Structural diversity and fate of intact polar lipids in marine sediments

Marine sediments harbor an enormous quantity of microorganisms, including a multitude of novel species. The habitable zone of the marine sediment column begins at the sediment-water interface and probably extends to depths of several thousands of meters. Studies of the microbial diversity in this ecosystem have mostly relied on molecular biological techniques. We used a complementary method - analysis of intact polar membrane lipids - to characterize the in-situ microbial community in sediments covering a wide range of environmental conditions from Peru Margin, Equatorial Pacific, Hydrate Ridge, and Juan de Fuca Ridge. Bacterial and eukaryotic phospholipids were only detected in surface sediments from the Peru Margin. In contrast, deeply buried sediments, independent of their geographic location, were dominated by archaeal diether and tetraether lipids with various polar head groups and core lipids. We compared ring distributions of archaeal tetraether lipids derived from polar glycosidic precursors with those that are present as core lipids. The distributions of these related compound pools were distinct, suggestive of different archaeal sources, i.e., the polar compounds derive from sedimentary communities and the core lipids are fossil remnants from planktonic communities with possible admixtures of decayed sedimentary archaea. This in-situ production of distinct archaeal lipid populations potentially affects applications of the TEX86 paleotemperature proxy as demonstrated by offsets in reconstructed temperatures between both pools. We evaluated how varying cell and lipid stabilities will influence the sedimentary pool by using a box-model. The results are consistent with (i) a requirement of continuous inputs of freshly synthesized lipids in subsurface sediments for explaining the observed distribution of intact polar lipids, and (ii) decreasing lipid inputs with increasing burial depth.     

Influence of lake water pH and alkalinity on the distribution of core and intact polar branched glycerol dialkyl glycerol tetraethers (GDGTs) in lakes

Branched glycerol dialkyl glycerol tetraethers (GDGTs) are bacterial membrane lipids, ubiquitously present in soils and peat bogs, as well as in rivers, lakes and lake sediments. Their distribution in soil is controlled mainly by pH and mean annual air temperature, but the controls on their distribution in lake sediments are less well understood. Several studies have found a relationship between the distribution of branched GDGTs in lake sediments and average lake water pH, suggesting an aquatic source for them, besides that for soil transported to the lake via erosion. We sampled the surface water suspended particulate matter (SPM) from 23 lakes in Minnesota and Iowa (USA), that vary widely in pH, alkalinity and trophic state. The SPM was analyzed for the concentration and distributions of core lipid (presumed fossil origin) and intact polar lipid (IPL, presumed to derive from living cells) branched GDGTs. The presence of substantial amounts (18–48%) of IPL-derived branched GDGTs suggests that branched GDGTs are likely of autochthonous origin. Temperature estimates based on their distribution using lake-specific calibrations agree reasonably with water temperature at time of sampling and average air temperature of the season of sampling. Importantly, a strong correlation between the distribution of branched GDGTs and lake water pH was found (r² 0.72), in agreement with a predominant in situ production. An stronger correlation was found with lake water alkalinity (r² 0.83), although the underlying mechanism that controls the relationship is not understood. Our results raise the potential for reconstructing pH/alkalinity of past lake environments, which could provide important knowledge on past developments in lake water chemistry.     

Distribution of heavy metals in the core sediments of a tropical wetland system

Five sediment cores from the fresh water region of the Vembanad wetland system were studied for the trace element contents The average concentration of iron, manganese, nickel, copper, zinc, cadmium, lead, mercury and chromium were determined. The core samples were collected using gravity type corer, digested with a mixture of nitric acid and perchloric acid and analyzed by atomic absorption spectrophotometry. Heavy metals such as iron, copper, nickel and zinc reported enrichment towards the surface of the core sediment sample collected from the centre of the lake. Lead, cadmium and mercury showed uniform distribution through out the core. Quality of the sediments were evaluated based on sediment quality guidelines, pollution load index, sum of toxic units and with effect range low/effect range median and threshold effect level/probable effect level values of Environmental Protection Agency guidelines. The degree of contamination for each station was determined. The concentration of different heavy metals has been compared with the world average concentration of shale values. Results of the analysis showed that Vembanad lake is facing serious metal pollution with increased rate of deposition.     

Distributions of branched GDGTs in soils and lake sediments from western Uganda: Implications for a lacustrine paleothermometer

Bacterially produced branched glycerol dialkyl glycerol tetraethers (GDGTs) are ubiquitous in soils and lake sediments and can potentially be used to reconstruct past temperatures. In lakes, however, it is still unclear if these compounds are derived from eroded soils or if they are produced in situ. To better understand environmental controls on the distributions of these compounds and the sources of branched GDGTs to lake sediments, we compare branched GDGT distributions and concentrations in lake sediments and catchment soils within a 3600 m altitudinal transect in western Uganda. Reconstructed mean annual air temperature (MAAT), determined from the degree of methylation (MBT) and cyclisation (CBT) of branched GDGTs in soils, decreases with increasing altitude, as is expected from the air temperature gradient in our transect. However, we observe significant offsets between observed and reconstructed temperatures in soils from wet, high elevation soils but not in most dry, low elevation soils. Branched GDGT distributions differ significantly between lake sediments and soils at all elevations, with greater differences at low elevations than at high elevations. These data support previous hypotheses that branched GDGTs are produced in situ in lakes and suggest that the abundance of water in soil environments may play a role in controlling the distribution of branched GDGTs. While branched GDGTs in lacustrine sediments can be used to reconstruct temporal temperature variations in lakes, we urge caution in utilizing this proxy in lacustrine systems with high soil loadings, especially if there is evidence of changing clastic fluxes through time.     

Microscopic gold in marine and oceanic sediments

The present-day contribution of coastal-marine placers into the bulk gold production is insignificant. As usual, only gold of coarse- and medium-grained classes is recovered while the fine-grained and dispersed gold are disposed into tailings. During the sedimentation, such a floating gold is removed far from the wave-surf zone. Despite the common belief about poor prospects of the Black Sea shelf for modern gold placers, we have proved the expediency to study the distribution of floating microscopic gold in Holocene marine sediments and carried out the respective works. Using the special concentrating methods, we enabled to detect the gold in most of the 830 samples collected. Geomorphological, lithological, hydrodynamic, and other factors controlling the gold potential were determined. In some cases, the gold content exceeds the minimal economic grade in continental placers. The prospective sites for further investigation were outlined. It was established that the polygenic microscopic gold can be divided into at least clastic, authigenic, and clastic-authigenic types. According to our data, the alluvial, lagoonal-marine, liman, and other sediments at the adjacent land also contain substantial amounts of microscopic gold. The pre10987nary study of oceanic bottom sediments near the Antarctic Peninsula and within the Argentine Basin proved the possibility of microscopic gold to accumulate under various facies conditions. The microscopic gold, mainly of clastic type, was detected here in 82% of samples. The obtained results testify to the global-scale deposition of floating microscopic gold in sedimentation basins of various age and may serve as a basis for the further comprehensive tackling of the problem in different regions.     

Sulfate reduction and methanogenesis in marine sediments

Methanogenesis and sulfate-reduction were followed in laboratory incubations of sediments taken from tropical seagrass beds. Methanogenesis and sulfate-reduction occurred simultaneously in sediments incubated under N₂, thereby indicating that the two processes are not mutually exclusive. Sediments incubated under an atmosphere of H₂ developed negative pressures due to the oxidation of H₂ by sulfate-respiring bacteria. H₂ also stimulated methanogenesis, but methanogenic bacteria could not compete for H₂ with the sulfate-respiring bacteria.     

中亚阿尔泰山南坡表土和泥炭沉积物GDGTs综合研究

相对于我国季风区,西北内陆地区表土和泥炭沉积物的甘油二烷基甘油四醚化合物（GDGTs）现代过程研究结果报道较少。对中亚干旱区阿尔泰山南坡海拔梯度表土、高山泥炭地哈拉沙子和那仁夏周边坡地表土以及哈拉沙子表层泥炭沉积物进行了GDGTs分析,结果表明：1）其海拔梯度表土当中细菌来源支链结构GDGTs（brGDGTs）的分子分布特征主要响应于湿度的变化;2）同样主要由于湿度变化的影响,奇古菌的影响和贡献在相对低海拔地区更为明显,产甲烷古菌的影响和贡献在相对高海拔地区上升,导致古菌来源的类异戊二烯结构GDGTs（isoGDGTs）的TEX₈₆参数随海拔上升具有显著的降低趋势;3）哈拉沙子和那仁夏泥炭地泥炭沉积物当中的brGDGTs和isoGDGTs都并非主要来自周边坡地土壤的异源输入,而主要都是泥炭地原地自生来源。这些研究结果,一方面为在该区域利用GDGTs开展古环境、古气候重建提供基础性参考;另一方面,也对其他区域相应研究结果形成有益补充。

     

Comparison of ladderane phospholipid and core lipids as indicators for anaerobic ammonium oxidation (anammox) in marine sediments

We investigated anaerobic ammonium oxidation (anammox) in continental shelf and slope sediments of the Irish and Celtic Seas by using anammox specific ladderane biomarker lipids. We used the presence of an intact ladderane phospholipid as a direct indicator for living anammox bacteria, and compared it with the abundance of ladderane core lipids derived from both living and dead bacterial biomass. All investigated sediments contained ladderane core lipids as well as the intact ladderane phospholipid, in agreement with ¹⁵N-labeling experiments, which revealed anammox activity at all sites. Ladderane core lipid and intact ladderane phospholipid concentrations were significantly correlated (R² = 0.957 and 0.464, respectively) with anammox activity over the transect of the continental shelf and slope sediments. In the Irish Sea (50-100 m water depth) highest abundances of the intact ladderane phospholipid were found in the upper 2 cm of the sediment, indicating a zone of active anammox. A sharp decline further down-core suggested a strong decrease in anammox biomass and rapid degradation of the intact lipids. In comparison, ladderane core lipids were 1-2 orders of magnitude higher in concentration than the intact ladderane phospholipid and accumulated as dead cell remnants with depth. In the slope sediments of the Celtic Sea both ladderane core lipids and the intact ladderane phospholipid were found in sediments at water depths ranging from 500 to 2000 m. Here, anammox seemed to be active at greater depths of the sediment (>2 cm). Mean abundances of both intact and core ladderane lipids in whole sediment cores increased downslope, indicating an increasing importance of anammox in deeper slope sediments.     

Silicate weathering in anoxic marine sediments

Two sediment cores retrieved at the northern slope of Sakhalin Island, Sea of Okhotsk, were analyzed for biogenic opal, organic carbon, carbonate, sulfur, major element concentrations, mineral contents, and dissolved substances including nutrients, sulfate, methane, major cations, humic substances, and total alkalinity. Down-core trends in mineral abundance suggest that plagioclase feldspars and other reactive silicate phases (olivine, pyroxene, volcanic ash) are transformed into smectite in the methanogenic sediment sections. The element ratios Na/Al, Mg/Al, and Ca/Al in the solid phase decrease with sediment depth indicating a loss of mobile cations with depth and producing a significant down-core increase in the chemical index of alteration. Pore waters separated from the sediment cores are highly enriched in dissolved magnesium, total alkalinity, humic substances, and boron. The high contents of dissolved organic carbon in the deeper methanogenic sediment sections (50-150 mg dm⁻³) may promote the dissolution of silicate phases through complexation of Al³⁺ and other structure-building cations. A non-steady state transport-reaction model was developed and applied to evaluate the down-core trends observed in the solid and dissolved phases. Dissolved Mg and total alkalinity were used to track the in-situ rates of marine silicate weathering since thermodynamic equilibrium calculations showed that these tracers are not affected by ion exchange processes with sediment surfaces. The modeling showed that silicate weathering is limited to the deeper methanogenic sediment section whereas reverse weathering was the dominant process in the overlying surface sediments. Depth-integrated rates of marine silicate weathering in methanogenic sediments derived from the model (81.4-99.2 mmol CO₂ m⁻² year⁻¹) are lower than the marine weathering rates calculated from the solid phase data (198-245 mmol CO₂ m⁻² year⁻¹) suggesting a decrease in marine weathering over time. The production of CO₂ through reverse weathering in surface sediments (4.22-15.0 mmol CO₂ m⁻² year⁻¹) is about one order of magnitude smaller than the weathering-induced CO₂ consumption in the underlying sediments. The evaluation of pore water data from other continental margin sites shows that silicate weathering is a common process in methanogenic sediments. The global rate of CO₂ consumption through marine silicate weathering estimated here as 5-20 Tmol CO₂ year⁻¹ is as high as the global rate of continental silicate weathering.     

Aerobic respiration in pelagic marine sediments

Analyses for dissolved oxygen, nitrate and total CO₂ in the interstitial water have been combined with solid phase sediment analyses of carbon and nitrogen to calculate the rates of reaction and stoichiometry of decomposing organic matter in central Equatorial Pacific pelagic sediments. The diagenesis is dominated by aerobic respiration and nitrification.Organic carbon and total nitrogen decrease exponentially with depth in both red clay and carbonate ooze sediments. In addition, there is a correlation between surface organic carbon and total nitrogen with distance from the equator. Fixed NH₄ is relatively constant with depth and constitutes 12 to 64% of the total nitrogen. The remainder is considered to be organic nitrogen.The $\text{C}\text{N}$ ratio of the decomposing organic matter was obtained using three approaches. Using the correlations of organic carbon with total nitrogen or organic nitrogen the molar ratios varied from 3.4 to 18.1. The average of all stations was 12.6 using total nitrogen and 13.7 using organic nitrogen. The Redfield ratio is 6.6. Approaches using interstitial water chemistry gave lower ratios. The average value using correlations between dissolved oxygen and nitrate was 8.1. The same approach using total CO₂ and nitrate gave an average of 9.1. Due to difficulties in unambiguously interpreting the solid phase data we favor the ratios obtained from the pore water analyses.The rate of organic matter decomposition can be obtained from model calculations using the dissolved oxygen and solid organic carbon data. Most gradients occur in the upper 10 to 20 cm of the sediments. Assuming that bioturbation is more important than sedimentation we have calculated first order rate constants. The average values using organic carbon and dissolved oxygen was 3.9 kyr^? and 4.2 kyr^? respectively using a biological mixing coefficient of 100 cm² kyr^?1. These rate constants decrease in direct proportions to the mixing coefficient.     

Sterols in interstitial waters of marine sediments

In order to attempt to elucidate the nature of biogeochemical processes occurring at the water-sediment interface, sterols have been analysed in near bottom sea and interstitial waters collected in the eastern and western intertropical Atlantic ocean. Free and esterified sterol concentrations range from 0.2 to 82 μg l^?1 and are much higher than those found in overlying sea water, which range from 0.2 to 1.7 μg l^?1 for the dissolved fraction and from 0.01 to 0.07 μg l^?1 for the particulate fraction. Cholest-5-en-3β-ol and 24-ethylcholest-5-en-3β-ol are the dominant sterols in sea and interstitial waters. The variability encountered for the relative importance of minor sterols such as 24-methylcholesta-5,24(28)-dien-3β-ol and stanols, 5α-cholest-22(E)-en-3β-ol, 5α-cholestan-3β-ol and 24-ethyl-5α-cholestan-3β-ol in interstitial water and their variation with depth is discussed in terms of diversity of inputs and bacterial activity. For sediments cored off the Mauritanian coast, a productive area characterized by an intense upwelling, the chemical signatures observed in interstitial water through stanol/stenol ratios occur at levels of very high heterotrophic aerobic bacterial biomass estimations. The study of the sterol composition of interstitial water could constitute a valuable tool in appreciating the intensity of chemical and biological processes occurring in the first few metres of recent marine sediments.     

Distribution of cadmium, chromium, copper, lead and zinc in marine sediments in Hong Kong waters

Partitioning of heavy metals (Cd, Cr, Cu, Pb, Zn) in marine sediments collected from various sites in Hong Kong waters were determined using sequential extraction method. Sediments from Kellette Bank, located in Victoria Harbour, had higher metal concentrations especially Cu and Zn than most other sites. Slightly over 20% of total Cu and Cr existed as readily available forms in Peng Chau and Kellette Bank. At most sampling sites, over 15% of the Cu existed as the exchangeable form indicating that Cu could be readily released into the aqueous phase from sediments. A significantly higher percentage of Pb and Zn was associated with the three non-residual fractions. Hence, there is a greater environmental concern for remobilization of Pb and Zn compared with Cr. The high amount of residual Cd (>50%) and the relatively lower Cd content indicate that little environmental concern is warranted for the remobilization of Cd. Distribution of metals in sediments collected from different depth at Kellette Bank shows that metal concentrations decreased with profile depth. The levels of Pb and Zn associated with the two readily available fractions increased sharply in the surface sediment. These metals represented the pollutants, which were introduced into the area in the mid-eighties through early nineties as a result of rapid economic and industrial development in the territory. As significant portions of these metals were bound to the readily available phases in the surface sediments, metal remobilization could be a concern. An erratum to this article can be found at     

Gold,palladium and iridium in marine sediments

The paper presents a preliminary evaluation of some processes affecting the noble metal content of deep-sea sediments. Neutron activation data for Au, Pd and Ir in deep-sea sediments, nearshore Arctic sediments and soils and Tahitian basalts and weathered derivatives are presented. A suite of sediment samples across the East Pacific Rise provide strong evidence that submarine volcanic exhalation has contributed significantly to the Pd and Au contents of these sediments. Limited data on continental weathering indicate that detritus contributed to the marine environment will not differ greatly in Au, Pd or Ir content compared to its continental source rocks.     

Vanadyl ions in ancient marine carbonaceous sediments

Vanadyl ions in ancient shaly-type sedimentary rocks of marine origin from a variety of world sources and geological periods have been investigated using electron spin resonance. These and other results provide evidence that there are two types of vanadyl ions. The first is inorganically bound in the clay/ silicate fraction of these rocks and the second type is associated with vanadyl porphyrin compounds.     

Solid-phase fluorescence determination of chlorins in marine sediments

Chlorophyll degradation products are preserved in marine sediments over timescales of thousands of years. The production of chlorophyll in the water column is related to biological productivity, so chlorophyll degradation products (chlorins) preserved in marine sediments can be used as indicators of paleoproductivity. A new, rapid, non-destructive method of determining chlorin concentrations in marine sediments is presented. Potential interferences associated with the solid-phase fluorescence (SPF) method are explored using reference materials, yet this method compares favorably with spectroscopic and high performance liquid chromatographic (HPLC) methods of analysis using marine sediments from Boston Harbor and the continental shelf off northwest Africa.     

Preservation of particulate non-lithogenic uranium in marine sediments

Particulate non-lithogenic uranium (PNU), excess U above detrital background levels found in marine particulate matter, is formed in surface waters throughout the ocean. Previous studies have shown that PNU is regenerated completely prior to burial of particles in sediments within well-oxygenated open-ocean regions. However, the fate of PNU has never been examined in ocean margin regions or in anoxic basins. Here we evaluate the preservation of PNU in ocean margin sediments and within semi-enclosed basins using samples from sediment traps deployed at multiple depths and surface sediments. Organic carbon fluxes at the sediment trap locations ranged from 0.1 to 4.3 g/cm² kyr, while the dissolved oxygen concentration in the water column ranged from <3 μM to ∼ 270 μM. Preservation of PNU increases with decreasing dissolved oxygen concentration, approaching 100% preservation at oxygen concentration < 25 μM. PNU contributes as much as 40 to 70% of the total authigenic U in sediments in the Santa Barbara Basin and seasonally anoxic Saanich Inlet, and some 10% to 50% of the total authigenic U in sediments off the central California Margin.