形成于相对碱性和偏还原的条件下。     

大气污染物向海洋的输入及其生态环境效应

纵观20年来，特别是近几年来逐渐成为生物地球化学循环研究热点之一的大气对海洋物质输入的研究，从大气物质入海通量，大气物质入海对海洋生态系统和环境的影响，大气物质入海的科学研究计划和项目等方面分析了这一领域的研究现状和未来趋势。给出了不同海区各种主要大气入海物质的通量或在同类物质入海总量中的比例，讨论了氮、磷、铁等营养物质和持续性有毒污染物，如PAH、PCBs、杀虫剂和重金属对海洋生态系统和环境的不同影响。     

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.     

Compositional fractionation of polyaromatic hydrocarbons in the karst soils, South China

This study aims to explore the condensation and fractionation trends of persistent organic pollutants (POPs) in the karst soils. The tiankeng is a karst surface expression that can act as a focal point for introduction of contaminants to a karst aquifer, which may serve both as condenser for vapor phase POPs and as barrier/sink for particulate associated less volatile POPs. The fractionation of POPs in soils from the upper rim and floor of tiankeng is of interest in understanding the role of tiankeng in the long-distance transport of POPs. In the present study, polycyclic aromatic hydrocarbons (PAHs) in the surface soils from the upper rim and floor of Dashiwei tiankeng in Southern China were analyzed. The total PAH concentrations in soils were 23.40–190 ng g⁻¹, with phenanthrene being the most abundant. The distribution patterns of PAH compounds in the soil samples matched well with their properties. It indicated the heavy PAHs were susceptible to retention by the floor soils of tiankeng than light PAHs. A plot of Cfloor/Crim against PAH molecular weight gave a good positive relationship in the molecular weight range of 152–276. It is suggested that the floor soils can be focal points of more concentrated PAH and deserve attention. The concentrations of total PAHs in the floor soils (43.40–190 ng g⁻¹, mean 87.76 ng g⁻¹) were higher than those in the upper rim (23.40–88.94 ng g⁻¹, mean 57.74 ng g⁻¹). In addition, there was a shift in compound pattern with an increase in the proportion of light PAHs (2–3 rings), a decrease in heavy PAHs (5–6 rings) and a relatively stable content of 4-ring PAHs. A combination of particulate scavenging and cold condensation is proposed as the major mechanism for the compositional fractionation of PAHs in the soils from the upper rim and floor of tiankeng.     

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.     

Application of spatial analysis and multivariate analysis techniques in distribution and source study of polycyclic aromatic hydrocarbons in the topsoil of Beijing,China

Surface soil samples were collected from 161 sites throughout the downtown and suburban area of Beijing, China. The samples were analyzed for polycyclic aromatic hydrocarbons (PAHs) concentrations. Through Kriging analysis, five heavily contaminated zones were identified in the study area. Sources of PAHs in the soil were apportioned using principal factor analysis and multiple linear regression. Three factors were identified representing coal combustion/vehicle emission, coking emission, and petroleum sources, respectively. The relative contributions of the three sources were 48% for coal/vehicle emission, 28% for coking emission, and 24% for petroleum sources. The contributions of total PAHs from the three sources were 16.4, 4.63 and 3.70 ng g⁻¹, respectively. Spatial analysis indicated that the contribution of coal/vehicle sources was higher in the downtown area than in the suburban area, the petroleum sources had a high contribution in the urban area, and the contribution of coking sources was high in the suburban area. The results indicated that PAH contamination in the surface soil in Beijing was closely related to the spatial characteristics of energy consumption and functional zoning. Improvement of the energy consumption structure and relocation of industries with heavy pollution are effective ways to control PAH contamination in surface soil in the area.     

Tendencies in the distribution and hypotheses of the genesis of condensed naphthides in magmatic rocks from various geodynamic environments

Literature data suggest that concentrated naphthides (CN)—bitumen and oil—can occur in intrusive and volcanic rocks of various silicity and alkalinity whose age ranges from the Proterozoic to Recent. The qualitative composition of heavy (high-molecular) hydrocarbons (HHC) in CN is the same in various rocks: heavy alkanes, polycyclic aromatic hydrocarbons (PAH), oxygen-bearing derivatives of hydrocarbons, etc. The presence of CN in rock-forming minerals in magmatic rocks and pegmatites confirms that CN condensed during the epimagmatic stage, and the molecular mass of the CN, for example, in the Khibina alkaline massif decreased with decreasing temperature simultaneously with the evolution of its mineral assemblages. The synthesis of CN continues during the hydrothermal stage, but high-temperature associations of HHC gave way during this stage to low-temperature ones. During all evolutionary stages of magmatic and related processes, the contents of CN are correlated with those of trace elements, which likely occur as organoelement compounds (OEC). Hypotheses of endogenic and exogenic genesis of CN in magmatic rocks are discussed. The endogenic hypotheses include HHC synthesis from inorganic gases and light hydrocarbons (HC) on catalytic minerals. The fact that HHC and CN occur in mantle xenoliths and high-pressure minerals and the results of experimental and thermodynamic modeling are discussed as supporting the hypothesis of the mantle genesis of CN in magmatic rocks. The metastable ascent of gaseous HHC, the low oxygen fugacity, and the high alkalinity of the melts could be favorable for the partial preservation of HHC in these rocks at crustal depth levels. Endogenic CN can serve as a nutrient medium for microorganisms in the upper lithosphere. Exogenic hypotheses for the genesis of HHC in magmatic rocks assume that the melts should have assimilated sedimentary rocks rich in organic matter and that biogenic oil could be transported from sedimentary reservoirs to magmatic rocks. An important role in determining the genesis of CN in magmatic rocks is played by endogenic and biogenic markers.     

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。     

Sediment-water column exchange of persistent organic pollutants (PAH<Subscript>s</Subscript> and PCB<Subscript>s</Subscript>) and their transport vector in El Bey watershed,Tunisia

El Bey river, which drains 60% of the pollutant load of several urban cities in the northeast of Tunisia, provides a good example of the transfer of organic and metallic pollutants that result from industrial and urban activity, and can be used to show how these charges are transported and discharged into the Gulf of Tunis. Persistent organic pollutants (PAH and PCB) in dissolved, particulate matter, bed sediments, and three wastewater effluents in El Bey watershed were analyzed. PAH (∑14PAHs) concentration ranged from 0.248 to 9.955 mg L^?1 and from 0.836 to 28.539 mg L^?1 in dissolved and particulate fraction respectively. The particulate/dissolved partition coefficient value (Kd) was less than one which confirmed the affinity of PAH to be adsorbed. In sediment, the high-molecular weight PAHs were found principally with percentage between 50 and 100% witch present 239.99 to 5362.19 μg kg^?1, which is relatively higher in comparison with other estuaries river. Contrary to PAH patterns, PCB were bound to dissolve fraction. Kd _(PCB) value (Kd?>?1) reflected this affinity which is related to environment energy. The spatial distribution and profile of analyzed organic pollutants confirmed the direct impact of wastewater effluent on the organic pollution level in three compartment of El Bey watershed and his profiles suggested different transport patterns.