The significance of 24-norcholestanes,triaromatic steroids and dinosteroids in oils and Cambrian–Ordovician source rocks from the cratonic region of the Tarim Basin,NW China

Two oil families in Ordovician reservoirs from the cratonic region of the Tarim Basin are distinguished by the distribution of regular steranes, triaromatic steroids, norcholestanes and dinosteroids. Oils with relatively lower contents of C₂₈ regular steranes, C₂₆ 20S, C₂₆ 20R + C₂₇ 20S and C₂₇ 20R regular triaromatic steroids, dinosteranes, 24-norcholestanes and triaromatic dinosteroids originated from Middle–Upper Ordovician source rocks. In contrast, oils with abnormally high abundances of the above compounds are derived from Cambrian and Lower Ordovician source rocks. Only a few oils have previously been reported to be of Cambrian and Lower Ordovician origin, especially in the east region of the Tarim Basin. This study further reports the discovery of oil accumulations of Cambrian and Lower Ordovician origin in the Tabei and Tazhong Uplifts, which indicates a potential for further discoveries involving Cambrian and Lower Ordovician sourced oils in the Tarim Basin. Dinosteroids in petroleum and ancient sediments are generally thought to be biomarkers for dinoflagellates and 24-norcholestanes for dinoflagellates and diatoms. Therefore, the abnormally high abundance of these compounds in extracts from the organic-rich sediments in the Cambrian and Lower Ordovician and related oils in the cratonic region of the Tarim Basin suggests that phytoplankton algae related to dinoflagellates have appeared and might have flourished in the Tarim Basin during the Cambrian Period. Steroids with less common structural configurations are underutilized and can expand understanding of the early development history of organisms, as well as define petroleum systems.     

Reconstruction of phytoplankton productivity and community structure in the South Yellow Sea

The sedimentary environment and ecological system in the South Yellow Sea (SYS) changed dramatically due to sea level change caused by glacial-interglacial cycles. The authors report the use of marine biomarkers (brassicasterol, dinosterol and C³⁷ alkenones) and terrigenous biomarkers (C²⁸+C³⁰+C³² n-alkanols) in core DLC70-3 from the SYS to reconstruct the variation in the phytoplankton productivity and community structure and possible mechanisms during the middle Pleistocene. The results show that the primary productivity and that of single algae presented a consistent trend for the whole core during the middle Pleistocene, which was high during interglacial periods and low during glacial periods, with the highest being in marine isotope stage (MIS) 5–9 and MIS 19–21. The main reason is that the Yellow Sea Warm Current (YSWC) carried much of high temperature, high salinity water into the SYS, causing upwelling and vertical mixing and stirring, which increased the nutrient supply in the photosynthetic layer. The phytoplankton community structure mainly showed an increase in the relative content of haptophytes in MIS 5–9 and MIS 19–21, while the relative content of diatoms and dinoflagellates decreased; there was no evidence for a haptophyte content in other stages. The results reveal a shift from a coccolitho-phorid-dominated community during MIS 5 –9 and MIS 19 –21 to a diatom-dominated community during the other stages, mainly as a result of surface salinity variation, attributed to the invasion of the YSWC during high sea level periods.     

The Hf-Nd isotopic composition of marine sediments

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world’s major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them.Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, ε_Hf = 1.55 × ε_Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (ε_Hf = 1.36 × ε_Nd + 2.89; Vervoort et al., 1999) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array.In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.     

Organic matter distribution in the modern sediments of the Pearl River Estuary

We determined biomarker concentrations and distributions for surface sediments from 54 sites in the Pearl River Estuary, China. We focus on a suite of four biomarker-based indicators for relative terrestrial to marine organic matter (OM) source: the branched-isoprenoid tetraether (BIT) index, the ratio of high/low molecular weight n-alcohols [(ΣC_26–34/(ΣC₁₆₊₁₈ + ΣC_26–34)], an analogous ratio for n-fatty acids and the ΣC₂₉-steroids/(ΣC₂₉-steroids + brassicasterol) ratio. All four exhibit the same terrestrial to marine transition seen in previous bulk δ¹³C studies, but with an abrupt decrease in the relative terrestrial contribution across the delta front to pro-delta transition. Concentrations of terrestrially-derived biomarkers show no systematic decrease across the transition. Instead, the decrease in the proportion of terrestrial OM is due to a decrease in the sedimentation rate and associated terrestrial OM burial across the delta toe. This suggests that diagenetic controls on the fate of terrestrial OM, such as increased biodegradation where sedimentation rate is low, are subordinate to sedimentological processes. Biomarker-derived temperature values are cooler than expected for the lower Pearl River catchment, suggesting that the dominant component of the terrestrial OM is derived from the cooler upland regions of the catchment. The dominance of input from more distal terrain with greater topographic relief is evidence for the importance of geomorphological control on terrigenous OM transport. Collectively, the results demonstrate the importance of sedimentological processes in the supply, deposition and transport of terrestrial OM.     

Compositions,sources and depositional environments of organic matter from the Middle Jurassic clays of Poland

The comprehensive biomarker characteristics from previously undescribed Middle Jurassic clays of Poland are presented. The molecular composition of the organic matter (OM) derived from clays of Aalenian to Callovian age has not changed significantly through time. High relative concentrations of many biomarkers typical for terrestrial material suggest a distinct dominance of OM derived from land plants. Increasing concentrations of C₂₉-diaster-13(17)-enes towards the northern part of the basin indicate an increase in terrestrial input. This terrestrial material would have originated from the enhanced transport of organic matter from land situated at the northern bank of the basin, i.e., the Fennoscandian Shield. The organic matter was deposited in an oxic to suboxic environment, as indicated by relatively low concentrations of C₃₃–C₃₅ homohopanes, moderate to high Pr/Ph ratio values, an absence of compounds characteristic for anoxia and water column stratification, such as isorenieratane, aryl isoprenoids and gammacerane, as well as common benthic fauna and burrows. δ¹⁸O measurements from calcitic rostra of belemnites suggest that the mean value of the Middle Jurassic sea-water temperature of the Polish Basin was 13.1 °C. It is suggested that this mirrored the temperature of the lower water column because belemnites are considered here to be necto-benthic. The organic matter from the Middle Jurassic basin of Poland is immature. This is clearly indicated by a large concentration of biomarkers with the biogenic configurations, such as ββ-hopanes, hop-13(18)-enes, hop-17(21)-enes, diasterenes and sterenes. The identification of preserved, unaltered biomolecules like ferruginol, 6,7-dehydroferruginol and sugiol in Protopodocarpoxylon wood samples from these sediments present particularly strong evidence for the presence of immature OM in the Middle Jurassic sediments. Moreover, the occurrence of these polar diterpenoids is important due to the fact that they are definitely the oldest known natural products detected in geological samples.     

Geochemical characteristics of stream sediments,sediment fractions,soils, and basement rocks from the Mahaweli River and its catchment,Sri Lanka

Geochemical variations in stream sediments (n = 54) from the Mahaweli River of Sri Lanka have been evaluated from the viewpoints of lithological control, sorting, heavy mineral concentration, influence of climatic zonation (wet, intermediate, and dry zones), weathering, and downstream transport. Compositions of soils (n = 22) and basement rocks (n = 38) of the catchment and those of <180 μm and 180–2000 μm fractions of the stream sediments were also examined. The sediments, fractions, soils and basement rocks were analyzed by X-ray fluorescence to determine their As, Pb, Zn, Cu, Ni, Cr, V, Sr, Y, Nb, Zr, Th, Sc, Fe₂O₃, TiO₂, MnO, CaO, P₂O₅ and total sulfur contents. Abundances of high field strength and ferromagnesian elements in the sediments indicate concentration of durable heavy minerals including zircon, tourmaline, rutile, monazite, garnet, pyriboles, and titanite, especially in <180 μm fractions. The sediments show strong correlation between Ti and Fe, further suggesting presence of heavy mineral phases containing both elements, such as ilmenite and magnetite. The basement rocks range from mafic through to felsic compositions, as do the soils. The river sediments lack ultrabasic components, and overall have intermediate to felsic compositions. Elemental spikes in the confluences of tributary rivers and high values in the <180 μm fractions indicate sporadic inputs of mafic detritus and/or heavy minerals to the main channel. Al₂O₃/(K₂O + Na₂O) and K₂O/Na₂O ratios of the sediments and LOI values of the soils correlate well with the climatic zones, suggesting intense weathering in the wet zone, lesser weathering in the intermediate zone, and least weathering in the dry zone. Low Sr and CaO contents and Cr/V ratios in stream sediments in the wet zone also suggest climatic influence. Fe-normalized enrichment factors (EFs) for As, Pb, Zn, Cu, Ni and Cr in stream sediments in the main channel are nearly all <1.5, indicating there is no significant environmental contamination. The chemistry of the sediments, rocks and the soils in the Mahaweli River are thus mainly controlled by source lithotype, weathering, sorting, and heavy mineral accumulation.     

Detection of manure-derived organic compounds in rivers draining agricultural areas of intensive manure spreading

It is essential to have suitable tools able to trace the fate of manure organic matter in the environment to assess whether manure disposal on the soils of catchments could affect the organic quality of rivers. Sterol compounds – mainly expressed as C_29 + 28/C₂₇ and 5β/C₂₇ ratios – have been shown to be specific molecular tracers of pig, dairy and poultry manures in soils. The objective of this study was to measure C_29 + 28/C₂₇ and 5β/C₂₇ ratios in five Brittany rivers (Elorn, Yar, Léguer, Min Ran and Couesnon) draining agricultural catchments receiving massive annual inputs of pig, poultry and dairy manures and compare these ratios with ratios published for enriched soils and manure samples. The particulate organic fractions from the studied rivers yielded steroid signatures typical of animal manures. More specifically, a stanol compound diagnostic of pig slurry – the 5β-stanol known as coprostanol – was found to be very widespread, with particularly high concentrations in one of the rivers (Elorn). The C_29 + 28/C₂₇ and 5β/C₂₇ ratios of the particulate fractions of the rivers were compared with ratios measured directly in pig, dairy and poultry manure samples, as well as with the breeding activities on river catchments. These comparisons show that the steroid profiles of the five investigated rivers correlate closely with the types of manure (i.e. pig, poultry or dairy) spread on soils in their catchments. For instance, the C_29 + 28/C₂₇ and 5β/C₂₇ ratios in the Elorn river are similar to the values typical of pig slurry (e.g. 5β/C₂₇ > 4); compared with other catchments, the soils in this area receive by far the largest amount of pig slurry. By contrast, the Yar river drains a catchment receiving only poultry and dairy manures, and its soils exhibit C_29 + 28/C₂₇ and 5β/C₂₇ ratios similar to those of dairy and poultry manures (e.g. 5β/C₂₇ ∼ 1). Thus, this study indicates that the organic quality of rivers is modified in catchments where there is intense manure spreading on soils. It also provides evidence that rivers draining areas receiving different manure types may exhibit differences in the long-term evolution of their OM content. Indeed, two of the investigated river catchments receive dominantly dairy and poultry manure, and exhibit clear long-term upward trends in OM. On the other hand, one catchment receiving high proportions of pig slurry clearly shows a long-term downward trend in OM contents. A survey of the literature shows that the relative amount of OM and N received by soils in agricultural catchments could be the key parameter in determining the direction of the long-term OM trend of the river, rather than the absolute amount and/or type of manure that is applied to the soil. In any case, the present study suggests that sterol/stanol compounds may be of diagnostic value in determining whether a stream or a river is undergoing contamination by manure-derived organic matter.     

Late Quaternary environmental change of Yellow River Basin: An organic geochemical record in Bohai Sea (North China)

Bulk geochemical characterization (total organic carbon, grain size distribution, carbon isotope composition) and molecular biomarkers (lignin phenols, straight chain aliphatic hydrocarbons, glycerol dialkyl glycerol tetraethers) were analyzed for a 21 m core from the Bohai Sea (North China), spanning ca 21 ka BP. These paleo-proxies presented remarkable differences between the late glacial period and the Holocene, reflecting continental and coastal environments, respectively. Two peat layers were deposited during the period of ca 9000-8460 yr BP. Thereafter the core site has been consistently covered by seawater until recent reclamation of land from the sea. The occurrence of a total organic carbon maximum from ca 6000-3800 yr BP was attributed to delivery of organic carbon enriched sediments via the Yellow River, consistent with increased vegetation density and higher development of soil under warm and humid mid-Holocene climate conditions. The distributions of lignin phenol compositions and C₃₁/C₂₉n-alkane ratio suggested the largest expansion of woody plants between ca 5300 and 4000 yr BP, corresponding to the extremely favorable climatic conditions. Since ca 3800 yr BP, an abrupt increase in the C₃₁/C₂₉n-alkane ratio suggested higher abundance of grasses, consistent with a drying climate trend after the mid-Holocene. Since our coastal sediments close to the Yellow River outflow contain catchment-integrated environmental signals of the river basin, molecular proxies demonstrate that the variability of vegetation distributions in the Holocene is a widespread phenomenon in those areas adjacent to Yellow River Basin.     

Salinity control on long-chain alkenone distributions in lake surface waters and sediments of the northern Qinghai-Tibetan Plateau, China

Long-chain alkenones in lacustrine settings are potentially excellent biomarkers for the reconstruction of past terrestrial environmental conditions, and have been found in many different types of lakes around the globe. A wider range of factors influence the occurrence and distribution of alkenones in lake sediments and waters when compared to marine systems. Lake environmental conditions, such as temperature (in particular) and salinity, are among the key factors controlling alkenone distributions in lacustrine settings. Here we investigated alkenone distribution patterns in lakes of the northern Qinghai-Tibetan Plateau, China, and their possible relationship with environmental conditions, by analyzing paired samples of suspended particulate matter in surface waters and surface sediments. Salinity of investigated lake waters ranges from almost 0 to ∼100 g/L, while temperature variation among the lakes is minimal, effectively eliminating temperature effects on the alkenone distribution patterns observed here. We show that (1) alkenone concentrations vary substantially between the lakes, yet controlling mechanisms remain elusive; (2) C₃₇/C₃₈ ratios are substantially lower in the lakes of the Qaidam Basin than in the Lake Qinghai region, probably indicating different alkenone producers in the two regions; and (3) large variations in %C_37:4 (the percentage of the C_37:4 alkenone), determined from both surface waters and sediments, are negatively correlated with salinity. We suggest that the %C_37:4 index could be used as a salinity indicator at least on a regional scale, with careful considerations of other potentially complicating factors. However, potential reasons for why salinity could significantly affect %C_37:4 values need further investigation.     

The variations of stable carbon isotope ratio of land plant-derived n-alkanes in deep-sea sediments from the Bering Sea and the North Pacific Ocean during the last 250,000 years

Two piston cores, one located far from the continents (The North Pacific Ocean: ES core), and another located comparatively closer to the continents (The Bering Sea: BOW-8a core) were investigated to reconstruct environmental changes on source land areas. The results show significant contribution of terrestrial organic matter to sediments in both cores. The δ¹³C values of n-C₂₇, n-C₂₉, and n-C₃₁ alkanes in sediments from the North Pacific ES core show significant glacial to interglacial variation whereas those from the Bering Sea core do not. Variations of δ¹³C values of land plant n-alkanes are related to the environmental or vegetational changes in the source land areas. Environmental changes, especially, aridity, rainfall, and pCO₂ during glacial/interglacial transitional periods can affect vegetation, and therefore C₃ / C₄ plant ratios, resulting in δ¹³C changes in the preserved land plant biomarkers. Maximum values of δ¹³C as well as maximum average chain length values of long chain n-alkanes in the ES core occur mostly at the interglacial to glacial transition zones reflecting a time lag related to incorporation of living organic matter into soil and transportation into ocean basins via wind and/or ability of C₄ plants to adapt for a longer period before being replaced by C₃ plants when subjected to gradual climatic changes. Irregular variations with no clear glacial to interglacial trends in the BOW-8a core may result from complex mixture of aerosols from westerly winds and riverine organic matter from the Bering Sea catchments. In addition, terrestrial organic matter entering the Bering Sea could originate from multiple pathways including eolian, riverine, and ice rafted debris, and possibly be disturbed by turbidity and other local currents which can induce re-suspension and re-sedimentation causing an obliterated time relation in the Bering Sea biomarker records.     

Calibrating n-alkane Sphagnum proxies in sub-Arctic Scandinavia

Moss covered, high latitude wetlands hold large amounts of terrestrial organic matter (OM), which may be vulnerable to expected climate warming. Molecular analysis of fluvially transported material from these regions can distinguish between different sources of terrestrial OM. Sphagnum moss may represent one of the major sources. This study aimed to quantitatively establish a molecular proxy for identifying Sphagnum-derived OM from high latitude peatlands in the sub-Arctic coastal ocean. We collected and analyzed Sphagnum species throughout northern Sweden and Finland. Results show that the C₂₅/(C₂₅ + C₂₉) n-alkane ratio is most suitable for terrestrial OM source apportionment in these coastal regions since, compared to other n-alkane Sphagnum proxies, it shows (i) the least variation between species, (ii) the most constant values for different latitudinal regimes and (iii) the largest dynamic range to the higher plant end member in two-source mixing models. Application of the proxy to surface sediments and suspended particulate matter in the sub-Arctic northern Baltic Sea shows that 68–103% of the terrestrial OM fraction is derived from Sphagnum-rich peatland. We recommend that future studies on terrestrial OM fluxes into (sub-)Arctic regions should apply the C₂₅/(C₂₅ + C₂₉) proxy to improve insight into the contribution of Sphagnum-derived terrestrial OM from climate-vulnerable, high latitude wetlands.     

Late Holocene environmental reconstruction using cave sediments from Belize

Cave sediments collected from Reflection Cave on the Vaca Plateau, Belize show variations in the δ¹³C values of their fulvic acids (FAs), which indicate periods of vegetation change caused by climatic and Maya influences during the late Holocene. The δ¹³C values range from − 27.11‰ to − 21.52‰, a shift of ∼ 5.59‰, which suggests fluctuating contributions of C₃ and C₄ plants throughout the last 2.5 ka, with C₄ plant input reflecting periods of Maya agriculture. Maya activity in the study area occurred at different intensities from ∼ 2600 cal yr BP until ∼ 1500 cal yr BP, after which agricultural practices waned as the Maya depopulated the area. These changes in plant assemblages were in response to changes in available water resources, with increased aridity leading to the eventual abandonment of agricultural areas. The Ix Chel archaeological site, located in the study area, is a highland site that would have been among the first agricultural settlements to be affected during periods of aridity. During these periods, minimal water resources would have been available in this highly karstified, well-drained area, and supplemental groundwater extraction would have been difficult due to the extreme depth of the water table.     

Disentangling marine, soil and plant organic carbon contributions to continental margin sediments: A multi-proxy approach in a 20,000 year sediment record from the Congo deep-sea fan

A 20 kyr long sediment sequence from the Congo deep sea fan (core GeoB 6518-1), one of the world’s largest deep sea river fans, has been analysed for bulk and molecular proxies in order to reconstruct the marine, soil and plant organic carbon (OC) contributions to these sediments since the last glacial maximum. The bulk proxies applied, C/N ratio and δ¹³C_org, ranged from 10 to 12.5 and from −24.5 to −21‰ VPDB, respectively. As molecular proxies, concentrations of marine derived alkenones and terrestrial derived odd-numbered n-alkanes were used, which varied between 0.2 and 4 μg/g dry weight sediment. In addition, the branched vs. isoprenoid tetraether (BIT) index, a proxy for soil organic matter input, was used, which varied from 0.3 to 0.5 in this core.Application of binary mixing models, based on the different individual proxies, showed estimates for terrestrial OC input varying by up to 50% due to the heterogeneous nature of the OC. Application of a three end-member mixing model using the δ¹³C_org content, the C/N ratio and the BIT index, enabled the distinction of soil and plant organic matter as separate contributors to the sedimentary OC pool. The results show that marine OC accounts for 20% to 40% of the total OC present in the deep sea fan sediments over the last 20 kyr and that soil OC accounts for about half (∼45% on average) of the OC present. This suggests that soil OC represents the majority of the terrestrial OC delivered to the fan sediments.Accumulation rates of the plant and soil OC fractions over the last 20 kyr varied by a factor of up to 5, and are strongly related to sediment accumulation rates. They showed an increase starting at ca. 17 kyr BP, a decline during the Younger Dryas, peak values during the early Holocene and lower values in the late Holocene. This pattern matches with reconstructions of past central African humidity and Congo River discharge from the same core and revealed that central African precipitation patterns exert a dominant control on terrestrial OC deposition in the Congo deep sea fan. Marine OC accumulation rates are only weakly related to sediment accumulation rates and vary only little over time compared to the terrigenous fractions. These variations are likely a result of enhanced preservation during times of higher sedimentation rates and of relative small fluctuations in primary production due to wind-driven upwelling.     

A 35 kyr record of organic matter composition and δ13C of n-alkanes in bog sediments close to Lake Baikal: Implications for paleoenvironmental studies

We characterized the compositions of organic compounds in a Cheremushka bog sediment core (deposited over the last 35 kyr), located at the eastern coast of Lake Baikal, to obtain basic information about the terrestrial organic matter (OM) which contributed to Lake Baikal sediments. The bog sediment was analyzed for the molecular composition of n-alkanes, lignin phenols and n-C₂₄ to C₃₀ alkanoic acids, as well as the carbon isotopic composition of plant wax derived n-C₂₇ to C₃₃ alkanes.Concentrations of lignin phenols [vanillyl (V) plus syringyl (S) phenols] normalized to total organic carbon (TOC) in the Holocene are twice those for the last glacial maximum (LGM), while concentrations of TOC-normalized n-C₂₄ to C₃₀ alkanoic acids do not change markedly in this period. Thus, the ratio of lignin phenols to n-C₂₄ to C₃₀ alkanoic acids increases from the LGM to the Holocene. This result is essentially consistent with pollen analysis indicating an expansion of woody plants in the Holocene and a prevailing herb-abundant environment for the LGM. The δ¹³C values of n-C₂₇ to C₃₃ alkanes (e.g. ?29‰ to ?33‰ for C₃₁) indicate the presence of C₃-dominant plants throughout the core.The contribution of terrestrial OM to Lake Baikal sediments was estimated using the biomarkers, on the assumption that the OM in the bog sediments is a representative of the terrestrial OM around the lake. Hence, the estimation using lignin phenol or n-C₂₄ to C₃₀ alkanoic acid parameters indicates that 11–24% of the TOC in the Academician Ridge sediments is land-derived for both the Holocene and the LGM, which is similar to the estimates from C/N values of bulk OM. However, the estimates for terrestrial OM using the n-C₂₇ to C₃₃ alkane parameter are generally higher than those using lignin phenol or n-C₂₄ to C₃₀ alkanoic acid parameters. The difference is thought to be associated with the difference in source and behavior of these biomarkers.     

Controls on the age of vascular plant biomarkers in Black Sea sediments

Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated.Here we show compound-specific radiocarbon (¹⁴C) ages of terrigenous biomarkers and bulk ¹⁴C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. ¹⁴C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C₂₉₊₃₁ alkanes and n-C₂₈₊₃₀ fatty acids ages from stations directly in front of the river mouths range from 900 ± 70 years to 4400 ± 170 years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C₂₉₊₃₁ alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C₂₉₊₃₁ alkanes show contributions from petrogenic sources, n-C₂₈₊₃₀ fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C₂₈ and n-C₃₀ fatty acids appear clearly much less influenced by autochthonous sources than n-C₂₄ and n-C₂₆ fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers.     

Investigation of amino acid δC signatures in bone collagen to reconstruct human palaeodiets using liquid chromatography-isotope ratio mass spectrometry

This research presents the individual amino acid δ¹³C values in bone collagen of humans (n = 9) and animals (n = 27) from two prehistoric shell midden sites in Korea. We obtained complete baseline separation of 16 of the 18 amino acids found in bone collagen by using liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). The isotopic results reveal that the humans and animals in the two sites had similar patterns in essential amino acids (EAAs) and non-essential amino acids (NEAAs). The EAA and NEAA δ¹³C values in humans are intermediate between those in marine and terrestrial animals. However, the threonine δ¹³C values in humans and animals measured in this study are more highly enriched than those of other amino acids. At both sites, all amino acids in marine animals are ¹³C-enriched relative to those of the terrestrial animals. The isotopic evidence suggests that the Tongsamdong human had EAAs and NEAAs from marine food resources, while the Nukdo humans mainly had EAAs from terrestrial food resources but obtained NEAAs from both terrestrial and marine resources. The δ¹³C isotopic differences in amino acids between marine and terrestrial animals were the largest for glycine (NEAA) and histidine (EAA) and the smallest for tyrosine (NEAA) and phenylalanine (EAA). In addition, threonine among the EAAs also had a large difference (∼8‰) in δ¹³C values between marine and terrestrial animals, and has the potential to be used as an isotopic marker in palaeodietary studies. Threonine δ¹³C values were used in conjunction with the established Δ¹³C_{Glycine-phenylalanine} values and produced three distinct dietary groups (terrestrial, omnivorous, and marine). In addition, threonine δ¹³C values and Δ¹³C_{Serine-phenylalanine} values were discovered to separate between two dietary groups (terrestrial vs. marine), and these δ¹³C values may provide a potential new indicator for investigating the distinction between marine and terrestrial protein sources in human diets.     

Benthic nitrogen cycling traversing the Peruvian oxygen minimum zone

Benthic nitrogen (N) cycling was investigated at six stations along a transect traversing the Peruvian oxygen minimum zone (OMZ) at 11°S. An extensive dataset including porewater concentration profiles and in situ benthic fluxes of nitrate (NO₃⁻), nitrite (NO₂⁻) and ammonium (NH₄⁺) was used to constrain a 1-D reaction-transport model designed to simulate and interpret the measured data at each station. Simulated rates of nitrification, denitrification, anammox and dissimilatory nitrate reduction to ammonium (DNRA) by filamentous large sulfur bacteria (e.g. Beggiatoa and Thioploca) were highly variable throughout the OMZ yet clear trends were discernible. On the shelf and upper slope (80-260 m water depth) where extensive areas of bacterial mats were present, DNRA dominated total N turnover (?2.9 mmol N m⁻² d⁻¹) and accounted for ?65% of NO₃⁻ + NO₂⁻ uptake by the sediments from the bottom water. Nonetheless, these sediments did not represent a major sink for dissolved inorganic nitrogen (DIN = NO₃⁻ + NO₂⁻ + NH₄⁺) since DNRA reduces NO₃⁻ and, potentially NO₂⁻, to NH₄⁺. Consequently, the shelf and upper slope sediments were recycling sites for DIN due to relatively low rates of denitrification and high rates of ammonium release from DNRA and ammonification of organic matter. This finding contrasts with the current opinion that sediments underlying OMZs are a strong sink for DIN. Only at greater water depths (300-1000 m) did the sediments become a net sink for DIN. Here, denitrification was the major process (?2 mmol N m⁻² d⁻¹) and removed 55-73% of NO₃⁻ and NO₂⁻ taken up by the sediments, with DNRA and anammox accounting for the remaining fraction. Anammox was of minor importance on the shelf and upper slope yet contributed up to 62% to total N₂ production at the 1000 m station. The results indicate that the partitioning of oxidized N (NO₃⁻, NO₂⁻) into DNRA or denitrification is a key factor determining the role of marine sediments as DIN sinks or recycling sites. Consequently, high measured benthic uptake rates of oxidized N within OMZs do not necessarily indicate a loss of fixed N from the marine environment.     

Millimeter-scale concentration gradients of hydrocarbons in Archean shales: Live-oil escape or fingerprint of contamination?

Archean shales from the Pilbara in Western Australia contain biomarkers that have been interpreted as evidence for the existence of cyanobacteria and eukaryotes 2.7 billion years (Ga) ago, with far reaching implications for the evolution of Earth’s early biosphere. To re-evaluate the provenance of the biomarkers, this study determined the spatial distribution of hydrocarbons in the original drill core material. Rock samples were cut into millimeter-thick slices, and the molecular content of each slice was analyzed. In core from the Hamersley Group (∼2.5 Ga), C_<13 alkanes had gradually increasing concentrations from the surfaces to the center of the rock while the abundance of steranes, hopanes and C₁₅₊ alkanes decreased with distance from the outer surfaces. In samples from the Fortescue Group (∼2.7 Ga), hydrocarbons were overwhelmingly concentrated on rock surfaces.Two mechanisms are proposed that may have caused the inhomogeneous distribution: diffusion of petroleum products into the rock (contamination model), and leaching of indigenous hydrocarbons out of host shales driven by pressure release after drilling (‘live-oil’ effect). To test these models, the hydrocarbon distributions in the Archean shales are compared with artificially contaminated rocks as well as younger mudstones where leaching of live-oil had been observed.The results show that chromatographic phenomena associated with live-oil escape and contaminant diffusion have strong effects on molecular ratios and maturity parameters, potentially with broad implications for oil-source rock correlation studies and paleoenvironmental interpretations.For the Archean shales, the live-oil effect is consistent with some of the observed patterns, but only the contamination model fully explains the complex chromatographic fingerprints. Therefore, the biomarkers in the Pilbara samples have an anthropogenic origin, and previous conclusions about the origin of eukaryotes and oxygenic photosynthesis based on these samples are not valid.However, the study also identified indigenous molecules. The spatial distribution of particular aromatic hydrocarbons suggests they are syngenetic. Although devoid of biological information, these aromatics now represent the oldest known clearly-indigenous terrestrial liquid hydrocarbons.     

Gases in Taiwan mud volcanoes: Chemical composition,methane carbon isotopes,and gas fluxes

Mud volcanoes are important pathways for CH₄ emission from deep buried sediments; however, the importance of gas fluxes have hitherto been neglected in atmospheric source budget considerations. In this study, gas fluxes have been monitored to examine the stability of their chemical compositions and fluxes spatially, and stable C isotopic ratios of CH₄ were determined, for several mud volcanoes on land in Taiwan. The major gas components are CH₄ (>90%), “air” (i.e. N₂ + O₂ + Ar, 1–5%) and CO₂ (1–5%) and these associated gas fluxes varied slightly at different mud volcanoes in southwestern Taiwan. The Hsiao-kun-shui (HKS) mud volcano emits the highest CH₄ concentration (CH₄ > 97%). On the other hand, the Chung-lun mud volcano (CL) shows CO₂ up to 85%, and much lower CH₄ content (<37%). High CH₄ content (>90%) with low CO₂ (<0.2%) are detected in the mud volcano gases collected in eastern Taiwan. It is suggestive that these gases are mostly of thermogenic origin based on C₁ (methane)/C₂ (ethane) + C₃ (propane) and δ¹³C_CH4 results, with the exception of mud volcanoes situated along the Gu-ting-keng (GTK) anticline axis showing unique biogenic characteristics. Only small CH₄ concentration variations, <2%, were detected in four on-site short term field-monitoring experiments, at Yue-shi-jie A, B, Kun-shui-ping and Lo-shan A. Preliminary estimation of CH₄ emission fluxes for mud volcanoes on land in Taiwan fall in a range between 980 and 2010 tons annually. If soil diffusion were taken into account, the total amount of mud volcano CH₄ could contribute up to 10% of total natural CH₄ emissions in Taiwan.     

Kinetics of microbial sulfate reduction in estuarine sediments

Kinetic parameters of microbial sulfate reduction in intertidal sediments from a freshwater, brackish and marine site of the Scheldt estuary (Belgium, the Netherlands) were determined. Sulfate reduction rates (SRR) were measured at 10, 21, and 30 °C, using both flow-through reactors containing intact sediment slices and conventional sediment slurries. At the three sites, and for all depth intervals studied (0-2, 2-4, 4-6 and 6-8 cm), the dependence of potential SRR on the sulfate concentration followed the Michaelis-Menten rate equation. Apparent sulfate half-saturation concentrations, K_m, measured in the flow-through reactor experiments were comparable at the freshwater and marine sites (0.1-0.3 mM), but somewhat higher at the brackish site (0.4-0.9 mM). Maximum potential SRR, R_max, in the 0-4 cm depth interval of the freshwater sediments were similar to those in the 0-6 cm interval of the marine sediments (10-46 nmol cm⁻³ h⁻¹ at 21 °C), despite much lower in situ sulfate availability and order-of-magnitude lower densities of sulfate-reducing bacteria (SRB), at the freshwater site. Values of R_max in the brackish sediments were lower (3.7-7.6 nmol cm⁻³ h⁻¹ at 21 °C), probably due to less labile organic matter, as inferred from higher C_org/N ratios. Inflow solutions supplemented with lactate enhanced potential SRR at all three sites. Slurry incubations systematically yielded higher R_max values than flow-through reactor experiments for the freshwater and brackish sediments, but similar values for the marine sediments. Transport limitation of potential SRR at the freshwater and brackish sites may be related to the lower sediment porosities and SRB densities compared to the marine site. Multiple rate controls, including sulfate availability, organic matter quality, temperature, and SRB abundance, modulate in situ sulfate-reducing activity along the estuarine salinity gradient.