Assessment of δ13C and C/N ratios in bulk organic matter as palaeosalinity indicators in Holocene and Lateglacial isolation basin sediments,northwest Scotland

Carbon isotopes (δ¹³C) and C/N ratios from bulk organic matter have recently been used as alternative proxies for relative sea‐level (RSL) reconstruction where there are problems associated with conventional biological indictors. A previous study on a single isolation basin (Upper Loch nan Eala) in northwest Scotland has shown a clear relationship between δ¹³C, C/N ratios and palaeosalinity from Younger Dryas and Holocene aged sediments. In this paper we present results of δ¹³C and C/N ratio analyses from other isolation basins in northwest Scotland over the Holocene and the Lateglacial period in order to validate this technique. The results from the Holocene sequences support the earlier findings that this technique can be used to identify RSL change from isolation basins over the Holocene in this region. The relationship between δ¹³C, C/N ratios and RSL change is not apparent in sediments of Lateglacial age. Other environmental variables such as atmospheric CO₂ concentration, poor vegetation development and temperature influence δ¹³C values during this period. Copyright © 2007 John Wiley & Sons, Ltd.     

Carbon and Oxygen Isotopic Compositions: How Lacustrine Environmental Factors Respond in Northwestern and Northeastern China

Surface lake sediments,28 from Hoh Xil,24 from northeastern China,99 from Lake Bosten,31 from Ulungur and 26 from Heihai were collected to determine δ13C and δ18O values.Considering the impact factors,conductivity,alkalinity,pH,TOC,C/N and carbonate-content in the sediments,Cl,P,S,and metal element ratios of Mg/Ca,Sr/Ca,Fe/Mn of bulk sediments as environmental variables enable evaluation of their influences on δ13C and δ18O using principal component analysis(PCA) method.The closure and residence time of lakes can influence the correlation between δ13C and δ18O.Lake water will change from fresh to brackish with increasing reduction and eutrophication effects.Mg/Ca in the bulk sediment indicates the characteristic of residence time,Sr/Ca and Fe/Mn infer the salinity of lakes.Carbonate formation processes and types can influence the δ13C–δ18O correlation.δ18O will be heavier from Mg-calcite and aragonite formed in a high-salinity water body than calcite formed in freshwater conditions.When carbonate content is less than 30%,there is no relationship with either δ13C or δ18O,and also none between δ13C and δ18O.More than 30%,carbonate content,however,co-varies highly to δ13C and δ18O,and there is also a high correlation between δ13C and δ18O.Vegetation conditions and primary productivity of lakes can influence the characteristics of δ13C and δ18O,and their co-variance.Total organic matter content(TOC) in the sediments is higher with more terrestrial and submerged plants infilling.In northeastern and northwestern China,when organic matter in the lake sediments comes from endogenous floating organisms and algae,the δ13C value is high.δ13C is in the range of 4‰ to 0‰ when organic matter comes mainly from floating organisms(C/N<6);in the range of 4‰ to 8‰ when organic matter comes from diatoms(C/N=6 to 8);and 8‰ to 4‰ when organic matter comes from aquatic and terrestrial plants(C/N>8).     

Elemental and isotopic carbon and nitrogen records of organic matter accumulation in a Holocene permafrost peat sequence in the East European Russian Arctic

A peat deposit from the East European Russian Arctic, spanning nearly 10 000 years, was investigated to study soil organic matter degradation using analyses of bulk elemental and stable isotopic compositions and plant macrofossil remains. The peat accumulated initially in a wet fen that was transformed into a peat plateau bog following aggradation of permafrost in the late Holocene (～2500 cal a BP). Total organic carbon and total nitrogen (N) concentrations are higher in the fen peat than in the moss‐dominated bog peat layers. Layers in the sequence that have lower concentrations of total hydrogen (H) are associated with degraded vascular plant residues. C/N and H/C atomic ratios indicate better preservation of organic matter in peat material dominated by bryophytes as opposed to vascular plants. The presence of permafrost in the peat plateau stage and water‐saturated conditions at the bottom of the fen stage appear to lead to better preservation of organic plant material. δ¹⁵N values suggest N isotopic fractionation was driven primarily by microbial decomposition whereas differences in δ¹³C values appear to reflect mainly changes in plant assemblages. Positive shifts in both δ¹⁵N and δ¹³C values coincide with a local change to drier conditions as a result of the onset of permafrost and frost heave of the peat surface. This pattern suggests that permafrost aggradation not only resulted in changes in vegetation but also aerated the underlying fen peat, which enhanced microbial denitrification, causing the observed ¹⁵N‐enrichment. Copyright © 2012 John Wiley & Sons, Ltd.     

Sources of fine-sized organic matter in North Atlantic Heinrich Layers: δC and δN tracers

Organic carbon (OC) and total nitrogen (TN) concentrations and stable isotope ratios (δ¹³C, δ¹⁵N) of fine (<50 μm) size fractions of deep-sea sediments from the central North Atlantic were employed to identify changes in sources of organic matter over the past 50 ka BP. Ambient glacial sediments are characterised by values that reflect mixtures of marine and terrestrial inputs (averages ± 1σ: OC/TN = 7.6 ± 0.8; δ¹³C = −22.8 ± 1.0‰; δ¹⁵N = 5.5 ± 0.6‰). δ¹³C, OC, and TN concentrations shift to higher values during the Holocene, indicating a gradual decrease of fine terrigenous supply to the North Atlantic. The unchanged δ¹⁵N record between last glacial and Holocene stages indicates that the central North Atlantic region remained oligotrophic at least during the past 50 ka BP, but additional studies are required to support this result in terms of nitrogen oceanic budget. During the phases of enhanced ice-rafted detrital supply corresponding to prominent Heinrich events (HL₁, HL₂, HL₄, and HL₅), fine-sized sedimentary organic matter has lower OC and TN concentrations, contrasting sharply with those of ambient glacial sediments. Lower δ¹³C (down to −28‰) and δ¹⁵N (down to 1.6‰) values and high OC:TN ratios (up to 14.7 ± 1.1) are found for HL₁, HL₂, and with lesser extent for HL₄. These values reflect enhanced detrital supply originating from poorly differentiated soil horizons that characterise periglacial climate conditions and from organic matter-bearing rock sources of the underlying geological basement. During HL₅, only the δ¹³C offset records the input of fine size ice-rafted organic matter. Gradually changing soil development conditions during the time interval covering HL₅ to HL₁ (marine isotope stages 5 to 2), as well as varying erosion levels, have been hypothesized on the basis of constant δ¹³C, increasing OC/TN and decreasing δ¹⁵N values.     

Stable C and N isotope record of short term changes in water level in lakes of different morphometry: Lake Anastazewo and Lake Skulskie,central Poland

We present the stable C isotope record of the changes within the past 20 yr in water level of two morphologically different lakes in central Poland. The aim was to explain the relationship between lake water level and the δ¹³C signature of bulk sedimentary organic matter (δ¹³C_TOC) and to assess the potential of δ¹³C_TOC as a paleolimnological proxy of lake level change. This was done by comparison of the fossil δ¹³C_TOC record with instrumental data for lake level change in a shallow and small lake as well as in one large and deep basin. In both lakes the water table varied greatly between 1980 and 2000 AD. The δ¹³C_TOC data were supplemented with δ¹⁵N and bulk geochemistry data, as well as paleoecological data. We show that δ¹³C_TOC reacted to short term and low amplitude fluctuation in water level, but the response was highly dependent on the morphometry of the lake. In the shallow and small basin, δ¹³C_TOC decreased along with lake level drop due to oxidation and greater input of organic matter from macrophytes colonizing the lake bottom. On the contrary, in the deep/large lake δ¹³C_TOC decreased with increasing water level due to enhanced delivery of soil-derived OM to the lake during highstands. Our results have broad paleolimnological implications as they show that δ¹³C_TOC cannot act as a universal paleohydrological proxy. Its interpretation for a particular lake can be ambiguous and must be supported with additional geochemical and paleocological information.     

The Medieval Warm Period and the Little Ice Age from a sediment record of Lake Ebinur,northwest China

Ma, L., Wu, J., Yu, H., Zeng, H. & Abuduwaili, J. 2011: The Medieval Warm Period and the Little Ice Age from a sediment record of Lake Ebinur, northwest China. Boreas, Vol. 40, pp. 518–524. 10.1111/j.1502‐3885.2010.00200.x. ISSN 0300‐9483. Lake Ebinur, Xinjiang, northwest China, is a closed‐basin, shallow lake that responds rapidly to changes in the ratio of precipitation to evaporation (P/E). A sediment record spanning the last 1500 years was obtained from the lake. We used δ¹⁸O and δ¹³C in bulk carbonate, and δ¹³C of organic matter in the lake sediments to infer environmental changes in the Ebinur region during the Medieval Warm Period (MWP) and the Little Ice Age (LIA). Decreased δ¹⁸O values of carbonate largely reflect an enhanced P/E ratio within the basin and a higher lake level. Bulk carbonates with higher δ¹³C values are deposited during periods when lake‐water pH is high, while lower δ¹³C values reflect a lower pH in the water column. δ¹³C in organic matter is associated with the amount of precipitation. The results indicate that the Ebinur region experienced a dry MWP and a wet LIA, although the MWP and LIA were warm and cold periods, respectively, as expected. Furthermore, the MWP and LIA were hydrologically complex and cannot be characterized as uniformly wet or dry. Peak wet periods are recorded in the sediment core around AD 1000, 1400 and 1700, and a dry event also occurred in the period of temperature change within the LIA (cold to warm around AD 1500). A comparison of the Lake Ebinur data with proxy records for the strength of the Siberian High and climate proxy indicators suggests that precipitation in the Ebinur region was a consequence, in part, of an enhanced Siberian High during the LIA.     

Change of Organic δ13C in Ornithogenic Sediments of the Xisha Archipelago, South China Sea and its Implication for Ecological Development

Organic carbon isotopes in sediments have been frequently used to identify the source of organic matter.Here we present a study of organic δ~(13)C on two sediment profiles influenced by guano from Guangjin and Jinqing islands in the Xisha Archipelago,South China Sea.Organic matter from ornithogenic coral sand sediments has two main sources,guano pellets and plant residues,and their organic δ~(13)C(δ~(13)C_(OM)) are significantly different.Organic carbon δ~(13)C_(guano) is much higher thanδ~(13)C_(plants),and δ~(13)C_(OM)of bulk samples is intermediate.Based on a two-end-member mixing model,the proportions of guano-and plant-derived organic matter in the bulk samples were reconstructed quantitatively.The results showed that seabirds began to inhabit the islands around approximately1200-1400 AD,and that guano pellets have been an important source of soil organic matter since then.With the accumulation of guano-derived nutrients,plants began to develop prosperously on the islands in the last 200 years,which is reflected by the significant increase of plant-derived organic matter in the upper sediment layer.However,guano-derived organic matter decreased greatly in recent decades,indicating a rapid decrease in seabird population.Our results show that organic δ~(13)C can be effectively used to quantitatively determine different source contributions of OM to bulk ornithogenic coral sand sediments.     

Preservation of organic matter and alteration of its carbon and nitrogen isotope composition during simulated and in situ early sedimentary diagenesis

The carbon and nitrogen isotope composition of organic matter has been widely used to trace biogeochemical processes in marine and lacustrine environments. In order to reconstruct past environmental changes from sedimentary organic matter, it is crucial to consider potential alteration of the primary isotopic signal by bacterial degradation in the water column and during early diagenesis in the sediments.In a series of oxic and anoxic incubation experiments, we examined the fate of organic matter and the alteration of its carbon and nitrogen isotopic composition during microbial degradation. The decomposition rates determined with a double-exponential decay model show that the more reactive fraction of organic matter degrades at similar rates under oxic and anoxic conditions. However, under oxic conditions the proportion of organic matter resistent to degradation is much lower than under anoxic conditions. Within three months of incubation the δ¹³C of bulk organic matter decreased by 1.6‰ with respect to the initial value. The depletion can be attributed to the selective preservation of ¹³C-depleted organic compounds. During anoxic decay, the δ¹⁵N values continuously decreased to about 3‰ below the initial value. The decrease probably results from bacterial growth adding ¹⁵N-depleted biomass to the residual material. In the oxic experiment, δ¹⁵N values increased by more then 3‰ before decreasing to a value indistinguishable from the initial isotopic composition. The dissimilarity between oxic and anoxic conditions may be attributed to differences in the type, timing and degree of microbial activity and preferential degradation. In agreement with the anoxic incubation experiments, sediments from eutrophic Lake Lugano are, on average, depleted in ¹³C (−1.5‰) and ¹⁵N (−1.2‰) with respect to sinking particulate organic matter collected during a long-term sediment trap study.     

Sedimentary organic matter record of recent environmental changes in the St. Marys River ecosystem,Michigan–Ontario border

Lake George, located in the St. Marys River, has been heavily impacted by human-induced environmental changes over the past century. The effects of human impacts starting in the late nineteenth century and of natural, gradual diagenesis can be distinguished in the bulk organic matter and molecular contents of the sedimentary record. Organic carbon concentrations increase from 0.5% in sediments deposited 200 years ago to ∼4% in recent sediments. A fourfold increase in organic carbon mass accumulation rates accompanies the change in concentrations. Elevated C/N ratios in near-modern sediments indicate that increased delivery of land-derived organic matter has been responsible for much of the recent increases in sedimentary organic carbon. Organic δ¹³C and δ¹⁵N values change significantly and coincidentally with the environmental changes, reflecting depressed algal productivity since the introduction of industrial effluents to the aquatic system, increased delivery of land-derived organic matter and some impacts of acid rain. Increases in microbial and petroleum hydrocarbon contributions occur in sediments deposited since 1900. Fatty acid distributions provide evidence of substantial microbial reworking of organic matter throughout the sedimentary record.     

Organic geochemical record of increased productivity in Lake Naukuchiyatal, Kumaun Himalayas, India

Organic geochemical proxies have been studied in a 45-cm-long core retrieved from Lake Naukuchiyatal in Kumaun Himalayas, India. Increase in TOC, N, hydrocarbons and pigments concentration from bottom to surface sediments of the core indicates increase in the lake productivity. Stable isotopes (δ¹³C and δ ¹⁵ N), biomarkers (TAR, CPI and n-ΣC_15,17,19) and C/N atomic (between 9 and 12) suggest dominance of algal derived organic matter in these sediments. Decrease in organic δ¹³C values (between ?27 and ?31‰) in surface sediments indicate influence of sewage and land runoff in shifting organic δ¹³C values, whereas low (between ?0.23 and 2.2‰) δ¹⁵N values together with high pigment concentrations (zeaxanthin and echinenone) represent dominance of cyanobacteria in the lake.     

Carbon, oxygen, strontium, and sulfur isotopic compositions in late Precambrian rocks of the Patom Complex, central Siberia: Communication 2. Nature of carbonates with ultralow and ultrahigh δ13C values

The Patom Complex is characterized by a unique association of carbonate rocks with ultralow (≤8‰) and ultrahigh (>6‰) δ¹³C values. The thickness, stable isotopic composition along the strike, and lithological and geochemical parameters suggest that these rocks could not form as a result of short-term local events or epigenetic processes. Ultralow δ¹³C values (less than ?8‰) in carbonate rocks of the Zhuya Group, which substantially exceed all the known negative C isotope anomalies in thickness (up to 1000 m) and amplitude (δ¹³C = ?10 ± 2‰), point to sedimentation under conditions of extreme “contamination” of water column by oxidized isotopically light organic (hereafter, light) carbon. The decisive role in this contamination belonged to melting and oxidation of huge volumes of methane hydrates accumulated in sediments during the powerful and prolonged Early Vendian glacial epoch. The accumulation of δ¹³C-depleted carbonates was preceded by the deposition of carbonates with anomalously high δ¹³C values. These carbonates formed at high rates of the burial of organic matter and methane in sediments during periods when the sedimentation basin consumed carbon dioxide from the atmosphere and organic carbon was conserved in sediments.     

Suspended sediments and organic matter in mountain headwaters of the Amazon River: Results from a 1-year time series study in the central Peruvian Andes

Few studies have examined the dynamics of sediments and suspended organic matter and their export from headwater basins in the Andes Mountains to the Amazon River, despite the fact that the Andes are the primary source of sediments to the lower Amazon basin. We measured river discharge as well as the concentration, δ¹⁵N, δ¹³C, %N, and %OC of coarse and fine suspended sediments (CSS and FSS) in the Chorobamba River, located in the central Andean Amazon of Peru. Samples were taken at least weekly over an entire year (July 2004-July 2005), with additional sampling during storms. Concentrations of particulate organic matter (POM) were generally low in the study river, with concentrations increasing by up to several orders of magnitude during episodic rain events. Because both overall flow volumes and POM concentrations increased under stormflow conditions, the export of POM was enhanced multiplicatively during these events. We estimated that a minimum of 80% of annual suspended sediment transfer occurred during only about 10 days of the year, also accounting for 74% of particulate organic carbon and 64% of particulate organic nitrogen transport. Significant differences occurred between seasons (wet and dry) for δ¹³C of coarse and fine POM in the Chorobamba River, reflecting seasonal changes in organic matter sources. The time series data indicate that this Andean river exports approximately equal amounts of fine and coarse POM to the lower Amazon. The observation that the vast majority of sediments and associated OM exported from Andean rivers is mobilized during short, infrequent storm events and landslides has important implications for our understanding of Amazon geochemistry, especially in the face of incipient global change.     

Organic Carbon Isotope Geochemistry of the Neoproterozoic Doushantuo Formation, South China

The Neoproterozoic Doushantuo Formation on the Yangtze Platform, South China, documents a sedimentary succession with different sedimentary facies from carbonate platform to slope and to deep sea basin, and hosts one of the world-class phosphorite deposits. In these strata, exquisitely preserved fossils have been discovered： the Weng＇an biota. This study presents carbon isotope geochemistry which is associated paired carbonate and organic matter from the Weng＇an section of a carbonate platform （shelf of the Yangtze Platform, Guizhou Province） from the Songtao section and Nanming section of a transition belt （slope of the Yangtze Platform, Guizhou Province） and from the Yanwutan section （basin area of the Yangtze Platform, Hunan Province）. Environmental variations and bio-events on the Yangtze Platform during the Late Neoproterozoic and their causal relationship are discussed. Negative carbon isotope values for carbonate and organic carbon （mean δ^13Corg = -35.0‰） from the uppermost Nantuo Formation are followed by an overall increase in δ^13C up-section. Carbon isotope values vary between -9.9‰ and 3.6‰ for carbonate and between -35.6‰ and -21.5‰ for organic carbon, respectively. Heavier δ^13Ccarb values suggest an increase in organic carbon burial, possibly related to increasing productivity （such as the Weng＇an biota）. The δ^13C values of the sediments from the Doushantuo Formation decreased from the platform via the slope to basin, reflecting a reduced environment with minor dissolved inorganic carbon possibly due to a lower primary productivity. It is deduced that the classical upwelling process, the stratification structure and the hydrothermal eruption are principally important mechanisms to interpret the carbon isotopic compositions of the sediments from the Doushantuo Formation.     

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.     

Carbon isotope and C/N ratios of suspended matter in rivers: an indicator of seasonal change in C4/C3 vegetation

A combination of δ ¹³C values with C/N ratios in suspended matter has been used to examine the seasonal relationship between C₄ and C₃ vegetation along the Loess Plateau, NW China. The C isotopic composition of suspended organic matter in rivers, together with C/N ratios can differentiate between soil and plant material, and can be used to estimate the relative contributions of soil organic C and plant litter to the suspended matter. The relationship between C isotopic composition and C/N ratios indicates that the samples are a mixture of two end members: (1) modern soils with relatively constant δ ¹³C values, low C content and low C/N ratios; (2) plant litter with varying δ ¹³C values, high C content and high C/N ratios. The results reflect the seasonal distribution of C₄/C₃ vegetation within the area studied, as part of the Loess Plateau. The abundance of C₄ grasses is about 20% for the current summer vegetation ecosystem in the eastern part of the Loess Plateau. Hence, the use of δ ¹³C values and C/N ratios of suspended matter in rivers and modern soil may be useful for reflecting seasonal distribution of C₄/C₃ vegetation in catchments. This could be a useful tool for distinguishing between catchments for GIS studies, and long term planning for ecological management of catchment areas.     

Organic matter sources and transport in an agriculturally dominated temperate watershed

The quality, quantity, and origin of suspended organic matter were studied in the highly agricultural Upper Scioto River in Central Ohio. Late summer baseflow conditions were compared to late autumn high flow conditions. Variables examined in the suspended matter were the total suspended solids concentration, semi-quantitative concentrations of lignin, carbohydrate concentrations, total organic C, total and organic P, and δ-¹³C. Also examined were ratios of C to N, organic C to organic P ratios and fluxes of total organic C. The primary hypothesis of this research was that the quality (or biodegradability) and quantity of organic matter in the Upper Scioto River would increase during autumn stormflow conditions due to inputs of fresh terrestrial organic matter. The autumn suspended matter was also expected to reflect C4 plant contributions from corn organic matter. Results show that the quality and quantity of organic matter were greater during summer, as reflected in low molar ratios (178:1) of organic C to organic P, and higher organic C content of the suspended matter in summer. Summer suspended matter was 3.6% organic C and autumn suspended matter was 2.3% organic C. Carbon to N molar ratios in both seasons were very close to the Redfield ratio (6.6:1 in summer and 6.7:1 in autumn). Total suspended matter and total organic C concentrations were lower in autumn (8.7 mg/l⁻¹ TOC and 17.7 mg/l⁻¹ TSS) than in summer (17.5 mg/l⁻¹ TOC and 39.0 mg/l⁻¹ TSS), but the fluxes were greater in autumn due to greater stream flow. Stable isotope analyses suggested a phytoplankton or C3 plant source (most likely corn) for summer organic C (mean δ¹³C of −24.8‰) and a phytoplankton or C4 plant source for autumn organic matter (δ¹³C=−21.5‰).     

Environmental evolution recorded by multi-proxy evidence in Lake Chenghai sediments, Yunnan Province during recent 100 years

Lacustrine sediments can provide potential information about environmental changes in the past. On the basis of high-resolution multi-proxy analysis including carbon and nitrogen contents of organic matter, C/N ratios, inorganic carbon contents, and carbon and oxygen isotopic composition of carbonate, together with precise 137Cs dating, the environmental evolution of Lake Chenghai, Yunnan Province, during the past 100 years has been investigated. It is shown that the carbonate in Lake Chenghai is authigenic, and the organic matter is mainly derived from aquatic plants and algae, instead of terrestrial-source materials. The environmental evolution of Lake Chenghai can be diverged into three periods with the contrasting characteristics during the past 100 years. Before 1940, the stable carbon and oxygen isotope values, the poor correlation between them and the lower carbon and nitrogen contents of organic matter suggested that Lake Chenghai was open, and the lake water was oligotrophic during that period. During 1940-1993, the negative δ13C values and the gradual increase of carbon and nitrogen contents of organic matter and C/N ratios indicated that the eutrophication was aggravated. The closeness of Lake Chenghai and human activities may be responsible for this eutrophication. After 1993, notable increases in carbon and oxygen isotopic values of carbonate, carbon and nitrogen contents of organic matter, C/N ratios and inorganic carbon contents demonstrated that the increase of lacustrine productivity and the serious eutrophication were resulted from strong human activities. Therefore, the multi-proxy in Lake Chenghai sediments has reliably recorded the natural environmental evolution and the impacts from human activities.     

Organic matter degradation in sediments of the York River estuary: Effects of biological vs. physical mixing

We investigated the influence of biological and physical seabed disturbance on the degradation of bulk organic matter and source specific lipid biomarker compounds by measuring downcore changes in bulk elemental composition, bulk stable isotopic (δ¹³C and δ¹⁵N) signatures, and lipid biomarker compounds in sediment cores collected from two sites in the York River, a subestuary of the Chesapeake Bay, USA. One site (LY) is influenced by biological mixing (bioturbation), restricted to the upper 15-20 cm, while the other site (POD) experiences intense, episodic physical mixing events that penetrate 50-100 cm into the sediment. We utilized a suite of auxiliary measurements to constrain the sources of organic matter, depositional environments, and general ages of the cores. Diagenetic modeling of total organic carbon and total nitrogen in sediments yielded higher apparent rate constants for POD than LY suggesting that the physical mixing regime promotes enhanced degradation of bulk organic matter. Apparent rate constants for select lipids representing distinct sources of organic matter were also higher at POD than LY for all but the most labile (i.e., diatom-derived fatty acids) biomarkers. Differences in stanol/stenol ratios also supported enhanced diagenesis of stenols at POD. The source-specific biomarkers, while useful in qualitatively identifying the sources of sedimentary organic matter, likely do not represent the full spectrum of its reactivity. However, based on our results, we hypothesize that the intense sediment disturbance at POD promotes degradation of more recalcitrant organic material, due to prolonged exposure to oxygen and other electron acceptors (e.g., NO₃⁻, Mn and Fe oxides). In contrast, the degradation of more labile constituents is equally facilitated by biological and physical disturbance.     

Stable carbon isotopic compositions of individual aromatic hydrocarbons as source and age indicators in oils from western Australian basins

The present study aims to establish the factors controlling the stable carbon isotopic compositions (δ¹³C) of individual aromatic hydrocarbons analysed by compound specific isotope analysis (CSIA) in crude oils from western Australian petroleum basins of varying age and facies type. This paper reports δ¹³C values of individual aromatic hydrocarbons, like alkylbenzenes, alkylnaphthalenes, alkylphenanthrenes and methylated biphenyls. The main aims are to confirm the origin (source) and age of these oils based on CSIA of selected aromatic compounds and to understand why the Sofer plot is ineffective in establishing the source of western Australian petroleum systems. The bulk δ¹³C of saturated and aromatic hydrocarbon fractions of crude oils have been previously used to differentiate sources, however, many Australian crude oils are not classified correctly using this method. The oils were classified as marine by the δ¹³C values of individual aromatic compounds and as terrigenous based on the bulk δ¹³C data (Sofer plot).The oils where the δ¹³C values of 1,6-DMN and 1,2,5-TMN isomers are most negative are indicative of a marine source, whereas oils with a less negative values for the 1,6-DMN and 1,2,5-TMN isomers are derived from marine source rocks that contain a significant terrigenous component. Similarly, oils with the least negative δ¹³C values for the 1-MP and 1,9-DMP isomers reflect varying inputs of terrigenous organic matter to the their marine source rocks. Plots of P/DBT and Pr/Ph concentration ratios versus δ¹³C values of DMP, 1,6-DMN, 1,2,5-TMN, 1-MP and 1,9-MP are constructed to establish the relative amount of terrigenous organic matter contributing to the source rock of a series of marine oils. The ratios of P/DBT and Pr/Ph plotted against the δ¹³C values of the aromatic isomers (such as 1,6-DMN, 1,2,5-TMN, 1-MP and 1,9-MP) provide a novel and convenient way to discriminate crude oils derived from different source rocks that contain varying amounts of marine and terrigenous organic matter.     

Enriched stable carbon isotopes in the pore waters of carbonate sediments dominated by seagrasses: Evidence for coupled carbonate dissolution and reprecipitation

Studies of the δ¹³C of pore water dissolved inorganic carbon (δ¹³C-DIC) were carried out in shallow water carbonate sediments of the Great Bahamas Bank (GBB) to further examine sediment-seagrass relationships and to more quantitatively describe the couplings between organic matter remineralization and sediment carbonate diagenesis. At all sites studied δ¹³C-DIC provided evidence for the dissolution of sediment carbonate mediated by metabolic CO₂ (i.e., CO₂ produced during sediment organic matter remineralization); these observations are also consistent with pore water profiles of alkalinity, total DIC and Ca²⁺ at these sites. In bare oolitic sands, isotope mass balance further indicates that the sediment organic matter undergoing remineralization is a mixture of water column detritus and seagrass material; in sediments with intermediate seagrass densities, seagrass derived material appears to be the predominant source of organic matter undergoing remineralization. However, in sediments with high seagrass densities, the pore water δ¹³C-DIC data cannot be simply explained by dissolution of sediment carbonate mediated by metabolic CO₂, regardless of the organic matter type. Rather, these results suggest that dissolution of metastable carbonate phases occurs in conjunction with reprecipitation of more stable carbonate phases. Simple closed system calculations support this suggestion, and are broadly consistent with results from more eutrophic Florida Bay sediments, where evidence of this type of carbonate dissolution/reprecipitation has also been observed. In conjunction with our previous work in the Bahamas, these observations provide further evidence for the important role that seagrasses play in mediating early diagenetic processes in tropical shallow water carbonate sediments. At the same time, when these results are compared with results from other terrigenous coastal sediments, as well as supralysoclinal carbonate-rich deep-sea sediments, they suggest that carbonate dissolution/reprecipitation may be more important than previously thought, in general, in the early diagenesis of marine sediments.