Terrigenous Lipids Research Articles

Lipid biomarkers in suspended particulate matter and surface sediments in the Pearl River Estuary, a subtropical estuary in southern China

Lipid biomarkers in sediments in the Pearl River Estuary (PRE) have been studied in several previous studies, but little is known about their occurrence in the overlying water. Here, we determined the concentrations of lipids (n-alkanes, n-alkanols, sterols and fatty acids) in suspended particulate matter (SPM) in surface water and in sediments from the PRE. The data will improve our understanding of the sources, transport and sedimentation of lipids in estuarine environments. Our results showed that short-chain (C14–20) n-alkyl lipids contributed more than long-chain (C21–34) n-alkyl lipids to the total lipid concentrations in both SPM and sediments, suggesting aquatic plants and bacteria were the main contributors, whereas terrestrial organic matter (OM) were the minor contributors of n-alkyl lipids. It suggested that phytoplankton and bacteria contributing >65% to the n-alkyl lipids of SPM based on the three end-member mixing models. The concentrations of most lipids, except n-alkanes, decreased quickly in the low-salinity mixing zone and slowly decreased thereafter, with a transient slight increased when the salinity was 20–25, which would have been caused by variations of primary production in the aquatic system. In May, when rainfall was highest, lipids were characterized by a substantial contribution of terrestrial n-alkanes in the upstream SPM. Microbial activity and lipid degradation were found to occur in the water, and were most intense in the low–salinity mixing zone. Terrigenous lipids contributed more to the total lipid concentrations in sediments than in SPM, which demonstrated that terrigenous OM is relatively recalcitrant, and aquatic phytoplankton-derived OM is labile.

Matrix protected organic matter in a river dominated margin: A possible mechanism to sequester terrestrial organic matter?

The provenance of organic matter in surface sediments from the northern Gulf of Mexico was investigated by analyzing the compositions of lipid biomarkers ( n-alkanes, fatty acids, sterols) liberated after a series of chemical treatments designed to remove different organo-mineral matrix associations (i.e. freely extractable, base-hydrolyzable, unhydrolyzable). Bulk analyses of the organic matter (carbon content, carbon:nitrogen ratios, stable and radiocarbon isotopic analyses) were also performed on the intact sediments and their non-hydrolyzable, demineralized residue. We found recognizable lipids from distinct sources, including terrestrial vascular plants, bacteria and marine algae and zooplankton, within each of the isolated fractions. Based on the lipid signatures and bulk compositions, the organic matter within the unhydrolyzable fractions appeared to be the most diagenetically altered, was the oldest in age, and had the highest abundance of terrigenous lipids. In contrast, the base-hydrolyzable fraction was the most diagentically unaltered, had the youngest ages and was most enriched in N and marine lipids. Our results indicate that fresh, autochthonous organic matter is the most important contributor to base-hydrolyzable lipids, whereas highly altered allochthonous sources appear to be predominant source of unhydrolyzable lipids in the surface sediments from the Atchafalaya River shelf. Overall, the lipid biomarker signatures of intact sediments were biased towards the autochthonous source because many of the organic compounds indicative of degraded, terrigenous sources were protected from extraction and saponification by organo-mineral matrices. It is only after these protective matrices were removed by treatment with HCl and HF that these compounds became evident.

Dissolved and particulate organic matter source-age characterization in the upper and lower Chesapeake Bay: A combined isotope and biochemical approach

In order to characterize the sources and ages of organic matter contributing to river and estuarine outflow waters, the present study investigated δ14C and δ13C signatures of the major operationally defined biochemical classes of ultrafiltered dissolved organic matter (UDOM) in conjunction with lipid biomarker and elemental compositions of UDOM and suspended particulate organic matter (POM) in the Chesapeake Bay. Freshwater (Susquehanna River) UDOM was dominated by a molecularly uncharacterized (MUC) fraction, followed by total carbohydrate (TCHO), total hydrolysable amino acid (THAA) and total lipid (TLE) components. In contrast, UDOM at the bay mouth (salinity ~22–24) was comprised mainly of TCHO, followed by MUC, THAA, and TLE. The δ14C and δ13C signatures of both UDOM and its major biochemical classes indicate that Susquehanna DOM is derived in part from old allochthonous terrestrial sources, whereas young marine sources dominate at the bay mouth. In contrast to the other biochemical classes, lipophilic DOM at both sites was very old (~5,000–7,000 years B.P.). In addition, factor analysis of lipid biomarker compounds revealed unique signatures for the UDOM and POM pools that imply disparate source and/or recycling properties as well as potential influences due to physical partitioning. Lipid biomarker compounds showed that although autochthonous riverine/estuarine sources dominated both the UDOM and POM pools, terrigenous lipids were elevated in the Susquehanna during high flow conditions. The presence of lipid biomarkers diagnostic of “fresh” algal material in UDOM further suggested its greater reactivity than POM. The observed biochemical and lipid biomarker compositions and isotopic signatures of UDOM and POM are consistent with previous findings suggesting that these two major organic matter pools have dissimilar reactivities and cycling times, and they derive from comparatively unique source-age materials in rivers and estuaries.

Lipids in suspended matter and sediments from the East China Sea Shelf

Total suspended matter (TSM) and sediment samples from the East China Sea (ECS) Shelf were analyzed for aliphatic hydrocarbons, alkanols and sterols. TSM samples showed a strong predominance of n-C 17, pristane, n-C 18, n-C 19, n-C 19:1, n-C 21:6 and squalene, being attributed to plankton inputs. Stations with high percentages of these hydrocarbons were generally situated near the Changjiang River mouth. Three stations with highest concentrations of n-C 21:6 were located in the hot spot of chlorophyll reported in the literature (Gong et al., 1996, Continental Shelf Research 16, 1561–1590). Phytol (the most abundant alcohol in TSM) and C 20:1 and C 22:1 n-alkenols were dominant in the alcohol fraction, being representative of plankton contributions. The sterol composition of TSM was dominated by 24-methylcholesta-5,22E-dien-3β-ol, cholest-5-en-3β-ol, cholesta-5,22E-dien-3β-ol, and 27-nor-24-methylcholesta-5,22E-dien-3β-ol. Terrigenous lipids from the Changjiang River did not play a significant role in TSM since they were transported mainly southward. The sedimentary composition of these lipids showed a significant depletion of planktonic compounds in relation to other organic molecules. A comparison of these planktonic hydrocarbons in TSM and in sediments showed that degradation is in the following order: n-C 21:6 > n-C 19:1, n-C 19, and n-C 17 > n-C 18, pristane, and squalene. A similar comparison for the alcohols showed the following degradation trend: C 20:1 and C 22:1 n-alkenols > phytol. Carbon preference indices (CPIs) of suspended matter varied from 1.04 to 1.82 (average 1.41), and those of sediment ranged between 1.82 and 3.74 (average 2.81), reflecting higher contributions of the more refractory higher plant n-alkanes in the sediments.

Distribution of terrigenous lipids in marine sediments off northeastern Taiwan

Surface sediments on the continental margin off northeastern Taiwan have been analyzed for terrigenous lipids including n-alkanes, n-fatty alcohols, and sterols. Marine input to the sediments is particularly low based on the average n-C17/n-C29 alkane and n-C16/n-C28 fatty alcohol ratios, 0.15±0.13 and 0.13±0.06, respectively; this may be due to the fact that marine lipids are more prone to degradation than terrestrial ones. The study area has the highest plant wax n-alkane contribution (average carbon preference index 3.9±1.2) among the coastal marine areas surrounding Taiwan; lateral particle transport from the southern East China Sea shelf and river runoff from the east Taiwan coast are considered to be the major contributors. The distributions of plant wax n-alkane and n-alkanol concentrations normalized to total organic carbon (TOC) in the study area generally show maximum values on the upper slope of the southernmost Okinawa Trough, but not for phytosterols. Linear regression of TOC versus plant wax n-alkane concentrations show a weak relationship (r=0.64, p=0.001), and an even weaker relationship (r=0.42, p=0.05) between TOC and plant wax n-fatty alcohol concentrations is found. This could be attributed to several factors: (1) a complex input (not a point source) of terrigenous organic matter to the study area, (2) TOC also including marine organic matter, (3) temporal variations in river flow due to flooding, and (4) different rates of degradation for TOC and individual biomarkers. However, in spite of those factors, TOC and phytosterol concentrations are positively linearly correlated (r=0.85, p<0.001), implying that the dilution of phytosterols in terrigenous organic carbon with marine organic carbon with or without the phytosterols follows a nearly constant ratio, which is remarkable. In addition, the predominant source of diploptene in the sediments does not appear to be of higher plant origin.

Marine and terrigenous lipids in coastal sediments from the Peru upwelling region at 15°S: Sterols and triterpene alcohols

The distributions of free 4-desmethyl sterols in sediments from the Peru coastal zone at 15°S have been determined. Major free sterols in the surface sediments include cholesterol, which is mainly derived from zooplankton, and two C 28 sterols: 24-methylcholesta-5,24(28)-dien-3β-ol and 24-methylcholesta-5,22E-dien-3β-ol both of which are derived fro diatoms. Their concentrations decrease by almost an order of magnitude in the top 20 cm of sediment depth, indicating that free sterols are rapidly degraded in this sedimentary environment. Lipids from higher plants were also detected: long chain fatty acids and alcohols and various triterpenoid alcohols, including taraxerol, lupeol and α- and β-amyrin. The concentrations of most terrigenous lipids varied by less than a factor of 3 over the same depth, and these changes were not correlated with changes in the concentrations of total organic carbon. Below 3 cm, lipids from higher plants predominated in the extractable lipid distributions due to the more rapid degradation of marine lipids. We postulate that there are significant marine sources of the higher plant sterols 24-ethylcholesterol, 24-ethylcholesta-5,22E-dien-3β-ol and 24-methylcholesterol in these sediments. A high proportion of many of the terrigenous lipids in these sediments are probably transported into the coastal zone by rivers, rather than from the atmosphere, and then redistributed by bottom currents.

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 C 12–C 19 fatty acids and polyunsaturated C 18 acids relative to TOC occured with the settling of organic matter ot the lake bottom, whereas the amounts of terrestial saturated C 20–C 30 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.

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.

The Black Sea, a sink for terrigenous lipids

Abstract Solvent-soluble organic matter in samples from four coring sites in the Black Sea has been analyzed. The samples cover geologic time from Recent to about 23,000 years b.p. and environmental transitions from oxic and marine to oxic and fresh, then to the present anoxic marine waters. The organic carbon content of these samples ranged from Terrigenous marker compounds were present in the lipids far in excess of those derived from marine sources. The δ 13 C values of the lipids from samples with terrigenous components were within the range observed for non-marine organic matter. This and the predominance of terrigenous lipid markers indicated that the bulk of the solvent-soluble organic matter represents such influx. The indicators of terrigenous lipids were n -alkanes ( n -C 25 to n -C 33 , odd-to-even predominance, maximum at n -C 29 or n -C 31 ), n -fatty acids ( n -C 22 to n -C 32 , even-to-odd predominance, maximum at n -C 24 or n -C 26 ) steroidal, triterpenoidal, and diterpenoidal compounds. The major input mechanisms were potamic transport, followed by turbidite redistribution. The more recent anoxic conditions have preserved organic matter in greater amounts in the upper than in the deeper sediments. The transition from oxic to anoxic was reflected in the sediments by a parallel change in the relative amounts of the compounds derived from phytol, i.e. in oxic sediments, the concentration of pristane was greater than phytane and in anoxic sediments, the opposite was the case.