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.     

Concentration and composition of hydrocarbons in bottom sediments from the Sakhalin shelf

Aliphatic and polycyclic aromatic hydrocarbons were examined in the surface layer of bottom sediments from the eastern part of the Sakhalin shelf (the materials were sampled in the summer of 2002). The concentrations of hydrocarbons were determined to have changed since the beginning of the development of oil fields (compared with earlier years). According to the distribution of markers in the hydrocarbon compositions, the bottom sediments are dominated by allochthonous (terrigenous) hydrocarbons, which are the most stable compounds. The presence of transformed anthropogenic oil alkanes, which have never been found before, may be indicative of the increasing pollution of the region.     

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.     

The early diagenesis of aliphatic hydrocarbons and organic matter in sedimentary particulates from Dabob Bay,Washington

Aliphatic hydrocarbon compositions were quantitatively characterized in plankton, sediment trap-collected particulate materials and sediments from Dabob Bay using high resolution glass capillary gas chromatography. The average net accumulation of individual hydrocarbons measured in a 1-yr series of sediment traps was compared with the net accumulation of corresponding compounds measured in three depth intervals of ²¹⁰Pb-dated bottom sediments. Systematic and rapid decreases in the net accumulation of individual hydrocarbons were observed from the sediment traps to the sediments. Most pronounced decreases were measured for planktonically derived hydrocarbon constituents (e.g. pristane and two unsaturated compounds) which are rapidly remineralized at or near the sediment-water interface. Consequently, the amount of each compound measured in deposited sediments is not necessarily a quantitative indication of its initial flux to the sediments. The n-alkanes (C_25,27,29,31). characteristic of terrestrial plant waxes, are the predominant hydrocarbons measured by 4–6 cm depth in these sediments and show reasonably constant net accumulation below this interval.Significant diagenetic alteration of the bulk organic matter contained in the average sediment trap particulate material is also noted through comparison with bottom sediments on the basis of organic C/N and δ¹³C measurements. Organic matter elementally similar to marine plankton is preferentially remineralized upon deposition of the sedimentary particulates. The residual organic matter remaining and buried in the bottom sediments closely resembles terrestrial organic matter.     

Early diagenesis of organic matter in the water column and sediments: Microbial degradation and resynthesis of lipids in Lake Haruna

Particulate matter, sediment trap, and surface sediment samples collected in freshwater Lake Haruna were studied to understand early diageesis of organic materials in the water column and in bottom sediments. The samples were analyzed for biomarkers, including aliphatic and aromatic hydrocarbons, fatty alcohols, saturated and unsaturated fatty acids, β- and ω-hydroxyacids, and α,ω-dicar☐ylic acids. Decreases in concentrations of autochthonous saturated C₁₂–C₁₉ fatty acids and polyunsaturated C₁₈ acids relative to TOC occured with the settling of organic matter ot the lake bottom, whereas the amounts of terrestial saturated C₂₀–C₃₀ acids remained almost constant. Conversely, the concentrations of monosaturated fatty acids, branched chain fatty acids, and β- and ω-hydroxyacids, which are probably produced by microbial activity, increased. These results indicate that preferential degradation of algal lipids accompanies microbial resynthesis of lipids during settling, however, terrigenous lipids are relatively stable.     

Composition and origin of organic matter in surface sediments of Lake Sarbsko: A highly eutrophic and shallow coastal lake (northern Poland)

We present an organic geochemical study of surface sediments of Lake Sarbsko, a shallow coastal lake on the middle Polish Baltic coast. The aim was to provide evidence concerning the origin of the organic matter (OM) and its compositional diversity in surface deposits of this very productive, highly dynamic water body. The content and composition of the OM in the bottom sediments were investigated at 11 sampling stations throughout the lake basin. OM sources were assigned on the basis of bulk indicators [total organic carbon (TOC), total nitrogen (TN), δ¹³C_TOC and δ¹⁵N and extractable OM yield], biomarker composition of extractable OM and compound-specific C isotope signatures. The source characterization of autochthonous compounds was verified via phytoplankton analysis. The distribution of gaseous hydrocarbons in the sediments, as well as temporal changes in lake water pH, the concentration of DIC (dissolved inorganic carbon) and δ¹³C_DIC were used to trace OM decomposition.The sedimentary OM is composed mainly of well preserved phytoplankton compounds and shows minor spatial variability in composition. However, the presence of CH₄ and CO₂ in the bottom deposits provides evidence for microbial degradation of sedimentary OM. The transformation of organic compounds in surface, bottom and pore waters via oxidative processes influences carbonate equilibrium in the lake and seasonally favours precipitation or dissolution of CaCO₃.The data enhance our understanding of the relationships between the composition of sedimentary OM and environmental conditions within coastal ecosystems and shed light on the reliability of OM proxies for environmental reconstruction of coastal lakes.     

Results of multiyear studies on the dynamics of pollution of lake Baikal by polycyclic aromatic hydrocarbons in the area waste water discharge from the Baikal Pulp and Paper Plant

New data on the concentration and spatial distribution of the benz(a)pyrene and polycyclic aromatic hydrocarbons in bottom sediments in the testing area of the Baikal Pulp and Paper Plant (BPPP) waste water discharge in 1981–1988 and 2010 are presented in this paper. The bottom sediments in this section of the lake are strongly polluted with polycyclic aromatic hydrocarbons.     

Diagenetic cycling of trace elements in the bottom sediments of the Swan River Estuary,Western Australia

Teflon strips were used in-situ in the bottom sediments at two sites in the Swan River Estuary to collect diagenetic Fe–Mn oxyhydroxides and monitor monthly changes in their morphology and trace element geochemistry. This study demonstrates that substantial concentrations of trace elements accumulate at the redox front during the formation of diagenetic Fe–Mn oxyhydroxides. It is likely that the Fe–Mn oxyhydroxides initially nucleate and grow on the Teflon strips via bacterial activity. Trace element geochemistry of the diagenetic Fe–Mn oxyhydroxides is influenced by changes in the supply of trace elements from either the bottom sediments and/or water column or changes in the physico-chemical status of bottom and porewaters. If sufficient diagenetic Fe–Mn oxyhydroxides are preserved in the upper layer(s) of the bottom sediment it is possible that diagenetic (secondary) trace element enrichment profiles may be produced which modify the historical input of natural or anthropogenic trace element sources. Alternatively, partial or complete dissolution of the diagenetic Fe–Mn oxyhydroxides in response to temporal changes in the redox status of the bottom sediment may lead to a substantial underestimate of trace element fluxes in historical bottom sediment profiles. This study highlights that considerable care must be taken when interpreting short- to long-term geochemical profiles in bottom sediments due to the possible occurrence of rapid, seasonally mediated diagenetic processes.     

Evaluation of hydrocarbon pollution in marine sediments of Sfax coastal areas from the Gabes Gulf of Tunisia,Mediterranean Sea

The Tunisian environmental legislation that follows the EC Directives requires monitoring of persistent, toxic and bio-accumulated substances commonly considered as hazardous substances. In order to comply with this requirement, samples of sea water, sediment and biota from the urbanized and industrialized coast line of Sfax city are investigated. This study presents the results of petroleum hydrocarbon content, distribution and probable origin (anthropogenic and/or biogenic) in 16 intertidal sediments of Sfax coastal area. Alkane distribution indices and hydrocarbon distribution patterns are used to identify natural and anthropogenic input. Non-aromatic hydrocarbons present a high concentration with a range varying from 180 to 1,400 μg/g of dry sediment. The total concentrations of polycyclic aromatic hydrocarbons (PAHs) varied from 0.41 to 5.6 μg/g dry weight. These concentrations are comparable to other marine areas that receive important inputs. n-Alkanes with carbon number ranging from 15 to 35 are identified to be derived from both biogenic and anthropogenic sources in varying proportions. Pristane/phytane ratio shows values lower than 1.4 suggesting the presence of petroleum contamination. This is confirmed by the presence of a large group of unresolved complex mixture and the identification of hopanes with predominant C29 and C30 compounds and steranes with predominance of C27 over C28 and C29 compounds. Ratios of selected PAH concentrations indicate petrogenic and pyrolytic origin of hydrocarbons. Anthropogenic hydrocarbon inputs were more apparent at sites associated with industrial discharges, shipping activities and sewage outfalls.     

Organic tracers in sediments from the coastal zone of Ras Abu el-Darag,Gulf of Suez

Sediment samples from the coastal zone of the Gulf of Suez contain a variety of organic compounds from anthropogenic and natural sources. A total of 12 surface samples of bottom sediments were collected with an Ekman grab sampler along an off-shore transect south of Ras Abu el-Darag. The samples were extracted with a mixture of dichloromethane and methanol (3:1 v/v) after drying and sieving through 250 μm mesh. The extracts were derivatized and analyzed by gas chromatography–mass spectrometry in order to characterize the chemical composition and sources of the organic components. Marine with minor terrestrial biota were the major natural sources of organic tracers and included n-alkanoic acids, sterols and saccharides (5.7–76.7%). Anthropogenic sources, from petroleum related activities, detergent usage for spill cleaning and littering, are indicated by the presence of n-alkanes with carbon preference index ≤1.0, hopanes, steranes, unresolved complex mixture of branched and cyclic hydrocarbons, alkyl nitriles, alkamides and plasticizers. Their total relative concentrations ranged from 23.3 to 97.3% of the total extracts. Petroleum residues from natural seepage may also be part of these hydrocarbons. The levels of anthropogenic inputs decrease from about 94% in coastal zone sediments to about 20% in sediments from the reef front.     

Volatile organic compounds in open ocean and coastal surface waters

Volatile organic compounds with volatilities ranging between those of n-hexane and n-pentadecane were identified in open ocean and coastal marine surface water samples taken in the north central part of the Gulf of Mexico. Approximately 40 organic compounds were found. The types and concentrations of the compounds found depended upon the extent of anthropogenic and terrestrial influences. Open ocean samples consisted mostly of aromatic hydrocarbons, whereas coastal samples included alkanes, cycloalkanes, cycloalkenes, aromatic hydrocarbons, aldehydes and chlorinated hydrocarbons. Unpolluted open ocean and coastal water samples had individual concentrations rarely exceeding 5 ng/kg; some aromatic hydrocarbons approached 15 ng/kg. n-Pentadecane dominated the hydrocarbons in these samples (50–100 ng/kg). The most polluted coastal water samples had individual volatile organic concentrations as great as 150 ng/kg with total concentrations approaching 1000 ng/kg. The terpene, limonene, was found extensively in the coastal samples (up to 40 ng/kg). Photooxidization of hydrocarbons in industrial/urban atmospheres was considered as a possible source of aldehydes present in coastal water. The dynamic headspace stripping/Tenax-GC adsorption method coupled with packed column gas chromatography, and gas chromatography-mass spectrometry were used for volatile organic analysis.     

Composition of organic compounds in bottom sediments of lakes in the taiga and steppe zones in Siberia

The paper presents chromatographic–mass spectrometric data on the individual composition of organic compounds in sapropel-like deposits of lakes in the steppe, forest–steppe, and three taiga natural climatic zones (NCZ) in Khakassia and western Siberia. Data on the individual composition of n-alkanes, carboxylic acids and their esters, thiophenes, phytol, phytone, steroids, and di- and triterpenoids and on their distribution in the sediments show systematic variations in the composition of the organic matter (OM) with increasing ambient temperature and the aridity of the climate. The concentrations of all groups of the compounds in lacustrine sediments decrease southward, and simultaneously esters with long (up to С₂₀) alkyl substituents appear. The concentrations of oxygen-bearing compounds increase among the acyclic structures and triterpenoids, as also do the concentrations of structures ketonic substituents among the steroids. The dominance of the carboxylic acids and their esters by high molecular weight homologues gives way to the dominance of palmic acid and its derivatives. Among n-alkanes, the dominance of С₂₇ and С₂₉ hydrocarbons typical of terrestrial plants gives way to a higher percentage of homologues С₂₁–С₂₅ (macrophytes) and С₃₁ (herbaceous plants). Among the tocopheroles, the concentration of the oxidized form of α-tocopherol (acetate) increases.     

The content and composition of organic compounds in the snow-ice cover of the White Sea

This paper reports data on the concentrations of organic compounds (organic carbon, C_org; lipids; aliphatic hydrocarbons, AHCs; and polycyclic 0aromatic hydrocarbons, PAHs) in snow, ice, and subice waters from the mouth of the Severnaya Dvina River (2005–2007) and Kandalaksha Gulf (Chupa Bay, 2004) at the end of winter. It was established that organic compounds are accumulated in the snow and upper ice layer near the town of Archangelsk. The distribution of molecular markers indicates that pollution was mainly caused by local fallouts. In Chupa Bay, organic compounds are concentrated in the lower ice layers, which is typical of the Arctic snow-ice cover. The high contents of organic compounds in the snow-ice cover of the White Sea are caused by the pollution of its air and water during the winter season.     

Sources and pathways of natural and anthropogenic hydrocarbons into the natural dump Arkona Basin (southern Baltic Sea)

 Surface sediments, suspended particulate matter and fluffy-layer material, collected in the Arkona Basin and the Pomeranian Bay during 1995–1997, as well as air particulate matter, collected on the island of Rügen during August 1995, were analysed for total organic carbon content, saturated and polycyclic aromatic hydrocarbons (PAH). The resulting concentrations and distributions of these compounds and molecular PAH ratios are discussed in terms of matrix, origin of the organic matter and seasonal variations. The data show that the Oder river can be identified as a major source for PAH transported into the southern part of the Arkona Basin. A strong atmospheric input of PAH is noted for the central and northern part of the basin. In general, anthropogenic and bacterially degraded hydrocarbons bound to organic carbon-rich and small particles are mainly deposited in the basin center, whereas their natural counterparts accumulate mainly on the basin flanks covered by coarser grained sediments. Received: 2 March 1999 · Accepted: 8 June 1999     

Sulfur Compounds in Bottom Sediments of Fresh-Water Basins (Mouth of the Severnaya Dvina River and Rybinsk Water Reservoir)

Composition and distribution of different forms of sulfur in bottom sediments of the Severnaya Dvina River mouth and Rybinsk water reservoir are studied. The sediments are characterized by low accumulation rate of reduced sulfur compounds and high content of organic matter. Common features of the distribution of products of hydrogen sulfide in sediments of the river and water reservoir and the specificity of anthropogenic influence in each basin are established.     

Assessment of metal concentrations in lake sediments of southwest Japan based on sediment quality guidelines

Geochemical analysis of the bottom sediments of Lakes Banryoko, Onbe, Hamahara and Kijima in Shimane prefecture of southwest Japan was carried out to determine their metal concentrations, and to assess the potential for ecological harm by comparison with sediment quality guidelines. The work conducted includes water quality measurement, and analyses of trace and major elements and rare earth element (REE) of sediments. Results showed that water quality of the lakes contrasts slightly between their upper and lower parts. Average abundances of As, Pb, Zn, Cu, Ni, and Cr in Banryoko sediments were 27, 33, 90, 27, 25, and 46 ppm, respectively, compared to 31, 52, 175, 44, 44, and 75 ppm at Onbe, 11, 26, 96, 13, 13, and 35 ppm at Hamahara, and 24, 43, 193, 31, 12, and 30 ppm at Kijima. These concentrations exceeded the lowest effect level that has moderate impact on aquatic organisms as proposed by the New York State Department of Environmental conservation. Pb and Cu abundances are comparable to the Coastal Ocean Sediment Database threshold, while As and Zn exceed this value, indicating the concentrations of these metals are potentially toxic. Increases in the abundances of these metals in lake sediments are probably related to the reducing condition of the sediments, anthropogenic sources and surface soil erosion. The REE patterns of sediments in the study areas are broadly comparable to the average upper continental crust, but show some contrast between lakes due to differing source litho type. Significant positive correlations between Fe₂O₃ and As, Pb, Zn, and Cu were found in the sediments, suggesting these metals may be adsorbed on Fe oxides in the lake sediments.     

Chemical evidence for advection of hydrothermal solutions in the sediments of the Galapagos Mounds Hydrothermal Field

Pore water profiles of Ca, Mg, F, PO₄^?3 and Mn in the Galapagos Mounds Hydrothermal Field are believed to reflect, in part, upwelling of hydrothermal solutions through the sediments. Concentration-depth profiles in a low heat flow area just north of the Mounds Field display diagenetic changes typical of those found in pore waters underlying highly productive surface waters, consistent with the inference of no water flow or very slow downwelling ($\text{w < 5}\text{cm/yr}$) of bottom water through these sediments. Rates of upward advection calculated from Mounds Field pore water profiles of Ca, Mg, and F profiles agree well with each other, averaging about 1 cm/yr in the pelagic sediments near the mounds and 15–30 cm/yr within the hydrothermal mounds themselves. The upward advection also modifies the shape of PO₄^?3 and Mn profiles.Advection rates inferred from the pore water data are generally in reasonable agreement with those made from heat flow data.The higher Ca and lower Mg, F, PO₄^?3 and Mn concentrations in Mounds Field pore waters (compared with those of the low heat flow area) suggest chemical exchange between the solution and basalt prior to upwelling. Li⁺, K⁺, Rb⁺, Sr⁺⁺ and SO₄^? concentrations are indistinguishable from bottom water. This suggests very high effective water/rock ratios during the reactions which produced the upwelling solutions, perhaps due to extensive prior alteration of basalt adjacent to the flow path of water through the crust Inferred reaction temperatures are between 70–150°C.     

Cause of elevated as concentrations in the Baltic Sea and Vistula Lagoon

As is less toxic than Hg, Cd, Pb, Se, Zn, and Cu. The As clarke for clays and shales is 10 ppm. Our samples of bottom sediments from Kurshskii Bay were determined to contain from 15 to 26 ppm As and up to 34 ppm As in the vicinity of the Neman River mouth. Elevated As concentrations (50–114 ppm) were detected in four columns of subsurface bottom sediments (at depths of 10–65 cm) from the Vistula Lagoon. Elevated As concentrations (50–180 ppm) were also found in a few surface samples of sand from the Gdansk Deep near oil platform D-6. These sediments are either partly contaminated with anthropogenic As or contain Fe sulfides and glauconite, which can concentrate As and contain its elevated concentrations. The As concentration in columns of bottom sediments from the Gulf of Finland were at the natural background level (throughout the columns) typical of the area (9–34 ppm). We repeatedly detected very high As concentrations (up to 227 ppm As) in pelitic ooze from Bornholm Deep, in the vicinity of the sunken vessel with chemical weapons. The sources of elevated As concentrations in the Baltic Sea are the following: (1) chemical weapon (CW) material buried in the floor of the Baltic Sea; (2) As-bearing pesticides, agricultural mineral fertilizers, and burned coal and other fuels; (3) kerogen-bearing Ordovician rocks exposed on the bottom; and (4) As-rich Fe sulfides brought to the area together with construction sand and gravel. This mixture was used in paper production and for the construction of hydraulic engineering facilities in the Vistula Lagoon in the early 20th century and later caused the so-called lagoon disease.     

Potential ecological risk assessment,enrichment, geoaccumulation,and source identification of metals in the surface sediments of Choghakhor Wetland,Iran

This study reported the first comprehensive research on identification of metal concentrations (Fe, Mg, Mn, Pb, Cd, Cr) in order to provide baseline data for future studies, identify possible sources, determine degree of pollution, and identify potential ecological risks of metals in surface sediments from Iran’s Choghakhor Wetland. The order of metal concentration was as follows: Fe > Mg > Mn > Pb > Cd > Cr, with mean concentrations of 6140.35, 1647.32, 289.03, 1.10, and 0.45 µg/g of dry weight, respectively. These results reveal that Choghakhor Wetland is not heavily polluted compared to other regions. The results of enrichment factor (EF) and geoaccumulation index (I _geo) showed that Fe, Pb, Mg, Cr, and Mn presented low levels of contamination and probably originated from natural sources. On the other hand, the results of EF and I _geo indices suggested that Cd concentrations in sediments of Choghakhor Wetland originated from anthropogenic sources. Based on the results of three sets of sediment quality guidelines, only Cd concentration in sediments of Choghakhor Wetland is a threat for aquatic organisms of Choghakhor Wetland. The results of multivariate analysis such as principal component analysis and cluster analysis showed that Fe–Mn, Cr–Mg, and Pb groups originated from natural sources, while Cd concentrations in sediments of Choghakhor Wetland originated from both natural and anthropogenic sources (mainly chemical fertilizers). To our knowledge, this is the first study about metal concentrations in sediments of Choghakhor Wetland, and because of low levels of these metals, these concentrations can be considered background levels for future investigation.     

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.