Molecular fossils from chemical degradation of macromolecular organic matter

Hydrogenolysis with rhodium-on-charcoal was found to be an effective method for degrading different types of macromolecular material of geological origin. Between 6 and 70% of coals, kerogens and humic substances were transferred into low-molecular-weight soluble materials. The reaction products contained a series of monomeric and dimeric lignin-derived compounds which strongly suggest intact fossil lignin as their source. The substitutional patterns of the released phenols reflect the type and amount of terrestrial organic matter input and diagenetic alterations.In addition to the lignin constituents, a complete suite of hydrocarbons differing from those of the low-molecular-weight fraction was obtained after hydrogenolysis of the sample material. Hydrocarbons released by the hydrogenolytic degradation technique were attached to the polymeric matrix as monoor polyethers. Deuterium was used in the degradation experiment to evaluate the sites of chemical bonds by which 4-methylsteranes and hopanes are attached to the kerogen matrix. These experiments suggested a linkage of the released molecules with ring A and the side-chain, respectively.     

Petrologic studies of terrestrial organic matter in Carpathian flysch sediments, southern Poland

In the Carpathian Flysch, coal is present either as exotics of Carboniferous coal deposits or as autochthonous, thin layers of lustrous coal. This paper present the results of the studies of coal-bearing rocks that are coeval with the enclosing flysch sediments. These coals form lenses up to 0.15 m thick. Their morphology precludes an exotic origin. The main petrographic component is collinite with admixtures of poorly fluorescing telinite. Minor components are: exudatinite, sporinite, fusinite, micrinite and sclerotinite. Mineral matter consists of framboidal pyrite clay minerals and quartz.The random reflectance of telocollinite varies from 0.38% to 0.72%, which corresponds to subbituminous and bituminous ranks. Correlation between chemical analysis, coking properties and relfectance measurements, leads to the conclusion that boundary between subbituminous and bituminous coals should be defined by the following values: C=80wt%, VOLATILES=43wt%; calorific VALUE=32.3 MJ/kg; and R^o=0.56–0.57%.Atypical properties, such as: upper C value (75–80wt%); high volatile matter contents (over 43wt%) and low random reflectance (^o about 0.38–0.57%) in subbituminous coals; low C value (about 80–82wt%); low reflectance (0.56–0.72%); and good coking properties, of the bituminous coals are attributed to quick coalification during increasing temperature as a result of tectonic stress.     

Phenolic aldehydes as indicators of terrestrially derived organic matter in the sea

The concentration of lignin degradation products (vanillin, $\text{p-}\text{hydroxybenzaldehyde}$ and syringealdehyde) generated by oxidizing sediment samples with nitrobenzene were considered in an approach to follow the seaward transport of terrestrially derived organic matter. The concentrations of vanillin and syringealdehyde ranged from about 1 per cent of the total ‘organic matter’ in samples taken from inland rivers along the Georgia coast to < 0.1 per cent in samples taken from the continental shelf off the coast of Georgia and Texas.     

Extensive degradation and fractionation of organic matter during subsurface weathering

Organic carbon, sulphur, ¹³C_org, iron, manganese and calcium have been measured across a subsurface-weathering front in Pliocene sediments in southern Sicily. The results show an almost quantitative removal of C_org and sulphur and an increase in iron and manganese oxides over the weathering front, accompanied with a significant shift of the ¹³C_org to lower values. These data are among the first to support the rapid, extensive weathering of sedimentary organic matter and sulphur, a basic assumption made in global biogeochemical models on a Phanerozoic timescale.     

The role of hydrology in annual organic carbon loads and terrestrial organic matter export from a midwestern agricultural watershed

Defining the control that hydrology exerts on organic carbon (OC) export at the watershed scale is important for understanding how the source and quantity of OC in streams and rivers is influenced by climate change or by landscape drainage. To this end, molecular (lignin phenol), stable carbon isotope, and dissolved organic carbon (DOC) data were collected over a range of flow conditions to examine the influence of hydrology on annual OC export from an 850 km² Midwestern United States agricultural watershed located in west central Indiana. In years 2002 and 2003, modeled annual DOC loads were 19.5 and 14.1 kg ha⁻¹yr⁻¹, while 71% and 85%, respectively, of the total annual OC was exported in flow events occurring during less than 20% of that time. These results highlight the importance of short-duration, high-discharge events (common in smaller watersheds) in controlling annual OC export. Based on reported increases in annual stream discharge coupled with current estimates of DOC export, annual DOC loads in this watershed may have increased by up to 40% over the past 50 years. Molecular (lignin phenol) characterization of quantity and relative degradation state of terrestrial OC shows as much temporal variability of lignin parameters (in high molecular weight dissolved organic carbon) in this one watershed as that demonstrated in previously published studies of dissolved organic matter in the Mississippi and Amazon Rivers. These results suggest that hydrologic variability is at least as important in determining the nature and extent of OC export as geographic variability. Moreover, molecular and bulk stable carbon isotope data from high molecular weight dissolved organic carbon and colloidal organic carbon showed that increased stream flow from the study watershed was responsible for increased export of agriculturally derived OC. When considered in the context of results from other studies that show the importance of flood events and in-stream processing of terrestrial organic carbon, our results show how hydrologic variability in smaller watersheds can reflect landscape-scale carbon dynamics in ways that cannot necessarily be measured at the outlets of large rivers due to multiple source signals and attenuated hydrology.     

Selected organic matter source indicators in the Orinoco,Nile and Changjiang deltas

Carbon isotopic composition, carbon to nitrogen ratios, carbon preference (n-C₂₃ to n-C₃₂), and microscopic examination of selected samples were compared and contrasted as organic matter source indicators. The Orinoco, Nile, and Changjiang deltas were sampled and analyzed. The δ ¹³C of organic matter increased with distance offshore at all three locations. Organic carbon content decreased seaward on the Orinoco and Changjiang deltas but increased on the Nile delta. C/N ratios decreased regularly with distance offshore on the Orinoco delta, ranged from 10 to 25, and correlated positively with δ ¹³C_OM. Estimations of the relative input of marine versus terrestrial organic matter to the sediments was dependent on the parameter analyzed. These discrepancies were primarily due to the definition of end-member compositions and the fraction of the total organic matter that is measured by a given parameter. Multiple-source indicators must be measured and integrated and end-members must be properly defined in order to obtain realistic input estimates.     

Enzymatic and Microbial Degradation of Organic Matter in Lake Hongfeng, Guizhou Province, China

1IntroductionEnzymaticandmicrobialdegradationoforganicmatterhasabearingnotonlyonearlydiagene sis,butalsoonelementcyclingandmicrobedistributioninlakesediments.Somereportsshowedtheabundancevariationsoforganicmatterinsediments (BurdigeandGardner,1998;ArthurandDean ,1998;WanGuojiangetal.,2 0 0 0 ) .However,duetothecomplexchemicalcompositionoforganicmatter,mechanismsofenzymaticandmicrobialdegradationandvariationsofeachchemicalcomponentneedtobestudiedfurther.Underanoxiccondition ,SO2 -4 isanimpo…     

Amino acid and amino sugar yields and compositions as indicators of dissolved organic matter diagenesis

Microbial decomposition experiments were used to characterize changes in the amino acid and amino sugar yields and compositions of natural marine substrates during early diagenesis in seawater. On average, 63% of added carbon and 68% of added nitrogen were removed within the first 30 days of decomposition. In all cases, amino acid utilization accounted for a substantial fraction of the removed C and N. Carbon-normalized amino acid yields decreased to less than 50% of their starting values and most of this change occurred within the first 10 days of decomposition. Increases in the concentrations of amino sugars and decreases in the GlcN:GalN ratio in particulate organic matter (POM) illustrated the significance of microbial production during the decomposition of added substrates. Changes in the mol % composition of amino acids during early diagenesis were substantial but highly variable with substrate. Previous survey data collected from the same region were used in conjunction with the experimental data to investigate the utility of several established amino acid-based indices of organic matter diagenesis. This comparison showed that a combination of these degradation indexes is most effective for describing the diagenetic state of dissolved organic matter (DOM). Carbon-normalized amino acid yields were found to be the most effective indicator for early diagenesis. Relative abundances of amino acids were effective indicators of intermediate stages of diagenesis and the mol % composition of the non-protein amino acid γ-Aba (γ-aminobutyric acid) was an effective indicator of advanced DOM diagenesis.     

Stabilisation of soil organic matter by interactions with minerals as revealed by mineral dissolution and oxidative degradation

Soil organic matter is known to contain a stable fraction with an old radiocarbon age. Size and stabilisation processes leading to the formation of this old soil carbon pool are still unclear. Our study aims to differentiate old organic matter from young and labile carbon compounds in two acid forest soils (dystric cambisol, haplic podzol). To identify such fractions soil samples were exposed to oxidation with Na₂S₂O₈ and to dissolution by hydrofluoric acid (HF). A negative correlation between ¹⁴C activity and carbon release after dissolution of the mineral matrix by HF indicates a strong association of stabilised carbon compounds with the mineral phase. A negative correlation between the ¹⁴C activity and the relative proportion of carbon resistant to oxidation by Na₂S₂O₈ shows that young carbon is removed preferentially by this treatment. The fraction remaining after oxidation represents a certain stabilised, long residence time carbon pool. This old fraction comprises between 1 and 30% of the total soil organic carbon in the surface horizons, but reaches up to 80% in the sub-surface horizons. Old OC is mainly stabilised by organo-mineral associations with clay minerals and/or iron oxides, whereas intercalation in clay minerals was not found to be important.     

Models of natural organic matter and interactions with organic contaminants

Adsorption of organic contaminants onto soils, sediments and other particulates has the potential to be a major controlling factor in their bioavailability, fate and behavior in the environment. Models for estimating the amount and stability of sorbed organic contaminants based on the fraction of organic carbon in a soil or sediment can oversimplify the process of sorption in the environment. In order to help understand sorption of organic contaminants in soils and sediments, we modeled various components of natural organic matter (NOM) that are possible substrates for sorption. These substrates include soot particles, lignin, humic and fulvic acids. The molecular scale interactions of selected aromatic hydrocarbons with different substrates were also simulated. Results of the simulations include the 3-D structures of the NOM components, changes in structure with protonation state and solvation and the sorption energy between PAH and substrate. This last parameter is an indicator of the amount of contaminant that will sorb and the energy required to free the contaminant from the substrate. Although the simulation results presented in this paper represent a first-order examination of NOM and contaminant interactions, the findings highlight a number of essential features that should be included in future molecular models of NOM and contaminant sorption.     

Influences of organic matter and calcification rate on trace elements in aragonitic estuarine bivalve shells

A suite of elements (B, Na, Mg, S, K, Ca, V, Mn, Cr, Sr, and Ba) was measured in aragonitic shells of the estuarine bivalve Corbula amurensis, the Asian clam, using the Sensitive High-Resolution Ion MicroProbe with Reverse Geometry (SHRIMP RG). Our initial intent was to explore potential geochemical proxy relationships between shell chemistry and salinity (freshwater inflow) in northern San Francisco Bay (SFB). In the course of this study we observed variations in shell trace element to calcium ([M]/Ca) ratios that could only be attributed to internal biological processes. This paper discusses the nature and sources of internal trace element variability in C. amurensis shells related to the shell organic fraction and shell calcification rates. The average organic content of whole C. amurensis shells is 19%. After treating whole powdered shells with an oxidative cleaning procedure to remove organic matter, shells contained on average 33% less total Mg and 78% less total Mn. Within our analytical uncertainty, Sr and Ba contents were unchanged by the removal of organic matter. These results show that aragonitic C. amurensis shells have a large component of non-lattice-bound Mg and Mn that probably contribute to the dissimilarity of [M]/Ca profiles among five same-sized shells. Non-lattice-bound trace elements could complicate the development and application of geochemical proxy relationships in bivalve shells. Because B, Ba and Sr occur exclusively in shell aragonite, they are good candidates for external proxy relationships. [M]/Ca ratios were significantly different in prismatic and nacreous aragonite and in two valves of the same shell that had different crystal growth rates. Some part of these differences can be attributed to non-lattice-bound trace elements associated with the organic fraction. The differences in [M]/Ca ratios were also consistent with the calcification rate-dependent ion transport model developed by Carré et al. [Carré M., Bentaleb I., Bruguier O., Ordinola E., Barrett N. T. and Fontugne M. (2006) Calcification rate influence on trace element concentrations in aragonitic bivalve shells: evidences and mechanisms. Geochim. Cosmochim. Acta70, 4906-4920] which predicts that [M]/Ca ratios increase as calcification rates increase and Ca²⁺ channel specificity decreases. This result, in combination with the possibility that there were ontogenetic variations in growth rates among individuals younger than 2 years, underscores the need to develop an independent age model for C. amurensis shells. If growth-rate effects on lattice-bound [M]/Ca ratios can be constrained, it may yet be possible to develop high-resolution geochemical proxies for external solution chemistry in low-salinity regions of SFB.     

Interception,degradation and contributions of terrestrial organic carbon obtained from lignin analysis in Wujiang River,southwest China

Acta Geochimica - Understanding the fate of terrestrial organic carbon (OC) in a cascade impoundment system is critical for recognizing the role of carbon sink for reservoirs. Surface sediments...     

The effect of organic matter and oxygen on the degradation of bacterial membrane lipids in marine sediments

The biodegradation of purified radiolabelled membrane lipids from a methanogenic bacterium and a pseudomonad were investigated in mangrove, beach and high marsh marine sediments under aerobic and anaerobic conditions. The effect of organic matter on the amount and rate of degradation was also examined by supplementing beach sediments with humic acids. In aerobic sediments, CO₂ was the major product of lipid degradation while under anaerobic conditions both CO₂ and CH₄ were major end products and the overall rates were reduced (up to 40%) relative to aerobic conditions. Total bacterial numbers increased during all incubations with the largest increases occurring in anaerobic sediments supplemented with humic acids. No lipid degradation occurred in aerobic or anaerobic sediments treated with formaldehyde or autoclaving. In low organic beach sediments, the ester-linked phospholipid of the pseudomonad was degraded much more rapidly than the diphytanyl glycerol diether of the methanogen with 69% of the phospholipid degraded in 96 hours versus only 4% of the methanogen lipid. Lipid degradation in both aerobic and anaerobic sediments was highly correlated to organic matter content with increasing amounts of organic matter inhibiting degradation. Long incubations (75 days) of the diphytanyl glycerol ether resulted in 51% degraded to CO₂ in low (0.5%) organic mangrove sediments while only 9% was mineralized in high (10.8%) organic marsh sediments. Physicochemical sorption of membrane lipids to the organic matrix is proposed as a mechanism which protects membrane lipids from microbial attack and degradation.     

Two examples of uranium associated with organic matter

Precambrian carbonaceous material from Cluff, Saskatchewan (Canada), and samples of Late Carboniferous material from Arlit (250 km NNW of Agadès, Niger), were studied by high resolution transmission electron microscopy and energy dispersive X-ray analysis. The Cluff sample is very rich in uranium, whereas those from Arlit are poorer. An intact organo-uranium complex is the major component of the Cluff sample, the carbon and oxygen content of which are high. Uraniferous fragments show very small molecular orientation, whereas those that are uranium-free present a statistical long range preferred orientation. The carbonaceous material of Arlit is entirely free of uranium and behaves as any other humic poorly evolved material; it acquires a small molecular orientation on heat treatment. Uranium was found associated with titaniferous illite in the form of poorly crystallized UTi₂O₆ (Brannerite). The formation of brannerite is attributed to a topotactic transformation of clay particles containing adsorbed organic matter. Clay yields TiO₂; organic matter is the source of UO₂. Destruction of clay leads to release of organic matter, free of uranium, which undergoes diagenesis.     

Evolution of organic matter degradation in Cretaceous black shales inferred from authigenic barite: A reaction-transport model

A reaction-transport model was used to infer the long-term evolution of anaerobic organic matter degradation in Cretaceous black shales from the distribution of authigenic barite in sediments drilled at Demerara Rise (ODP Leg 207, Site 1258). In these sediments, sulfate-reduction and methanogenesis are the major pathways of organic matter decomposition and the depth-distribution of authigenic barite serves as an indicator for the temporal evolution of the sulfate-methane transition zone (SMTZ), the strength of the biogenic methane flux and, ultimately, the organic matter reactivity in the black shales over geological timescales. Organic matter degradation is described according to the reactive continuum model approach and parameters values are determined by inverse modeling, based on present-day porewater and authigenic barite profiles. Fully transient simulations were performed over a period of 100 Myrs and indicate that important features of the biogeochemical dynamics are associated to changes in the boundary forcing. Hiatuses in sediment accumulation rate result in quasi-steady-state conditions and lead to distinct accumulations of authigenic barites in the SMTZ. The inversely determined parameters reveal that the reactivity of the organic matter was already low (apparent first order rate constant ) at the time of its deposition in the Cretaceous. The geochemical characteristics of sediments drilled at Demerara Rise, as well as the presence of specific biomarkers, suggest that this low reactivity is most likely due to the euxinic palaeo-conditions which favored the sulfurization of the organic matter. Simulation results predict average initial organic carbon contents between 8.1 and 9.5 wt%, implying a high preservation efficiency of the organic matter (between 79% and 89%). Calculated mass accumulation rates (between 0.43 and 0.5 ) compare well with estimations for the western basin of the Cretaceous southern North Atlantic. Simulation results thus indicate that the enhanced preservation of organic matter under euxinic conditions may have been the main cause for the formation of organic-rich Cretaceous black shales at Demerara Rise.     

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.     

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.     

Understanding the enhanced aqueous solubility of styrene by terrestrial dissolved organic matter using stable isotope mass balance and FTIR

We present a new stable isotope mass balance method for measuring the enhanced aqueous solubility of specific organic compounds in the presence of natural dissolved organic matter (DOM). It involves interfacing a standard dissolved organic carbon (DOC) analyzer with a stable isotope ratio monitoring system, is applicable to a wide range of model organic compounds and can be tuned to provide maximum precision for a given range of compound solubility and initial natural DOC concentration. Using ¹³C-labeled styrene as a model compound, we applied the method to investigate the reactivity of Dismal Swamp DOM as a function of season, nominal molecular size and chemical composition as determined using Fourier Transform Infrared Spectroscopy (FTIR). The solubility enhancement of styrene ranged from 23% to 118% relative to deionized water, while DOC-normalized enhancements varied from about 0.04 to 0.35 μM styrene/μM DOC as a function of season and nominal molecular weight. Statistical analysis of FTIR spectra reveals a strong positive correlation between the styrene concentration and the carboxyl content of the natural DOM. Reactivity differences between high molecular weight (HMW), low molecular weight (LMW) and total DOM samples are consistent with potential variations in their higher order structures.     

The significance of organic matter degradation in the interpretation of historical pollution trends in depth profiles of estuarine sediment

The quantitative significance of organic matter degradation in bringing about the early diagenetic mobility of anthropogenic trace metals (Cu, Zn, Pb) is assessed specifically in relation to the use of estuarine sediments as historical records of pollution. A 1,500 mm salt-marsh sediment depth profile from Tites Point, Severn Estuary, England, was sampled at 10-mm intervals. Organic carbon determinations were carried out by a wet oxidation technique, and ‘organic fraction’ metals were separated by sequential leaching. Results demonstrated that organic phase metals are quantitatively significant in Severn Estuary sediments, particularly Cu and Zn (Cu>Zn), and that metals are probably released from this fraction during early diagenesis. The degree of release, and the apparent loss of the released trace metals from the sediment, would suggest that the use of estuarine sediments as historical records of pollution requires qualification.