Influence of organic-mineral aggregates on microbial degradation of the dinoflagellate Scrippsiella trochoidea

Aggregation of particulate organic matter (POM) and mineral grains may result in physical protection of organic matter (OM). To test this, phytoplankton cells of the dinoflagellate Scrippsiella trochoidea were inoculated with a natural bacterial assemblage and incubated with or without the clay montmorillonite. Within 5 h, aggregation of phytoplankton OM and clay resulted in transfer of the majority (∼80%) of OM into the >1.6 g cm⁻³ density fraction. Degradation of particulate organic carbon (POC), particulate nitrogen (PN), dissolved organic carbon (DOC), and dissolved and particulate total hydrolyzable amino acids (THAA), were modeled with a multi-G approach. Quantity of resistant OM was between two and four times larger during clay incubation relative to clay-free incubation. The two incubations did not exhibit significant differences in degradation state of particulate amino acids nor were there indications of preferential sorption of basic amino acids. The results suggest that a considerable fraction of phytoplankton OM can become resistant, at least on a timescale of weeks, mostly due to aggregation of POM and clay mineral grains.     

The radiocarbon age of organic carbon in marine surface sediments

Long-term carbon cycling and climate change are strongly dependent on organic carbon (OC) burial in marine sediments. Radiocarbon (¹⁴C) has been widely used to constrain the sources, sinks, and processing of sedimentary OC. To elucidate the dominant controls on the radiocarbon content of total organic carbon (¹⁴C_TOC) accumulating in surface sediments we construct a box model that predicts ¹⁴C_TOC in the sediment mixed layer (measured as fraction modern, Fm). Our model defines three distinct OC pools (“degradable,” “semi-labile,” and “refractory”) and assumes that ¹⁴C_TOC flux to sediments is exclusively derived from surface ocean primary productivity, and hence follows a “generic” surface ocean dissolved inorganic carbon (DIC) bomb curve. Model predictions are compared to a set of 75 surface sediment samples, which span a wide geographic range and reflect diverse water column and depositional conditions, and for which sedimentation rate and mixed-layer depth are well characterized. Our model overestimates the Fm value for a majority (65%) of these sites, especially at shallow water depths and for sites characterized by depleted δ¹³C_TOC values. The model is most sensitive to sedimentation rate and mixed-layer depth. Therefore, slight changes to these parameters can lead to a match between modeled and measured Fm values at many sites. Yet, in some cases, we find that measured Fm values cannot be simulated without large and unrealistic changes to sedimentation rate and mixed-layer depth. These results point to sources of pre-aged OC to surface sediments and implicate soil-derived terrestrial OC, reworked marine OC, and/or anthropogenic carbon as important components of the organic matter present in surface sediments. This approach provides a valuable framework within which to explore controls on sedimentary organic matter composition and carbon burial over a range of spatial and temporal scales.     

Spectroscopic and Chromatographic studies of organic carbon in Recent marine sediments from the Peruvian Upwelling Zone

Early diagenesis of organic matter in sediments from two sites in the Peruvian Upwelling Zone (12°05′S, 77°39′W; 15°17′S, 75°24′W) has been studied by observing changes in the total organic carbon and lipid and humin fractions with depth. Transformations of the total carbon and humin fraction have been characterized by conventional and time-dependent solid state NMR techniques, while lipid diagenesis was monitored by measuring the concentration of sterols in the same sedimentary horizons. Both the quantity of total sterols and the relative abundances of individual sterols vary with sampling location, suggesting a difference in the input of biomass to the sediments at the two sites. Total sterol concentrations decrease with depth at both sites, but the loss of sterols occurs much more slowly at the more anoxic northern site, where sedimentation rates and organic carbon contents are approximately twice those at the southern site. ¹³C-NMR spectra of the total organic carbon and the humin fraction suggest that humin-like compounds are an original component of the sedimentary biomass, and dipolar-dephased spectra of the humin residue indicate that diagenetic alterations of the humin fraction are occurring even in these very young sediments. Conventional and time-dependent spectroscopic data support the hypothesis that humin formation results from selective preservation of microbially-resistant biopolymers which are an original component of the sedimentary biomass combined with loss of certain labile compounds.     

Amino acid nitrogen isotopic fractionation patterns as indicators of heterotrophy in plankton, particulate, and dissolved organic matter

Bulk nitrogen (N) isotope signatures have long been used to investigate organic N source and food web structure in aquatic ecosystems. This paper explores the use of compound-specific δ¹⁵N patterns of amino acids (δ¹⁵N-AA) as a new tool to examine source and processing history in non-living marine organic matter. We measured δ¹⁵N-AA distributions in plankton tows, sinking particulate organic matter (POM), and ultrafiltered dissolved organic matter (UDOM) in the central Pacific Ocean. δ¹⁵N-AA patterns in eukaryotic algae and mixed plankton tows closely resemble those previously reported in culture. δ¹⁵N differences between individual amino acids (AA) strongly suggest that the sharply divergent δ¹⁵N enrichment for different AA with trophic transfer, as first reported by [McClelland, J.W. and Montoya, J.P. (2002) Trophic relationships and the nitrogen isotopic composition of amino acids. Ecology83, 2173-2180], is a general phenomenon. In addition, differences in δ¹⁵N of individual AA indicative of trophic transfers are clearly preserved in sinking POM, along with additional changes that may indicate subsequent microbial reworking after incorporation into particles.We propose two internally normalized δ¹⁵N proxies that track heterotrophic processes in detrital organic matter. Both are based on isotopic signatures in multiple AA, chosen to minimize potential problems associated with any single compound in degraded materials. A trophic level indicator (ΔTr) is derived from the δ¹⁵N difference between selected groups of AA based on their relative enrichment with trophic transfer. We propose that a corresponding measure of the variance within a sub-group of AA (designated ΣV) may indicate total AA resynthesis, and be strongly tied to heterotrophic microbial reworking in detrital materials. Together, we hypothesize that ΔTr and ΣV define a two dimensional trophic “space”, which may simultaneously express relative extent of eukaryotic and bacterial heterotrophic processing.In the equatorial Pacific, ΔTr indicates an average of 1.5-2 trophic transfers between phytoplankton and sinking POM at all depths and locations. The ΣV parameter suggests that substantial variation may exist in bacterial heterotrophic processing between differing regions and time periods. In dissolved material δ¹⁵N-AA patterns appear unrelated to those in POM. In contrast to POM, δ¹⁵N-AA signatures in UDOM show no clear changes with depth, and suggest that dissolved AA preserved throughout the oceanic water column have undergone few, if any, trophic transfers. Together these data suggest a sharp divide between processing histories, and possibly sources, of particulate vs. dissolved AA.     

Methyl mercury distributions in relation to the presence of nano- and picophytoplankton in an oceanic water column (Ligurian Sea, North-western Mediterranean)

Recent findings on the distribution of methylated mercury (MeHg_T) in waters have highlighted the importance of organic carbon remineralization on the production of these compounds in the open ocean. Here, we present the first time-series (20 monthly samplings between July 2007 and May 2009) of high-resolution vertical profiles (10-12 depths in a 2350 m water column) of MeHg_T distributions in an open ocean environment, the Ligurian Sea (North-western Mediterranean Sea). Concentrations varied within the sub-picomolar range (general mean: 0.30 ± 0.17 pmol L⁻¹, n = 214) with the lowest values at the surface, increasing with depth up to the oxygen minimum zone, and decreasing slowly at greater depth. Concentrations in the surface waters never exceeded 0.15 pmol L⁻¹, while the highest concentrations (up to 0.82 pmol L⁻¹) were associated to the hypoxycline during the autumn bloom. A detailed vertical MeHg_T profile reveals a “double-peak” pattern, coincidental with the two microbial layers described by Tanaka and Rassoulzadegan (2002), the so-called “microbial food web” in the euphotic zone (<100 m) and the “microbial loop” in the aphotic zone (>100 m). Temporal variations in the MeHg_T abundance and distribution in the water column were linked to seasonality. The highest MeHg_T concentrations were found in the oxygen minimum zone during the period of stratification, and coincide with the greatest abundance of nano- and picophytoplankton (cyanobacteria, nanoflagellates, etc.) in the euphotic layer. None of our deep MeHg_T measurements (∼100 m above the sea bottom) revealed a significant sedimentary source of MeHg_T. We explored the correlation between MeHg_T concentrations and the apparent oxygen utilization, a proxy of organic matter remineralization, over the study period. Results of this study strengthen the hypothesis that net mercury methylation in the open ocean occurs in the water column, is linked to organic matter regeneration, and is promoted by the presence of small-sized nano- and picophytoplankton, that dominate under oligotrophic conditions.     

Structural changes of humic acids from sinking organic matter and surface sediments investigated by advanced solid-state NMR: Insights into sources, preservation and molecularly uncharacterized components

Knowledge of the structural changes that particulate organic matter (POM) undergoes in natural systems is essential for determining its reactivity and fate. In the present study, we used advanced solid-state NMR techniques to investigate the chemical structures of sinking particulate matter collected at different depths as well as humic acids (HAs) extracted from these samples and underlying sediments from the Saguenay Fjord and the St. Lawrence Lower Estuary (Canada). Compared to bulk POM, HAs contain more non-polar alkyls, aromatics, and aromatic C-O, but less carbohydrates (or carbohydrate-like structures). In the two locations studied, the C and N contents of the samples (POM and HAs) decreased with depth and after deposition onto sediments, leaving N-poor but O-enriched HAs and suggesting the involvement of partial oxidation reactions during POM microbial degradation. Advanced NMR techniques revealed that, compared to the water-column HAs, sedimentary HAs contained more protonated aromatics, non-protonated aromatics, aromatic C-O, carbohydrates (excluding anomerics), anomerics, OC_q, O-C_q-O, OCH, and OCH₃ groups, but less non-polar alkyls, NCH, and mobile CH₂ groups. These results are consistent with the relatively high reactivity of lipids and proteins or peptides. In contrast, carbohydrate-like structures were selectively preserved and appeared to be involved in substitution and copolymerization reactions. Some of these trends support the selective degradation (or selective preservation) theory. The results provide insights into mechanisms that likely contribute to the preservation of POM and the formation of molecules that escape characterization by traditional methods. Despite the depletion of non-polar alkyls with depth in HAs, a significant portion of their general structure survived and can be assigned to a model phospholipid. In addition, little changes in the connectivities of different functional groups were observed. Substituted and copolymerized carbohydrates and fused-ring aromatics detected in the present study likely represented an important part of molecularly uncharacterized components (MUC).     

Wetland soil organic matter composition in a Mediterranean semiarid wetland (Las Tablas de Daimiel, Central Spain): Insight into different carbon sequestration pathways

Wetland soils from a Mediterranean semiarid wetland (Las Tablas de Daimiel, Central Spain) were studied to characterize the organic matter (OM) and determine its origin and transformation. Cross polarization magic angle spinning (CPMAS) ¹³C nuclear magnetic resonance (NMR) spectroscopy and mathematical molecular mixing allowed analysis of the organic fraction in terms of six generic components (carbohydrate, protein, lignin, lipid, char and “carbonyl”). Las Tablas is an active carbon sink, with total organic carbon (TOC) content independent of soil OM quality; the TOC content of the upper sediment is 10.0 ± 7.8%. The inorganic carbon content is also high (5.4 ± 3.3%) and is associated mainly with OM of aliphatic character. The OM composition is variable; samples predominantly aliphatic (carbohydrate, lipid and protein) are characteristic of the northern sector, whereas predominantly aromatic samples are typical of the southern Tablas. A strong negative relationship between protein content and lignin content was found, interpreted as a consequence of different proportions of vascular vs. non-vascular (mostly charophyte) litter input. The effect of perturbation is apparent in the extended presence of char, particularly abundant in fire-prone areas. OM quantity and quality do not seem to depend on hydrology (although seasonal flooding is associated with lower TOC wetland soils) or soil characteristics. Dominant vegetation and fire are the main drivers of OM content and composition. Structural carbohydrate, protein and lipid (>60% of total organic fraction) dominate. Widespread anaerobic conditions and the recent character of the sediments could explain the preservation of different fractions of the original detritus composition (due to different vegetation and presence of microbes).     

Organic matter diagenesis in shallow water carbonate sediments

Muddy carbonate deposits near the Dry Tortugas, Florida, are characterized by high organic carbon remineralization rates. However, approximately half of the total sedimentary organic matter potentially supporting remineralization is occluded in CaCO₃ minerals (intracrystalline). While a portion of nonintracrystalline organic matter appears to cycle rapidly, intracrystalline organic matter has an approximately constant concentration with depth, suggesting that as long as its protective mineral matrix is intact, it is not readily remineralized. Organic matter in excess of intracrystalline organic matter that is preserved may have a variety of mineral associations (e.g., intercrystalline, adsorbed or detrital). In surface sediment, aspartic acid contributed ∼22 mole % and ∼50 mole % to nonintracrystalline and intracrystalline pools, respectively. In deeper sediment (1.6-1.7m), the composition of hydrolyzable amino acids in both pools was similar (aspartic acid ∼40 mole %). Like amino acids, intracrystalline and nonintracrystalline fatty acids have different compositions in surface sediments, but are indistinguishable at depth. These data suggest that preserved organic matter in the nonintracrystalline pool is stabilized by its interactions with CaCO₃. Neutral lipids are present in very low abundances in the intracrystalline pool and are extensively degraded in both the intracrystalline and nonintracrystalline pools, suggesting that mineral interactions do not protect these compounds from degradation. The presence of chlorophyll-a, but absence of phytol, in the intracrystalline lipid pool demonstrates that chloropigments are present only in the nonintracrystalline pool. Sedimentary chloropigments decrease with depth at similar rates in Dry Tortugas sediments as found in alumino-silicate sediments from the Long Island Sound, suggesting that chloropigment degradation is largely unaffected by mineral interactions. Overall, however, inclusion and protection of organic matter by biominerals is a major pathway for organic matter preservation in this low-organic carbon, biomineral-rich regime.     

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.     

Speciation of rare earth elements in natural terrestrial waters: assessing the role of dissolved organic matter from the modeling approach

Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., pK_MHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. pK_MHA values were further refined by comparison of calculated Model V “fits” to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl⁻, F⁻, OH⁻, SO₄²⁻, CO₃²⁻, PO₄³⁻), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V’s ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to “speciation” data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5.4 to 7.9, 4.8 to 7.3, and 4.9 to 6.9, respectively. For acidic waters, the model predicts that the free metal ion (Ln³⁺) and sulfate complexes (LnSO₄⁺) dominate, whereas in alkaline waters, carbonate complexes (LnCO₃⁺ + Ln[CO₃]₂⁻) are predicted to out-compete humic substances for dissolved REEs. Application of the modified Model V to a “model” groundwater suggests that natural organic matter complexes of REEs are insignificant. However, groundwaters with higher dissolved organic carbon concentrations than the “model” groundwater (i.e., >0.7 mg/L) would exhibit greater fractions of each REE complexed with organic matter. Sensitively analysis indicates that increasing ionic strength can weaken humate-REE interactions, and increasing the concentration of competitive cations such as Fe(III) and Al can lead to a decrease in the amount of REEs bound to dissolved organic matter.     

Quantitative C NMR of whole and fractionated Iowa Mollisols for assessment of organic matter composition

Both the concentrations and the stocks of soil organic carbon vary across the landscape. Do the amounts of recalcitrant components of soil organic matter (SOM) vary with landscape position? To address this question, we studied four Mollisols in central Iowa, two developed in till and two developed in loess. Two of the soils were well drained and two were poorly drained. We collected surface-horizon samples and studied organic matter in the particulate organic matter (POM) fraction, the clay fractions, and the whole, unfractionated samples. We treated the soil samples with 5 M HF at ambient temperature or at 60 °C for 30 min to concentrate the SOM. To assess the composition of the SOM, we used solid-state nuclear magnetic resonance (NMR) spectroscopy, in particular, quantitative ¹³C DP/MAS (direct-polarization/magic-angle spinning), with and without recoupled dipolar dephasing. Spin counting by correlation of the integral NMR intensity with the C concentration by elemental analysis showed that NMR was ?85% quantitative for the majority of the samples studied. For untreated whole-soil samples with <2.5 wt.% C, which is considerably less than in most previous quantitative NMR analyses of SOM, useful spectra that reflected ?65% of all C were obtained. The NMR analyses allowed us to conclude (1) that the HF treatment (with or without heat) had low impact on the organic C composition in the samples, except for protonating carboxylate anions to carboxylic acids, (2) that most organic C was observable by NMR even in untreated soil materials, (3) that esters were likely to compose only a minor fraction of SOM in these Mollisols, and (4) that the aromatic components of SOM were enriched to ∼53% in the poorly drained soils, compared with ∼48% in the well drained soils; in plant tissue and particulate organic matter (POM) the aromaticities were ∼18% and ∼32%, respectively. Nonpolar, nonprotonated aromatic C, interpreted as a proxy for charcoal C, dominated the aromatic C in all soil samples, composing 69-78% of aromatic C and 27-36% of total organic C in the whole-soil and clay-fraction samples.     

Characterization of soil organic carbon in drained thaw-lake basins of Arctic Alaska using NMR and FTIR photoacoustic spectroscopy

Arctic soils contain a large fraction of Earth’s stored carbon. Temperature increases in the Arctic may enhance decomposition of this stored carbon, shifting the role of Arctic soils from a net sink to a new source of atmospheric CO₂. Predicting the impact of Arctic warming on soil carbon reserves requires knowledge of the composition of the stored organic matter. Here, we employ solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared-photoacoustic spectroscopy (FTIR-PAS) to investigate the chemical composition of soil organic matter collected from drained thaw-lake basins ranging in age from 0 to 5500 years before present (y BP). The ¹³C NMR and FTIR-PAS data were largely congruent. Surface horizons contain relatively large amounts of O-alkyl carbon, suggesting that the soil organic matter is rich in labile constituents. Soil organic matter decreases with depth with the relative amounts of O-alkyl carbon decreasing and aromatic carbon increasing. These data indicate that lower horizons are in a more advanced stage of decomposition than upper horizons. Nonetheless, a substantial fraction of carbon in lower horizons, even for ancient thaw-lake basins (2000-5500 y BP), is present as O-alkyl carbon reflecting the preservation of intrinsically labile organic matter constituents. Climate change-induced increases in the depth of the soil active layer are expected to accelerate the depletion of this carbon.     

Relative contribution of foliar and fine root pine litter to the molecular composition of soil organic matter after in situ degradation

The influence of litter quality on soil organic matter (SOM) stabilization rate and pathways remains unclear. We used ¹³C/¹⁵N labeled litter addition and Curie-point pyrolysis gas chromatography–mass spectrometry combustion-isotope ratio mass spectrometry (Py–GC–MS–C–IRMS) to explore the transformation of litter with different composition and decay rate (ponderosa pine needle vs. fine root) to SOM during 18 months in a temperate conifer forest mineral (A horizon) soil. Based on ¹³C Py–GC–MS–C–IRMS the initial litter and bulk soil had ∼1/3 of the total pyrolysis products identified in common. The majority was related either to carbohydrates or was non-specific in origin. In bulk soil, carbohydrates had similar levels of enrichment after needle input and fine root input, while the non-specific products were more enriched after needle input. In the humin SOM fraction (260 yr C turnover time) we found only carbohydrate and alkyl C-derived compounds and greater ¹³C enrichment in the “carbohydrate” pool after fine root decomposition. ¹⁵N Py–GC–MS–C–IRMS of humic substances showed that root litter contributed more than needle litter to the enrichment of specific protein markers during initial decomposition.We found little evidence for the selective preservation of plant compounds considered to be recalcitrant. Our findings suggest an indirect role for decomposing plant material composition, where microbial alteration of fine root litter seems to favor greater initial stabilization of microbially derived C and N in SOM fractions with long mean turnover times, such as humin, compared to needles with a faster decay rate.     

Stable carbon and nitrogen isotopic compositions of high molecular weight dissolved organic matter from four U.S. estuaries

High molecular weight dissolved organic matter (HMW-DOM) represents an important component of dissolved organic carbon (DOC) in seawater and fresh-waters. In this paper, we report measurements of stable carbon (δ¹³C) isotopic compositions in total lipid, total hydrolyzable amino acid (THAA), total carbohydrate (TCHO) and acid-insoluble “uncharacterized” organic fractions separated from fourteen HMW-DOM samples collected from four U.S. estuaries. In addition, C/N ratio, δ¹³C and stable nitrogen (δ¹⁵N) isotopic compositions were also measured for the bulk HMW-DOM samples. Our results indicate that TCHO and THAA are the dominant organic compound classes, contributing 33-46% and 13-20% of the organic carbon in HMW-DOM while total lipid accounts for only <2% of the organic carbon in the samples. In all samples, a significant fraction (35-49%) of HMW-DOM was included in the acid-insoluble fraction. Distinct differences in isotopic compositions exist among bulk samples, the compound classes and the acid-insoluble fractions. Values of δ¹³C and δ¹⁵N measured for bulk HMW-DOM varied from −22.1 to −30.1‰ and 2.8 to 8.9‰, respectively and varied among the four estuaries studied as well. Among the compound classes, TCHO was more enriched in ¹³C (δ¹³C = −18.5 to −22.8‰) compared with THAA (δ¹³C = −20.0 to −29.6‰) and total lipid (δ¹³C = −25.7 to −30.7‰). The acid-insoluble organic fractions, in general, had depleted ¹³C values (δ¹³C = −23.0 to −34.4‰). Our results indicate that the observed differences in both δ¹³C and δ¹⁵N were mainly due to the differences in sources of organic matter and nitrogen inputs to these estuaries in addition to the microbial processes responsible for isotopic fractionation among the compound classes. Both terrestrial sources and local sewage inputs contribute significantly to the HMW-DOM pool in the estuaries studied and thus had a strong influence on its isotopic signatures.     

Benthic fluxes and porewater concentration profiles of dissolved organic carbon in sediments from the North Carolina continental slope

Numerous studies of marine environments show that dissolved organic carbon (DOC) concentrations in sediments are typically tenfold higher than in the overlying water. Large concentration gradients near the sediment–water interface suggest that there may be a significant flux of organic carbon from sediments to the water column. Furthermore, accumulation of DOC in the porewater may influence the burial and preservation of organic matter by promoting geopolymerization and/or adsorption reactions. We measured DOC concentration profiles (for porewater collected by centrifugation and “sipping”) and benthic fluxes (with in situ and shipboard chambers) at two sites on the North Carolina continental slope to better understand the controls on porewater DOC concentrations and quantify sediment–water exchange rates. We also measured a suite of sediment properties (e.g., sediment accumulation and bioturbation rates, organic carbon content, and mineral surface area) that allow us to examine the relationship between porewater DOC concentrations and organic carbon preservation. Sediment depth-distributions of DOC from a downslope transect (300–1000 m water depth) follow a trend consistent with other porewater constituents (ΣCO₂ and SO₄²⁻) and a tracer of modern, fine-grained sediment (fallout Pu), suggesting that DOC levels are regulated by organic matter remineralization. However, remineralization rates appear to be relatively uniform across the sediment transect. A simple diagenetic model illustrates that variations in DOC profiles at this site may be due to differences in the depth of the active remineralization zone, which in turn is largely controlled by the intensity of bioturbation. Comparison of porewater DOC concentrations, organic carbon burial efficiency, and organic matter sorption suggest that DOC levels are not a major factor in promoting organic matter preservation or loading on grain surfaces. The DOC benthic fluxes are difficult to detect, but suggest that only 2% of the dissolved organic carbon escapes remineralization in the sediments by transport across the sediment-water interface.     

Degradation of grass-derived pyrogenic organic material, transport of the residues within a soil column and distribution in soil organic matter fractions during a 28 month microcosm experiment

The microbial recalcitrance of char accumulated after vegetation fires and its transport within a soil column were studied in microcosms using ¹³C- and ¹⁵N-enriched pyrogenic organic material (PyOM). The PyOM from rye grass (Lolium perenne L.) was produced by charring at 350 °C under oxic conditions for 1 and 4 min to examine the impact of the charring degree. After 28 months, ¹³C recovery decreased to values between 62% and 65%, confirming that this material can be attacked by microorganisms and that the degradation occurs rapidly after accumulation of PyOM at the soil surface. The respective ¹⁵N recovery followed the same trend but tended to be higher (between 67% and 80%). Most of the added PyOM isotopic labels were recovered in the particulate organic matter (POM) fraction, containing between 84% and 65% of the added ¹³C and ¹⁵N after the first 2 months, being reduced by half at the end of the experiment. After 1 month, up to 13.8% of the ¹³C label and 12.4% of the ¹⁵N label were detected in the POM-free mineral fractions. This fast association of PyOM with the mineral phase indicates that physical soil properties have to be considered for the elucidation of PyOM stability. Addition of fresh unlabelled grass material as co-substrate resulted in comparable trends as for the pure PyOM but the total recovery of the isotopic labels clearly increased with respect to the amount of mineral-associated PyOM. Between 73% and 82% of the mineral-associated PyOM occurred in the clay separates (<2 μm) for which the highest values were obtained for the experiment with the more intensively charred PyOM and co-substrate addition.In summary, the study demonstrates the degradability of grass-derived PyOM. The addition of fresh plant material as an easily degradable co-substrate promoted the formation of partially decomposed PyOM and subsequently its association with the mineral phase, but did not increase the respective mineralisation rates. Detection of ¹³C and ¹⁵N content at different depths of the microcosm column demonstrated an additional loss of PyOM from top soil by way of mobilisation and transport to deeper horizons. All these processes have to be taken into account in order to obtain a more realistic view about the behaviour of PyOM in environmental systems and for estimation of the C and N sequestration potential.     

20 My of nitrogen fixation during deposition of mid-Cretaceous black shales on the Demerara Rise,equatorial Atlantic Ocean

Thick sequences of dark colored, organic carbon rich, finely laminated Santonian–Cenomanian claystones and homogeneous Albian siltstones were recovered from Ocean Drilling Program Sites 1257, 1258 and 1260 on the Demerara Rise in the western equatorial Atlantic Ocean. Total organic carbon (TOC) concentrations vary from 2 to over 20 wt% in the sequences of “black shales” that were deposited over a period of ～20 million years. Similarly long periods of elevated marine productivity implied by the high TOC concentrations are uncommon in the geological record and must have required unusual paleoceanographic conditions. The importance of nitrogen fixing bacteria to sustaining the amplified export production of organic matter is indicated by δ¹⁵N values that remain between ?4‰ and 0‰, a range that is notably less positive than the average of +5‰ for modern ocean sediments. Although containing mostly marine organic matter, the black shales have TOC/TN molar ratios between 20 and 40 that mimic those of land plant organic matter. The anomalously large TOC/TN ratios suggest selective organic matter degradation, probably associated with low oxygen conditions in the water column, that favored preservation of nitrogen poor forms of organic matter relative to nitrogen rich components. Deposition of black shales on the Demerara Rise was likely a consequence of the mid-Cretaceous warm and wet greenhouse climate that strengthened thermohaline stratification of this part of the Atlantic Ocean, which in turn encouraged bacterial nitrogen fixation, enhanced primary production, magnified organic matter export, and ultimately established anoxic conditions at the seafloor that improved preservation of organic matter for much of the 20 My period represented by these thick sequences.     

Aragonite and calcite preservation in sediments from Lake Iznik related to bottom lake oxygenation and water column depth

This study examines the forcing mechanisms driving long‐term carbonate accumulation and preservation in lacustrine sediments in Lake Iznik (north‐western Turkey) since the last glacial. Currently, carbonates precipitate during summer from the alkaline water column, and the sediments preserve aragonite and calcite. Based on X‐ray diffraction data, carbonate accumulation has changed significantly and striking reversals in the abundance of the two carbonate polymorphs have occurred on a decadal time scale, during the last 31 ka cal bp . Different lines of evidence, such as grain size, organic matter and redox sensitive elements, indicate that reversals in carbonate polymorph abundance arise due to physical changes in the lacustrine setting, for example, water column depth and lake mixing. The aragonite concentrations are remarkably sensitive to climate, and exhibit millennial‐scale oscillations. Extending observations from modern lakes, the Iznik record shows that the aerobic decomposition of organic matter and sulphate reduction are also substantial factors in carbonate preservation over long time periods. Lower lake levels favour aragonite precipitation from supersaturated waters. Prolonged periods of stratification and, consequently, enhanced sulphate reduction favour aragonite preservation. In contrast, prolonged or repeated exposure of the sediment–water interface to oxygen results in in situ aerobic organic matter decomposition, eventually leading to carbonate dissolution. Notably, the Iznik sediment profile raises the hypothesis that different states of lacustrine mixing lead to selective preservation of different carbonate polymorphs. Thus, a change in the entire lake water chemistry is not strictly necessary to favour the preservation of one polymorph over another. Therefore, this investigation is a novel contribution to the carbon cycle in lacustrine systems.     

青海湖底沉积物的矿物物相及有机质保存研究

盐湖沉积环境是烃源岩发育的重要地质环境。本文以青海湖湖底沉积物为例，根据有机质与粘土矿物含最及矿物表面积的关系，分析了矿物学因素对盐湖相富有机质沉积物中有机质保存的影响。研究发现：湖底沉积物中有机质丰富，为上层水中的浮游生物和南河流携带束的陆地高等植物两种来源。矿物物相分析发现沉积物中粘土矿物含量达到32．4％，以伊利石为主。沉积物经密度分离后测试发现，有机碳含量与粘土矿物含量及矿物表面积之间具有很好的正相关性，说明粘土矿物吸附是青海湖底沉积物中有机质的主要赋存形式。     

Identifying “free” and “bound” lipid fractions in stalagmite samples: An example from Heshang Cave,Southern China

Stalagmites are good archives for paleoecological change, as they are easy to date, and contain multiple environmental proxy records, including climatic records from oxygen isotopes. Lipid biomarkers preserved within stalagmites have recently been used to investigate changes in the overlying soil and vegetation. However, the understanding of lipid records from stalagmites is still at an early stage, and is hindered by the low abundances of lipids preserved and the complexity of the organic matter signal. Here the first results of a sequential extraction procedure are presented, that enables examination of the distribution patterns of “free” (solvent extraction) and “bound” (including physically bound within the calcite matrix and chemically bound to macromolecules) lipids in a stalagmite from southern China. In both groups the dominant compounds are saturated fatty acids, which are an order of magnitude more abundant in the “bound” phase. n-alkanes and n-alcohols chiefly appear in the “free” lipids. In contrast, 3-hydroxy acids are predominantly released under strong acid reflux conditions, suggesting a principal input from bacterial membrane compounds. A direct comparison between the present results and the published data from an Ethiopian stalagmite shows significant differences in the lipid signals from separate sites, with a stronger microbial signal in the Chinese sample. This preliminary investigation of lipid distributions in different modes highlights the importance of microbial geochemical processes in karst systems and supports the use of stalagmites in paleoecological reconstruction.