The concentration and composition of hydrocarbons in water,particulate matter,and bottom sediments of the Kara Sea

Data are presented on the content of aliphatic and polycyclic aromatic hydrocarbons (AHC and PAH, respectively) in the interstitial waters and bottom sediments of the Kara Sea compared to the distribution of the particulate matter and organic carbon. It was found that the AHC concentrations within the water mass (16 μg/l on average) are mainly formed by natural processes. The AHC distribution represents the variability of the hydrological and sedimentation processes in different regions of the sea. The widest ranges of the concentrations were registered in the Ob Bay-Kara Sea section: in the water (10–310 μg/l for the AHC and 0.4–7.2 ng/l for the PAH) and in the surface layer of the bottom sediments (8–42 μg/l for the AHC and 9–94 ng/g for the PAH). The differentiation of the hydrocarbons (HC) in the different media follows the marginal filter’s regularities; therefore, no oil and pyrogenic compounds are supplied to the open parts of the sea. In the sediment mass, the HC content is determined by the variations in the oxidative conditions in the sediment and its material’s composition.     

Hydrocarbons in the Bay of Bengal and Central Indian Basin bottom sediments: indicators of geochemical processes in the lithosphere

A study on the bulk distributions and molecular structures of n-alkanes and polycyclic aromatic hydrocarbons (PAH) in organic matter of the sediments from the Bay of Bengal and the Eastern and Central Indian Basins was undertaken. The former two regions represent areas characterised by “normal” sedimentation while the third one mainly represents a region of “active tectonism”. Content of the hydrocarbons in the sediments of “normal” sedimentation ranges between 4.6 and 10.5 μg/g and aromatic hydrocarbons ranges between 0 and 0.38 μg/g. n-Alkanes in the sediments of the northern deep part of the Bay of Bengal consist mostly of long-chain structures (total C₂₅–C₃₃ up to 70%) with a high carbon preference index (CPI=3.01–3.43), indicating a large contribution of organic matter from terrigenous sources. The sediments from the Eastern Indian Basin have n-alkane distributions in which the long-chain components did not exceed 52.5% and the CPI was 1.7–1.90, indicating that the hydrocarbons are mostly derived from marine sources. Sharp increases of hydrocarbons are found in the vicinity of the tectonically active region of the Central Indian Basin, particularly in the sediments collected from the fracture zone. The total concentration of hydrocarbons increase to 170 μg/g and the aromatic hydrocarbons fraction to 156.3 μg/g. The proportion of short-chain n-alkanes increases up to 70%, CPI decreases to 0.76–1.12, and high concentrations of n-C₁₆ (16–40%) occur, all of which are absent in the other samples. The molecular content of PAH includes the unsubstituted individual structures: biphenyl, fluorene, pyrene, perylene, benzo(ghi)perylene, and the groups of homologues of naphthalene, benzofluorene, phenanthrene and chrysene. The association of the PAH and composition of paraffin hydrocarbons in the surficial sediments of deformation zone indicate that these are the resultant products of hydrothermal processes. It is, therefore, suggested that the association and composition of the hydrocarbons in sediments can be utilised as a paleoceanographic parameter to decipher the history of tectonism of an area.     

Origin of hydrocarbons in the particulate matter and bottom sediments of the northern shelf of the Caspian Sea

Data are presented on the content and composition of hydrocarbons (HC) (aliphatic, AHC and polyaromatic, PAH) in the filtered particulate matter and in the surface layer of the bottom sediments on the northern shelf of the Caspian Sea and related to the data on their content in the Volga River estuary. Because of the transformation and precipitation of anthropogenic and natural compounds, the HC composition in the particulate matter and bottom sediments undergoes transformations caused by the mixing of fresh and saline waters (in the bottom sediments, within the concentration ranges 70.4–4557.9 μ g/g for AHC and 3.8–4800 ng/g for PAH). It was found that the greatest concentrating of HC proceeds in the region of the avalanche sedimentation, and their content is independent of the grain-size type of the sediments. The anthropogenic HC (oil and pyrogenous) do not get over the marginal filter of the Volga River and do not pass to the open part of the sea.     

东海表层水体中的多环芳烃及其沉积通量估算

以东海陆架水体中溶解态多环芳烃(PAHs)含量为基础,引入颗粒相-水相间的物质吸附系数(Koc)计算悬浮颗粒物中PAHs有机碳归一化含量,结合陆架沉积物有机碳的年埋藏通量,估算东海陆架沉积物中PAHs沉积通量。结果显示:水体中溶解态的15种PAHs总含量为(701±392)ng/L,变化范围为412~1 032ng/L,PAHs组成以3环为主。计算得到的悬浮颗粒物中15种PAHs有机碳归一化含量为20~28μg/g,对应的PAHs沉积通量为150~210t/a。估算结果与实测沉积物中PAHs含量和沉积通量结果基本吻合,表明实验室模拟实验获取的化合物Koc值适用于东海颗粒相-水相间的分配模型,证实悬浮颗粒物有机碳含量在控制PAHs两相分布过程中起着重要作用。同时,该方法为海洋沉积物中PAHs沉积通量的估算提供一种新途径。     

Polycyclic aromatic hydrocarbons in surface sediments of the Zhelin Bay in the South China Sea

This study examined the concentrations of polycyclic aromatic hydrocarbons (PAHs) in surface sediments collected in July 2004 from eight stations in the Zhelin Bay, one of the most important bays for large-scale mariculture in Guangdong Province. Thirteen individual parent PAH compounds were identified using high performance liquid chromatography with UV detection. The overall average concentration of total PAHs was 477.0 ng/g, ranging from 146.1 to 928.8 ng/g. Low molecular mass PAHs with two to three rings (e.g., acenaphthene) were dominant in each sample. The PAH concentration varied among sampling stations, with the highest concentration observed at bay outlets and the lowest found at stations outside the bay. Ratios of low to high molecular mass PAHs and fluoranthene to pyrene were used to determine the origin of PAHs, and results indicated mainly petroleum-derived contamination. Compared with other bays and harbors around the world, the total concentrations of PAHs in surface sediments at the Zhelin Bay are moderate, but this does not exclude the possibility of potential impact on human consumers because some strong carcinogenic PAHs with high molecular mass were found at the station with a nearby caged-fish and oyster farm. Long-term monitoring of PAH contamination in the Zhelin Bay is recommended to reduce the potential toxicological effects on aquatic organisms and humans.     

Marine organic geochemistry of the Eastern Mediterranean: 1. Aliphatic and polyaromatic hydrocarbons in Cretan Sea surficial sediments

As part of a lipid biogeochemical study, aliphatic and polyaromatic hydrocarbons were determined in surficial sediments from the Cretan Sea (South Aegean Sea) in the Eastern Mediterranean. Total concentrations of both aliphatic (AHC) and polyaromatic (PAH) hydrocarbons were low (562–5697 and 14.6–158.5 ng/g, respectively) with respect to other coastal sediments worldwide and compare with concentrations found in open sea areas. The composition of AHC was dominated by unresolved complex mixture (UCM) indicating the presence of petroleum-related hydrocarbon inputs as confirmed by the detection of specific α,β-hopanes. PAH consisted mainly of pyrolytic four- to five-ring compounds. UCM and PAH amounts revealed that Cretan Sea receives low supply of anthropogenic material compared to NW Mediterranean. The spatial distributions of AHC and PAH indicated that urban run-off and transport from the continental self are the major input pathway of anthropogenic and biogenic hydrocarbons from terrestrial sources in the near shore area, whereas atmospheric transport might be the significant source of hydrocarbons in the deep area.     

The PAH composition of surface sediments from Stagnone coastal lagoon, Marsala (Italy)

This paper examines the presence, distribution, nature and sources of 22 Aromatic Hydrocarbons (PAHs), which are important environmentally and toxicologically, in sediments from the Stagnone coastal lagoon at Marsala (Italy). Analysis was performed by gas chromatography/mass spectrometry (GC/MS) with selected ion monitoring (SIM). The total concentration of polycyclic aromatic hydrocarbons ranged from 72 to 18381 μg/kg of dry matrix. The relative standard deviation (RSD) of the replicates on the concentrations of individual compounds ranged from 5% to 20%. The accuracy of method was estimated by analyzing “blank” samples added of known quantities of analytes and the recover percentage was 88 ± 9%. The detection limit (LOD) of analytical procedure was less than 0.2 μg/kg d.w. for all analytes. The quantification limit (LOQ) of analytical procedure was less than 0.7 μg/kg d.w.The resulting distributions and weight ratios of specific compounds are discussed in terms of sampling location and origin of organic matter. A comparison with other studies of total PAHs suggests that the levels are within the concentration ranges already reported by other authors. From an eco-toxicological point of view, total PAH concentrations at seven out of the eight sites studied represent a relatively clean environment when compared to other sites.Organic matter content and PAH concentrations were found to be correlated and the compounds present in Stagnone sediments were shown to be mainly of pyrolitic origin, while a negligible quantity of PAHs may derive from biogenic sources since all the sediments contain perylene traces. There is no evidence of coal-tar contamination.Cluster analysis was carried out in order to discriminate between different PAH origins.     

PAH-biodegradation potential of indigenous microorganisms: evidence from the respiratory activity of surface sediments in the Quanzhou Bay in China

Seven stations were established in the Quanzhou Bay (24.73°-24.96°N, 118.50°-118.70°E) in China on three cruises to determine the concentrations of polycyclic aromatic hydrocarbons (PAHs) and the numbers of PAH-degrading bacteria in surface sediments. Assessing the biodegradation poten- tial of indigenous microorganisms by measuring the respiratory intensity with the addition of PAHs in sediment samples was also one of the aims of this study. The results show that the total PAH concentrations of the sedimen...     

Peculiarities in the distribution of hydrocarbons in the southeastern part of the Baltic Sea

Data on the contents and compositions of the hydrocarbons (HCs)—aliphatic (AHCs) and polycyclic aromatic (PAHs)—are provided in comparison with the contents of the total organic carbon (C_org), the lipids in the particulates, and the C_org in bottom sediments. Particular attention has been paid to the distribution of the HCs in the water area of the Kravtsov oil field. It has been established that the concentrations of AHCs in the water are governed by the content of particulates, and the elevated AHC concentrations are confined to the coastal areas. In the water area of platform D-6, the sandy bottom sediments were notable for the great variability of the HC concentrations, both laterally and from year to year. In the summer of 2010, the content of AHCs averaged 40 μg/g (19% in the C_org), and that of PAHs, 23 ng/g. Natural seepage from the sediment mass is considered to be a source of HCs along with oil contamination.     

Comparison of polycyclic aromatic hydrocarbon distributions and sedimentary organic matter characteristics in contaminated, coastal sediments from Pensacola Bay, Florida

In this study, we examined the distribution of polycyclic aromatic hydrocarbons (PAHs) in a contaminated coastal area and the characteristics of the natural organic matter in tandem. We present a detailed study of PAH concentration, distribution, and organic matter characteristics of three core samples from Pensacola Bay, Florida. Solid-state 13C Nuclear Magnetic Resonance (NMR), pyrolysis gas chromatography coupled with mass spectrometry (GC-MS), and tetramethyl ammonium hydroxide (TMAH) thermochemolysis GC-MS were applied to obtain structural details about the sedimentary organic matter. Elemental compositions (carbon and nitrogen) and estimates of black carbon contents are also reported. These coastal sediments were found to contain more PAHs in the upper 15 cm layers than in the bottom 15-25 cm samples. The samples that contained the most PAHs also contained the least amount of aromatic carbon and contained a significant amount of paraffinic carbon. Lignin-derived pyrolysis and TMAH thermochemolysis products were abundant and generally higher in all of the samples in comparison to those reported for modern coastal sediments, indicating a large flux of terrestrial carbon. The black carbon contents were found to range from 4.3% to 6.8%, which are significantly lower than other reports of black carbon in sediments, which represent as much as 65% of the total organic carbon content. The low black carbon content suggests that this type of refractory carbon may not be as responsible for regulating PAH distribution as indicated by other researchers.     

Mussels document loss of bioavailable polycyclic aromatic hydrocarbons and the return to baseline conditions for oiled shorelines in Prince William Sound, Alaska

Polycyclic aromatic hydrocarbons (PAH) were measured in mussels (Mytilus trossulus) collected between 1990 and 2002 from 11 sites on the shores of Prince William Sound (PWS), Alaska, that were heavily oiled by the 1989 Exxon Valdez oil spill (EVOS). This study, utilizing the methods of the NOAA Status and Trends Mussel Watch Program, found that concentrations of PAH released from spill remnants have decreased dramatically with time and by 2002 were at or near the range of total PAH (TPAH) of 3-355 ng/g dry weight obtained for mussels from unoiled reference sites in PWS. Time-series TPAH data indicate a mean TPAH half-life in mussel tissues of 2.4 years with a range from 1.4 to 5.3, yielding an annual mean loss of bioaccumulated TPAH of 25%. The petroleum-derived TPAH fraction in mussel tissues has decreased with time, reflecting the decreasing release of EVOS residues in shoreline sediments. These results show that PAH from EVOS residues that remain buried in shoreline sediments after the early 1990s are in a form and at locations that have a low accessibility to mussels living in the intertidal zone.     

Trace metals and hydrocarbons in sediments from the Southampton water region,with particular reference to the influence of oil refinery effluent

The concentrations of a number of trace metals (Co, Ni, Cu, Zn, Ag, Cd and Hg) have been determined in sediments from cores collected in the Southampton Water region. Measurements of total hydrocarbons were also made on several of the cores. Markedly elevated concentrations of copper, up to 362 μg/g dry wt, were found in sediments which were collected close to the discharge points of oil refinery outfalls and which also showed concentrations of total hydrocarbons considerably greater than the background levels for the estuary. The results of selective chemical extractions showed that much of the copper was present in the non-lattice fraction of the sediment. Although the concentrations of Co, Ni, Zn and Cd were significantly correlated with those of copper in the core showing the highest concentrations of this element, these metals were not enhanced in comparison with the levels found in several other parts of the estuary. Variations in concentrations of metals in sediments throughout the estuary were not correlated with differences in organic carbon content.     

Assessment of Aliphatic and Polycyclic Aromatic Hydrocarbons and Trace Elements in Coastal Sediments of the Saronikos Gulf,Greece (Eastern Mediterranean)

Surface sediments from the Saronikos Gulf were analyzed for their aliphatic hydrocarbon (AHC) and polycyclic aromatic hydrocarbon (PAH) content by gas chromatography – mass spectrometry (GC/MS). The concentrations of Fe, Cr, As, Sb, Co and Sc were also determined by neutron activation analysis (NAA). The survey was performed at the beginning of the operation of Athens’ sewage primary treatment unit and the results can be used to monitor the unit's long-term effects in the area. The composition of aliphatic hydrocarbons indicated a chronic oil-pollution in the Saronikos Gulf sediments. The industrially impacted Elefsis Bay sediments suffered from heavy petroleum pollution, while the sediments near the sewage outfall had a moderate degree of pollution. Mixed source patterns of polycyclic aromatic hydrocarbons with dominant pyrolytic inputs have been identified in the sediments. Total concentrations of Fe, As and Sb along with their Sc normalized values presented elevated values in Elefsis Bay sediments. Chromium was found enriched in the sediments near the Athens sewage outfall. Factor analysis results showed that a part of As and Sb in Elefsis Bay sediments could be associated with organic or sulphidic phases. In addition, the lithogenic fraction of the sediments and the Fe oxides/hydroxides were important trace element carriers. Chromium and PAH inputs from the sewage outfall were also detected. Comparison of PAH and trace element concentrations with internationally-used sediment quality guidelines (SQG) revealed that Elefsis Bay sediments had the greatest potential of causing adverse effects in benthic organisms.     

Sources of polycyclic aromatic hydrocarbons in marine sediments from southern and northern areas of the Norwegian continental shelf

Variability in levels and sources of polycyclic aromatic hydrocarbons (PAH) in sediments from one large sea area off the coast of northern Norway (“North area”, NA) have been compared to similar data from another large area off the coast of southern Norway (“South area”, SA). Samples from NA were collected at the Norwegian continental shelf in south-western Barents Sea and north-eastern Norwegian Sea. Samples from SA were from the Norwegian Trench and the Skagerrak. Sediment cores have been dated, characterised by grain size distribution (GS) and organic carbon content (TOC), and the composition of PAH and geochemical biomarkers (alkanes and triterpanes) studied to provide an insight into the different sources of PAH. Generally, PAH levels are higher in sediments from SA compared to NA. A mixture of pyrogenic and petrogenic sources contribute to PAH levels in SA, while the contents of petrogenic PAH is negligible in surface sediments in NA. At some locations in NA, petrogenic PAH levels are elevated in the deepest sediment layers from pre-industrial times, indicating a natural input of petroleum through seepage. Occurrence of elevated levels of microbial hopanoids (hopenes) in the deepest sediment layers at some locations both in the north and the south indicate the presence of petroleum.     

Evaluation of atmospheric transport as a nonpoint source of polycyclic aromatic hydrocarbons in marine sediments of the Eastern Mediterranean

Coastal marine sediment, air and seawater samples were collected at six sampling stations in the Eastern Mediterranean Sea distant from pollutant point sources. All sediment samples were analyzed to determine polycyclic aromatic hydrocarbon (PAH), black carbon (BC) and organic carbon (OC) contents. The PAH contents of gaseous and seawater samples of the study were determined in order to evaluate the role of air–sea exchange as PAH nonpoint source to the marine sediments. The average concentration of the total PAHs (∑PAHs) in the sediments varied from 2.2 to 1056.2 ng g⁻¹ dry weight. The average BC and OC contents varied from 0.3 to 5.6 and from 2.9 to 21.4 mg g⁻¹ dry weight, respectively. ∑PAH concentration in the marine atmosphere varied from 20.0 to 83.2 ng m⁻³. Air–water exchange flux (F_A–W) estimation has indicated air transport as a significant source of PAHs to pristine marine sediments of Eastern Mediterranean. In addition, the significant correlation between the PAHs and the organic and soot carbon content further suggests the importance of atmospheric input of PAHs to the sediments.     

Natural background and anthropogenic inputs of polycyclic aromatic hydrocarbons (PAH) in sediments of South-Western Barents Sea

Polycyclic aromatic hydrocarbons (PAH) were measured in sediment cores from 13 locations in South-Western Barents Sea as part of a detailed study of the Norwegian seabed under the MAREANO program. The generally low PAH levels found, an average around 200 ng g⁻¹ dry weight for sum PAH, indicate low inputs of petroleum hydrocarbons to the marine environment in the area. Differences in PAH composition and various PAH ratios indicate a natural, mostly petrogenic origin of PAH in sediments from the open sea locations, while the fjord locations show higher pyrogenic PAH contents with an increase towards upper sediment layers, indicating low inputs from human activities. Petrogenic PAH levels increase in deeper sediments at open sea locations, also when normalised to total organic carbon (TOC) contents, suggesting natural leakages of oil-related hydrocarbons in the area.     

环雷州半岛近海表层沉积物有机碳分布及其控制因素分析

对环雷州半岛近海43个海底表层沉积物的总有机碳(TOC)、总氮(TN)、沉积介质条件(包括沉积物粒度)进行了分析,探讨了沉积物TOC、TN的区域分布特征以及影响有机碳分布的主要因素。结果表明,环雷州半岛近海海域海底表层沉积物有机碳含量在0~0.79%之间,平均值为0.26%。与中国其它近海海域相比,环雷州半岛大部分近海区域海底表层沉积物有机碳含量明显偏低,为有机质贫乏区,仅雷州半岛西南部流沙湾近海海域为TOC相对高值区。总氮含量也不高,在0.011%到0.100%之间,TOC与TN存在较强的正相关性,且平面上TOC与TN分布高度重合,显示氮元素主要以有机化合物形式存在。TOC/TN比值在5.1~14.3之间,表明沉积有机质具有陆源输入和海洋自生来源的混合特征,但以雷州半岛西侧北部及东侧中部海域受陆源有机质输入影响更大。大多数站位海底沉积物粒度构成以粉砂为主、粘土次之,少数站位以砂质沉积为主。沉积物有机碳含量与粘土及粉砂含量呈弱正相关性,与沉积物pH值、Eh值及砂含量呈弱负相关性,这表明海底沉积物有机质丰度受有机质来源输入、海底氧化还原状态和沉积水动力条件(沉积物粒度)等因素综合控制。     

Organic components in size-separated aerosols from the western North Pacific

Marine aerosols in the western North Pacific were collected using a cascade impactor. Size-separated aerosols were analyzed for organic carbon, alkanes and polycyclic aromatic hydrocarbons (PAH). The results showed that the rate of decrease of the atmospheric concentrations of these organic components with increase in distance from Japan as well as from the coast of the Eurasian Continent was in the order PAHalkanes>organic carbon. The bulk of all these organic components occurred in the smallest size fraction of particles (<1m). Analysis of the alkanes and PAH indicated that the hydrocarbons in aerosols in Japanese coastal marine areas are primarily derived from terrestrial anthropogenic sources which also contribute to a lesser extent to aerosols in marine areas about 1,000 km off the coast of Japan. In remote marine areas the hydrocarbons on small particles (<1m) have principally a natural terrestrial origin while those on larger particles are marine in origin.     

Hydrocarbons in the Surface Layer of Bottom Sediments in the Northwestern Caspian Sea

The paper presents research results on the concentrations and compositions of aliphatic and polycyclic aromatic hydrocarbons in the surface layer of bottom sediments in the Northwestern Caspian Sea (2014) and compares them to data for sediments of the Middle and Southern Caspian (2012–2013). The seepage of hydrocarbons out of the sediment mass, resulting in abnormally high concentrations of aliphatic hydrocarbons per dry weight (up to 468 μg/g), as well as within the C_org composition (up to 35.2%), is considered the main source of hydrocarbons in sediments in the surveyed area of the Northern Caspian. This is also confirmed by the absence of any correlation between the hydrocarbon and C_org distributions, as well as by the transformed oil composition of high-molecular alkanes. The distribution of markers within polycyclic aromatic hydrocarbons points to a mixed genesis—petrogenic and pyrogenic—with prevalence of the latter. Unlike the shallow-water northern part of the Caspian Sea, the content and composition of hydrocarbons in deep-seated sediments are affected by facial conditions of sedimentation and by matter exchange at the water–bottom interface. Therefore, despite high C_org concentrations (up to 9.9%), sediments in deep-water depressions are characterized by a quite low concentration of aliphatic hydrocarbons (52 μg/g on average; 0.2% of C_org) with prevailing natural allochthonous alkanes.     

黄河口及近海表层沉积物中烃类化合物的组成和分布

为探讨黄河口近海表层沉积物有机质中烃类化合物的分布特征及输运过程,2003年9月采集了南北两个断面表层沉积物样品,对沉积物中正构烷烃和多环芳烃进行了分析,结果表明,黄河口表层沉积物中正构烷烃和多环芳烃的含量分别为0.38~2.55和0.371~0.650μg/g。在南北断面两种烃类化合物的分布明显不同:北断面受石油平台影响,烃类化合物在口门含量较高;南断面受黄河输入影响,由于大颗粒易于沉降,而吸附烃类化合物的能力较强的小颗粒易长距离输运,使这两种烃类化合物的含量从河口到近海整体呈上升的趋势。与北断面相比,南断面受水生源影响相对较弱,而且水生源的贡献随着离岸距离的增加而加强,在最大浑浊带后水生源急剧增强;在南断面多环芳烃主要来源为热解源,北断面多环芳烃受热解源和石油污染的共同影响。