Geochemistry of organic matter of bottom sediments in the rises of the central Arctic Ocean

Based on geomorphological, lithological, and facial characteristics of the East Arctic continental margin, we studied the main factors controlling the Late Cenozoic supply of organic matter (OM) to the bottom sediments of the Central Arctic rises of the Arctic Ocean. Complex analysis of dispersed OM in the samples taken during the expeditions of the R/V “Akademik Fedorov” in 2000 and 2005 showed a significant difference between the sediments of the Lomonosov Ridge and Mendeleev Rise. The bottom sediments of the latter are strongly transformed and lack terrigenous components, as evidenced results from the main geochemical characteristics (contents of C_org, C_carb, N_org, bitumens, and humic acids) and the composition and distribution of hydrocarbon molecular markers (alkanes, saturated and aromatic cyclanes). The obtained data evidence that ancient sedimentary rocks containing genetically uniform deeply transformed (up to mesocatagenesis) OM played a significant role in the formation of the Pleistocene–Holocene sediments of the axial part of the Mendeleev Rise.     

Organic matter in present-day ecosystems of the Arctic Ocean

Doklady Earth Sciences -     

The dissolved Beryllium isotope composition of the Arctic Ocean

We present the first comprehensive set of dissolved ¹⁰Be and ⁹Be concentrations in surface waters and vertical profiles of all major sub-basins of the Arctic Ocean, which are complemented by data from the major Arctic rivers Mackenzie, Lena, Yenisey and Ob. The results show that ¹⁰Be and ⁹Be concentrations in waters below 150 m depth are low and only vary within a factor of 2 throughout the Arctic Basin (350-750 atoms/g and 9-15 pmol/kg, respectively). In marked contrast, Be isotope compositions in the upper 150 m are highly variable and show systematic variations. Cosmogenic ¹⁰Be concentrations range from 150 to 1000 atoms/g and concentrations of terrigenous ⁹Be range from 7 to 65 pmol/kg, resulting in ¹⁰Be/⁹Be ratios (atom/atom) between 0.5 and 14 × 10⁻⁸. Inflowing Atlantic water masses in the Eurasian Basin are characterized by a ¹⁰Be/⁹Be signature of 7 × 10⁻⁸. The inflow of Pacific water masses across the Bering Strait is characterized by lower ratios of 2-3 × 10⁻⁸, which can be traced into the central Arctic Ocean, possibly as far as the Fram Strait. A comparison of the high dissolved surface ¹⁰Be and ⁹Be concentrations (corresponding to low ¹⁰Be/⁹Be signatures of ∼2 × 10⁻⁸) in the Eurasian Basin with hydrographic parameters and river data documents efficient and rapid transport of Be with Siberian river waters across the Siberian Arctic shelves into the central Arctic Basin, although significant loss and exchange of Be on the shelves occurs. In contrast, fresh surface waters from the Canada Basin also show high cosmogenic ¹⁰Be contents, but are not enriched in terrigenous ⁹Be (resulting in high ¹⁰Be/⁹Be signatures of up to 14 × 10⁻⁸). This is explained by a combination of efficient scavenging of Be in the Mackenzie River estuary and the shelves and additional supply of cosmogenic ¹⁰Be via atmospheric fallout and melting of old sea ice. The residence time of Be in the deep Arctic Ocean estimated from our data is 800 years and thus similar to the average Be residence time in the global ocean.     

Spectral fingerprinting of soil organic matter composition

Large scale environmental monitoring schemes would benefit from accurate information on the composition of soil organic matter (SOM), but so far routine procedures for describing SOM composition remain a chimera. Here, we present the initial assessment of a two step strategy for expeditious determination of SOM composition that involves: (i) building infrared fingerprints from near and mid infrared spectroscopies, two rapid and cheap yet reliable technologies; and (ii) calibrating such infrared fingerprints with multivariate chemometrics from a molecular mixing model based on the more expensive and time consuming ¹³C nuclear magnetic resonance technique, which discriminates five biochemical components: carbohydrate, protein, lignin, lipid and black carbon. We show fair to excellent predictive ability of the calibrated infrared fingerprints for four out of these five biochemical components, with cross-validated ratios of performance to inter-quartile distance from 3.2 to 8.3, on a small set of 23 soil samples with a wide range of organic carbon content (12–500 g/kg). Multivariate calibration models were highly selective (<2% of infrared data were used for all models). However, the specificity to one particular biochemical component of the infrared wavebands automatically selected by each model was relatively low, except for lipid. Achieving direct predictions of SOM composition on unknown soil samples with infrared spectroscopy alone will require further independent validation and a larger number of samples. Overall, the implementation of our strategy at a broader scale, based on available ¹³C nuclear magnetic resonance soil libraries, could provide a cost effective solution for the routine assessment of SOM composition.     

Burial of redox-sensitive metals and organic matter in the equatorial Indian Ocean linked to precession

Authigenic metals (uranium, cadmium, and molybdenum), organic carbon (OC) and total C₃₇ alkenone (totC₃₇) concentrations were measured for the last 350 kyr in core MD900963, located in the eastern equatorial Arabian Sea. Authigenic metal concentrations on a carbonate-free basis range between 1 and 17 ppm, 0.5 and 6 ppm, and 0.5 and 4 ppm for U, Cd, and Mo, respectively. The profiles are characterized by well-defined 23 kyr cycles between oxic and mildly suboxic conditions. The redox-sensitive metal profiles also follow variations in the concentrations of OC (0.2-0.9%) and alkenones (0.2-6.7 ppm). The coupled variations in inorganic and organic constituents are attributed to a 23-kyr cycle in primary production above site MD900963, as suggested by clear correlations with independent micropaleontologic proxies (primary productivity indices based on foraminifera and coccoliths and fragmentation of foraminiferal shells). The 23-kyr cycles do appear to be primarily driven by productivity rather than changes in bottom water oxygen. Comparison with other records indicates that if this interpretation is correct, productivity variations across much of the Indian Ocean have been dominated by precessional forcing, with high productivity in phase with low summer insolation in the Northern Hemisphere. This interpretation contrasts with the traditional attribution of enhanced productivity in the Indian Ocean with periods of high summer insolation.     

Chemical composition of late Pleistocene-Holocene pelagic sediments in Gakkel Ridge,Arctic Ocean

The paper presents data on the chemical composition of Late Pleistocene-Holocene sediments in the Gakkel Ridge according to data on sediment core PS 70/306-3, offers a hypothetical litho-stratigraphic model, and provides data on chemo-stratigraphic horizons distinguished based on the distribution of carbonates, organic carbon, metals (Fe, Mn, Cu, Zn, Co, Ni, V, Pb), As, and P in the core. Chemical transformations of sediments at the redox barrier are discussed, along with relations between the composition of the sediments and the facies sedimentation conditions.     

Microanalysis of carbon isotope composition in organic matter by secondary ion mass spectrometry

An analytical procedure has been developed for the in situ measurement of carbon isotope composition of organic matter, with a spatial resolution of 20-30 μm, using a Cameca IMS 1270 ion microprobe. Instrumental mass fractionation (IMF) of carbon isotopes was observed to be independent of primary ion beam intensity and sputtering time, but did depend on vacuum conditions and on the chemical composition of the sample. To evaluate such “matrix effects”, a set of 9 standards representative of the natural chemical variability of organic matter was prepared, with H/C atomic ratios and organic carbon contents (C_org) ranging between 0.04 and 1.74 and between 41 and 100 wt.%, respectively. Under the analytical conditions tested, IMF was not found to be influenced by the presence of silicate mineral impurities in the organic matter, but variations in IMF up to 5‰ were observed over the set of standards with the magnitude of IMF negatively correlated to the H/C ratios of samples. Aliphaticity ratios determined using Fourier transform infrared microspectroscopy provided an in situ estimation of H/C ratios with a spatial resolution barely exceeding that of the ion microprobe and permit a correction for matrix effects with a standard error of ± 0.2‰ (1σ). Taking into account all sources of uncertainty, ion microprobe δ¹³C were accurately determined with a ± 0.7‰ (1σ) total uncertainty. The mechanism for the matrix effect of H/C ratios upon IMF is still to be determined but it is likely related to the difference in proportion of atomic vs. molecular carbon ions observed between samples of different H/C ratios.     

The isotopic composition of particulate organic carbon in mountain rivers of Taiwan

Small rivers draining mountain islands are important in the transfer of terrestrial particulate organic carbon (POC) to the oceans. This input has implications for the geochemical stratigraphic record. We have investigated the stable isotopic composition of POC (δ¹³C_org) in rivers draining the mountains of Taiwan. In 15 rivers, the suspended load has a mean δ¹³C_org that ranges from −28.1±0.8‰ to −22.0±0.2‰ (on average 37 samples per river) over the interval of our study. To investigate this variability we have supplemented suspended load data with measurements of POC in bedrock and river bed materials, and constraints on the composition of the terrestrial biomass. Fossil POC in bedrock has a range in δ¹³C_org from −25.4±1.5‰ to −19.7±2.3‰ between the major geological formations. Using coupled δ¹³C_org and N/C we have found evidence in the suspended load for mixing of fossil POC with non-fossil POC from the biosphere. In two rivers outside the Taiwan Central Range anthropogenic land use appears to influence δ¹³C_org, resulting in more variable and lower values than elsewhere. In all other catchments, we have found that 5‰ variability in δ¹³C_org is not controlled by the variable composition of the biomass, but instead by heterogeneous fossil POC.In order to quantify the fraction of suspended load POC derived from non-fossil sources (F_nf) as well as the isotopic composition of fossil POC (δ¹³C_fossil) carried by rivers, we adapt an end-member mixing model. River suspended sediments and bed sediments indicate that mixing of fossil POC results in a negative trend between N/C and δ¹³C_org that is distinct from the addition of non-fossil POC, collapsing multiple fossil POC end-members onto a single mixing trend. As an independent test of the model, F_nf reproduces the fraction modern (F_mod) in our samples, determined from ¹⁴C measurements, to within 0.09 at the 95% confidence level. Over the sampling period, the mean F_nf of suspended load POC was low (0.29 ± 0.02, n = 459), in agreement with observations from other mountain rivers where physical erosion rates are high and fossil POC enters river channels. The mean δ¹³C_fossil in suspended POC varied between −25.2±0.5‰ and −20.2±0.6‰ from catchment to catchment. This variability is primarily controlled by the distribution of the major geological formations. It also covers entirely the range of δ¹³C_org found in marine sediments which is commonly thought to derive from mixing between marine and terrigenous POC. If land-sourced POC is preserved in marine sediments, then changes in the bulk δ¹³C_org observed offshore Taiwan could instead be explained by changes in the onshore provenance of sediment. The range in δ¹³C_org of fossil organic matter in sedimentary rocks exposed at the surface is large and given the importance of these rocks as a source of clastic sediment to the oceans, care should be taken in accounting for fossil POC in marine deposits supplied by active mountain belts.     

Alkane and PAH biomarkers as tracers of terrigenous organic carbon in Arctic Ocean sediments

We present the first sedimentary biomarker study encompassing the entire Arctic Ocean. A large data set of organic markers for terrigenous, petroleum and combustion inputs [alkanes, hopanes and steranes, parent and alkyl polycyclic aromatic hydrocarbons (PAHs)] is examined for patterns in space and time using principal components analysis (PCA) and partial least squares (PLS). Biomarker patterns reveal the central Arctic Ocean basin sediments to be compositionally distinct from those of the Mackenzie River/Beaufort Sea and Barents Sea, but similar to those of the Laptev Sea. PAH distributions reflected in PAH ratios and PCA projections demonstrate that Arctic Ocean sediment is dominated by natural inputs to the extent that anthropogenic combustion PAHs are not significant. We find only modest changes between the glacial and post-glacial sediments for atmospherically transported hydrocarbon biomarkers, while particle associated biomarkers were captured strongly at basin edges during the glacial period, and much more evenly transported across basins during the post-glacial period. The orders of magnitude decreases in particle associated petrogenic alkanes and PAHs in central basins during glacial times, coupled with the uniformity of most petrogenic biomarker parameters for most basin and shelf locations, reflect a massive reduction in ice transport that makes the margins the most likely source of petrogenic material for the Pleistocene/Holocene central Arctic basins. The proximity of large coal deposits of various maturity levels along the Lena River, the overlap in PAH and biomarker composition of the Laptev Sea and surficial sediments from the central Arctic Ocean and the location of the Laptev Sea at the origin of the main Transpolar Drift all point to eroded coals from the Lena River/Laptev Sea as the likely source of petrogenic hydrocarbons to the central Arctic Ocean. The ubiquitous presence of allochthonous coal in Arctic Ocean surface sediments provides a major constraint on the use of petrogenic biomarkers to infer the presence of subsurface petroleum reserves.     

Natural abundance of 15N in particulate organic matter in the North Pacific Ocean

The abundance of ¹⁵N in particulate organic matter in the euphotic layer of the North Pacific Ocean was investigated. δ¹⁵N values ranged from ?1.7 to +9.7% relative to atmospheric nitrogen. ¹⁵N contents in plankton samples collected in the central and northwestern North Pacific were inversely correlated with concentrations of NO^?₃. The ¹⁵N contents of Trichodesmium sp. (?1.7 to +0.5%) and associated Zooplankton (ca. + 2%) were low, suggesting the significance of nitrogen supply via molecular nitrogen fixation which is assumed to involve little isotope fractionation. The variation of ¹⁵N in particulate organic nitrogen in the euphotic layer of the ocean can be explained by biochemical isotope fractionation in the assimilation of nitrate and fixation of molecular nitrogen.     

Iron colloids/organic matter associated transport of major and trace elements in small boreal rivers and their estuaries (NW Russia)

The chemical status of major and trace elements (TE) in various boreal small rivers and watershed has been investigated along a 1500-km transect of NW Russia. Samples were filtered in the field through a progressively decreasing pore size (5, 0.8 and 0.22 μm; 100, 10, and 1 kD) using a frontal filtration technique. All major and trace elements and organic carbon (OC) were measured in filtrates and ultrafiltrates. Most rivers exhibit high concentration of dissolved iron (0.2–4 mg/l), OC (10–30 mg/l) and significant amounts of trace elements usually considered as immobile in weathering processes (Ti, Zr, Th, Al, Ga, Y, REE, V, Pb). In (ultra)filtrates, Fe and OC are poorly correlated: iron concentration gradually decreases upon filtration from 5 μm to 1 kD whereas the major part of OC is concentrated in the <1–10 kD fraction. This reveals the presence of two pools of colloids composed of organic-rich and Fe-rich particles. According to their behavior during filtration and association with these two types of colloids, three groups of elements can be distinguished: (i) species that are not affected by ultrafiltration and are present in the form of true dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, Si, B, As, Sb, Mo) or weak organic complexes (Ca, Mg, Sr, Ba), (ii) elements present in the fraction smaller than 1–10 kD prone to form inorganic or organic complexes (Mn, Co, Ni, Zn, Cu, Cd, and, for some rivers, Pb, Cr, Y, HREE, U), and (iii) elements strongly associated with colloidal iron in all ultrafiltrates (P, Al, Ga, REE, Pb, V, Cr, W, Ti, Ge, Zr, Th, U). Based on size fractionation results and taking into account the nominal pore size for membranes, an estimation of the effective surface area of Fe colloids was performed. Although the total amount of available surface sites on iron colloids (i.e., 1–10 μM) is enough to accommodate the nanomolar concentrations of dissolved trace elements, very poor correlation between TE and surface sites concentrations was observed in filtrates and ultrafiltrates. This strongly suggests a preferential transport of TE as coprecipitates with iron oxy(hydr)oxides. These colloids can be formed on redox boundaries by precipitation of Fe(III) from inflowing Fe(II)/TE-rich anoxic ground waters when they meet well-oxygenated surface waters. Dissolved organic matter stabilizes these colloids and prevents their aggregation and coagulation. Estuarine behavior of several trace elements was studied for two small iron- and organic-rich rivers. While Si, Sr, Ba, Rb, and Cs show a clear conservative behavior during mixing of freshwaters with the White sea, Al, Pb and REE are scavenged with iron during coagulation of Fe hydroxide colloids.     

Accumulation of organic matter in Cretaceous oxygen-deficient depositional environments in the central Pacific Ocean

Complete records of organic-carbon-rich Cretaceous strata were continuouslycored on the flanks of the Mid-Pacific Mountains and southern Hess Rise in the central North Pacific Ocean during DSDP Leg 62. Organic-carbon-rich laminated silicified limestones were deposited in the western Mid-Pacific Mountains during the early Aptian, a time when that region was south of the equator and considerably shallower than at present. Organic-carbon-rich, laminated limestone on southern Hess Rise overlies volcanic basement and includes 136 m of stratigraphic section of late Albian to early Cenomanian age. This limestone unit was deposited rapidly as Hess Rise was passing under the equatorial high-productivity zone and was subsiding from shallow to intermediate depths. The association of volcanogenic components with organic-carbon-rich strata on Hess Rise in the Mid-Pacific Mountains is striking and suggests that there was a coincidence of mid-plate volcanic activity and the production and accumulation of organic matter at intermediate water depths in the tropical Pacific Ocean during the middle Cretaceous.Pyrolysis assays and analyses of extractable hydrocarbons indicate that the organic matter in the limestone on Hess Rise is composed mainly of lipid-rich kerogen derived from aquatic marine organisms and bacteria. Limestones from the Mid-Pacific Mountains generally contain low ratios of pyrolytic hydrocarbons to organic carbon and low hydrogen indices, suggesting that the organic matter may contain a significant proportion of land-derived material, possibly derived from numerous volcanic islands that must have existed before the area subsided. The organic carbon in all samples analyzed is isotopically light (δ¹³C ? 24 to ? 29 per mil) relative to most modern rine organic carbon, and the lightest carbon is also the most lipid-rich.There is a positive linear correlation between sulfur and organic carbon in samples from Hess Rise and from the Mid-Pacific Mountains. The slopes and intercepts of C-S regression lines however, are different for each site and all are different from regression lines for samples from modern anoxic marine sediments and from Black Sea cores.The organic-carbon-rich limestones on Hess Rise, the Mid-Pacific Mountains, and other plateaus and seamounts in the Pacific Ocean are not synchronous but do occur within the same general middle Cretaceous time period as organic-carbon-rich lithofacies elsewhere in the world ocean, particularly in the Atlantic Ocean. Strata of equivalent age in the deep basins of the Pacific Ocean are not rich in organic carbon, and were deposited in oxygenated environments. This observation, together with the evidence that the plateau sites were considerably shallower and closse to the equator during the middle Creataceous suggests that local tectonic and hydrographic conditions may have resulted in high surface-water productivity and the preservation of organic matter in an oxygen-deficient environment where an expanded mid-water oxygen minimum developed and impinged on elevated platforms and seamounts.     

Characterization of a major refractory component of marine dissolved organic matter

Refractory carboxyl-rich alicyclic molecules (CRAM) are characterized in marine dissolved organic matter (DOM) using nuclear magnetic resonance spectroscopy and ultrahigh resolution mass spectrometry. CRAM are distributed throughout the water column and are the most abundant components of deep ocean DOM ever characterized. CRAM are comprised of a complex mixture of carboxylated and fused alicyclic structures with a carboxyl-C:aliphatic-C ratio of 1:2 to 1:7. CRAM are expected to constitute a strong ligand for metal binding, and multiple coordination across cations could promote aggregation and marine gel formation thereby affecting CRAM reactivity and the bioavailability of nutrients and trace metals. It appears CRAM are ultimately derived from biomolecules with structural similarities to sterols and hopanoids. The occurrence of CRAM in freshwater and terrestrial environments seems likely, considering the global distribution of biomolecules and the similarities of biogeochemical processes among environments.     

HT-IRMS测定有机物氧同位素过程的影响因素及方法改进

高温裂解元素分析仪与气体同位素质谱仪联用系统（HT-IRMS）是测定有机物氧同位素的重要方法,优化HT-IRMS的参数、提高其可靠性和稳定性一直是各实验室努力的方向。本研究基于国际标准物质IAEA-601和IAEA-C3的多次测量,对HT-IRMS测定结果的稳定性进行了检验。结果显示,手动进样模式下,测定值比较稳定（标准偏差分别为0.16‰和0.25‰）,而自动进样模式的测定结果波动变化显著且呈现偏负漂移趋势,IAEA-601和IAEA-C3最大波动程度分别达到3.00‰和4.26‰。通过对比分析测定结果,本文推断自动进样模式下氧同位素的漂移可能源于空气中的水汽的污染。通过在自动进样盘位置加装隔离罩装置,将自动进样盘与实验室空气进行隔离之后,自动进样模式下再次重复测定结果较为稳定（标准偏差分别为0.35‰和0.25‰）,有机物氧同位素负漂移趋势基本消除,表明使用隔离罩装置可以有效减少实验室空气中水汽对样品的干扰,降低实验室环境参数变化对同位素测定结果的影响,提高HT-IRMS系统测定有机物氧同位素的稳定性。

     

Lipid composition of the pelagic crab Pleuroncodes planipes, its feces, and sinking particulate organic matter in the Equatorial North Pacific Ocean

Fecal pellets from the pelagic crab Pleuroncodes planipes were a substantial portion of the particulate organic matter in a sediment trap deployed at the bottom of the mixed layer in the eastern tropical North Pacific Ocean. The lipids of fresh P. planipes feces were compared to lipids of the sediment trap material, of mixed zooplankton which may comprise part of the diet of the crab, and of the crab itself in order to elucidate the source of organic compounds found in the trap. Hydrocarbons, wax esters, triacylglycerols, steroidal alcohols, steroidal ketones, and fatty acids were determined by capillary gas chromatography and gas chromatography/mass spectrometry. Significant input of lipids via sedimentation of crab fecal material is indicated, and modification of dietary lipid within the gut of the crab is inferred. Labile dietary fatty acids are depleted and sterols enriched in the fecal pellets and trap material relative to the zooplankton and crab. Nuclear saturated and unsaturated 3-ketosteroids and unsaturated steroidal hydrocarbons were detected in the crab, its feces, and in the sediment trap particulate material.     

Depth-to-magnetic source analysis of the Arctic Ocean region

Approximately 400,000 line kilometers of high quality, low level Arctic aeromagnetic data collected by the Naval Research Laboratory, the Naval Oceanographic Office and the Naval Ocean Reseach and Development Activity from 1972 through 1978 have been analyzed for depth to magnetic source. This data set covers much of the Canada Basin, the Alpha Ridge, the central part of the Makarov Basin, the Lincoln Sea, the Eurasia Basin west and south of the 55°E meridian and the Norwegian-Greenland Sea north of the Jan Mayen Fracture Zone. The analysis uses the autocorrelation algorithm developed by Phillips (1975, 1978) and based on the maximum entropy method of Burg (1967, 1968, 1975). The method is outlined, examples of various error analysis techniques shown and final results presented. Where possible, magnetic source depth estimates are compared with basement depths derived from seismic and bathymetric data.All major known bathymetric features, including Vesteris Bank and the Greenland, Molloy and Spitsbergen fracture zones, as well as the Mohns, Knipovich and Nansen spreading ridges and the Alpha Cordillera appear as regional highs in the calculated magnetic basement topography. Shallow basement was also found under the northeastern Yermak Plateau, the Morris Jesup Rise and under the southern (Greenland-Ellesmere Island) end of the Lomonsosov Ridge. Regional magnetic source deeps are associated with such bathymetric depressions as the Canada, Makarov, Amundsen, Nansen, Greenland and Lofoten basins; more localized magnetic basement deeps are found over the Molloy F.Z. deep and over the Mohns, Knipovich and Nansen rift valleys. A linear magnetic basement deep follows the extension of Nares Strait through the Lincoln Sea toward the Morris Jesup Rise, suggesting the continuation of the Nares Strait or Wegener F.Z. into the Lincoln Sea. A sharp drop in the regional magnetic source depths to the southeast of the Alpha Ridge suggests the Alpha Ridge is not connected to structures in northwest Ellesmere Island as previously postulated from high altitude aeromagnetic collected by Canadian workers. A regional deep under the east Greenland shelf west of the Greenland Escarpment suggests the presence of 5–10 km of post-Paleozoic sediments.     

Organic matter of the World Ocean

Available data on synthesis, input, and decomposition of organic matter (OM) in the water column and recent bottom sediments of the World Ocean are generalized. The most reliable values of OM production and masses in the ocean, the total supply of organic carbon, and the input of terrigenous OM with coastal erosion, river runoff, and eolian matter are estimated. Maps of fossilization coefficients, distribution, and accumulation of OM in recent bottom sediments of the World Ocean are presented. A numerical expression is proposed for the main circumcontinental pattern of OM accumulation in the ocean. The group and elemental compositions of living matter of the ocean, land, and the Earth as a whole and the organic composition of bottom sediments are briefly considered.