Reactivity of organic matter in aquifer sediments: geological and geochemical controls

Reduction rates in aquifers are commonly carbon limited, but little is known about the molecular composition and degradability of sedimentary organic matter (SOM) in aquifer sediments. The composition, source and degradation status of SOM in aquifer sediments of fluvio-glacial (Pleistocene) and shallow marine (Pliocene) origin, were determined using flash pyrolysis-gas chromatography/mass spectrometry. Incubation experiments (106 d) were used to assess the reactivity of SOM towards molecular oxygen. A dominance of lignin-derived components and long chain odd-over-even predominant alkanes indicate that terrestrial higher land plants were the main source of SOM even in the shallow marine sediments, while bacterial lipid-derived hopanoids and iso- and anteiso-C₁₅ and C₁₇ fatty acids indicate a minor contribution of microbial biomass. No compositional difference was observed between SOM present in the fine (<63 μm) and coarse fraction (63-2000 μm). A significant part of SOM was not present as low-molecular-weight compounds but was macromolecularly bound. For the fluvio-glacial sediments, a relatively higher abundance of resistant macromolecular compounds was in agreement with stronger signs of aerobic lignin, alkane and hopanoid oxidation. The more degraded status of SOM in the fluvio-glacial sediments was consistent with their significantly lower SOM mineralization (2-6%) during incubation, as compared with the shallow marine sediments (9-14%). The reactivity towards oxygen of SOM was controlled by the extent of past aerobic oxidation. Not the age of SOM, but the extent of oxygen exposure during syn- and postdepositional conditions seems most important in affecting the degradation status of SOM in aquifer sediments and thus their ability to reduce oxidants.     

Hydrothermal pyrolysis of organic matter in Riphean mudstone

The catagenesis of organic matter (OM) was modeled by the hydrothermal pyrolysis of a source rock (Riphean mudstone from eastern Siberia). Isothermal experiments 72-h long were carried out in an aqueous environment in autoclaves at temperatures of 300, 310, 320,..., 370°. The pyrolysis products were analyzed for yield of extract, organic carbon, and parameters of Rock-Eval pyrolysis. The amount of the generated liquid hydrocarbon (HC) compounds increased to a temperature of 340°C and then decreased. The experimental trend of the hydrogen index (HI) dependence on the T _Max temperature generally coincided with that for natural OM maturation. The carbon isotopic composition of the insoluble (in organic solvents) OM remained practically unchanged in the course of the experiments. The carbon structure of the solid remnants of the experimental samples was ordered (after the experiments) with the origin of turbostratic graphite with a spacing of d ₀₀₂≈3.5 A°. We also conducted pyrolysis in a diamond anvil cell equipped with a digital camera in order to obtain additional qualitative and quantitative information on oil generation and emigration in the source rock and isolated kerogen. Chemical kinetic parameters of kerogen cracking were calculated for pyrolysis in an open system. The extrapolation of the high-temperature experimental results is discussed with reference to natural OM maturation.     

Europium sorption to sediments in the presence of natural organic matter: A laboratory and modeling study

Cellulosic materials, such as wood, paper products and cardboard that have been co-disposed with low-level nuclear waste have been shown to produce leachate with natural organic matter (NOM) concentrations of hundreds of mg/L C and, as such, have the potential to influence the fate and transport of radionuclides in the subsurface environment. The objective of this study was to examine the influence of NOM on the sorption of Eu (an analogue for trivalent radionuclides) to two coastal plain sediments from the US Department of Energy’s Savannah River Site. Particular attention was directed at quantifying Eu interactions with NOM sorbed to sediments (NOM_sed) in laboratory experiments and developing conditional stability constants for that interaction using the thermodynamic equilibrium speciation model MINTEQA2. Europium sorption to the two sediments systematically increased as pH increased from 3.9 to 6.7. With increasing additions of NOM to the aqueous phase from 0 to 222 mg/L C, Eu sorption initially increased to a maximum at 10 mg/L C NOM_aq and then decreased with increasing NOM_aq concentrations. Increases in Eu sorption at low NOM additions was attributed to the sorption of NOM to the sediment surface increasing the number of sorption sites on the low cation-exchange capacity sediments and/or increasing the association constant (log K) for the Eu-sediment surface reaction. Decreases in Eu sorption at higher NOM levels was attributed to Eu_aq complexation to NOM_aq being more favored than Eu sorption to the solid phase. A component additivity model was developed to describe the Eu–NOM-sediment system by the additive effects of the three binary system models: Eu–NOM, Eu-sediment and NOM-sediment. The model generally captured the data trends in the ternary system. Conditional stability constants developed from the experimental data for the complexation of Eu to NOM_sed were as much as four orders of magnitude greater than Eu complexation with NOM_aq, presumably due to the NOM_sed deriving additional negative (attractive) charge from the sediment surface. At high initial NOM_aq levels, >99 mg/L C, the model captured the trend of reduced Eu sorption but tended to over-estimate Eu sorption. The additivity approach of combining binary models to form a ternary model was only successful when the unique complexation properties of the NOM_sed were properly calculated.     

The effect of organic matter type and organic carbon content on Rock-Eval hydrogen index in oil shales and source rocks

The amount of “gas-prone” kerogen (woody, fungal and “inert”) and the organic carbon content (TOC) are the two predominant factors affecting the hydrogen index (HI) in the 226 samples of lacustrine and marine oil shales and source rocks studied. HI decreases as a function of the amount of “gas-prone” kerogen and increases as a function of TOC. In addition, the type of amorphous kerogen influences the hydrogen index, and this can be roughly estimated from the fluorescence intensity of the amorphous kerogen. Nearly eighty percent of the variation in HI in these samples can be accounted for by the percentage of “gas-prone” kerogen, the TOC content, and the fluorescence of the amorphous kerogen in a multiple regression analysis.Hydrogen index increases as a function of TOC up to about 10% TOC (the relationship can be approximated by a quadratic equation) and then levels off. A possible explanation for this is that the capability of a rock to generate and expel hydrocarbons during pyrolysis increases with TOC. When the retention capacity of the rock matrix is saturated (at about 10% TOC) further increases in TOC have no effect on HI. It is also possible that the quality (i.e. oil-proneness) of the amorphous kerogen is poorer in low TOC samples than in high TOC samples.The samples came from the following oil shales and source rocks: Rundle (Queensland Eocene-Miocene), Mae Sot (northwestern Thailand, Eocene-Pliocene), River River (northwestern Colorado, Eocene), Toolebuc (western Queensland, Late Albian), the “Posidonienschiefer” (southwestern Germany, Toarcian), an Argentinian lacustrine deposit (Eocene-Miocene), the Kimmeridgian sections from four North Sea wells (blocks 21, 30, and 210), Monterey Shale (California, Miocene), and sections from six wells from the Alaskan Tertiary (North Slope, North Aleutian Shelf, Navarin Basin, Norton Sound). Most samples appear to be thermally immature (T.A.I. less than 1.8; R_o less than 0.6%) so they should be considered only potential source rocks.The lacustrine oil shales have a higher conversion ratio (yeild/TOC or S₁ + S₂/TOC) than do the marine oil shales in samples with only amorphous and algal kerogen. These, in turn, have a higher conversion ratio than the marine source rocks. These differences are roughly reflected in the fluorescence intensity of the amorphous kerogen. Free hydrocarbons are higher in the marine source rocks than in the marine oil shales, and are lowest in the lacustrine oil shales.     

Evolution of organic matter in lignite-containing sediments revealed by analytical pyrolysis (Py–GC–MS)

Newly vegetated sites provide opportunities to enlighten organic matter (OM) transformation mechanisms in soils and sediments at very early stages of development which, in turn, is relevant to better understand general ecosystem functioning. Mine acid soils and sediments in the Lusatian open cast lignite mining district (Germany) contains a high concentration of fossil carbon (lignite) in ad mixture with recent OM from the local vegetation, both contributing to the humified OM pool. In this study, analytical pyrolysis (Py–GC–MS) was used to monitor the different C sources (lignite or plant derived) in developing mine tailing soils and sediments and their degree of degradation in contrasting environments. Representative vegetation and the organic carbon (OC) rich soil/sediment fraction (humus fraction) were sampled at two depths (0–5 and 5–10 cm) in three plots along a transect covering an upland forest soil, a partially submerged sediment at the land–water interface and a constantly submerged sediment. The analysis of plant (lipds, isoprenoids, methoxyphenols and carbohydrates) and possible lignite (alkyl napththalenes, alkyl benzenes and PAHs) biomarkers released after pyrolysis supports previous findings in the area using other proxies. It was possible to discern OM sources in soil/sediment humus fractions, both from the substrate (lignite) as well as from the prevailing vegetation of the area. Environmental conditions in the submerged sediment seem to favour OM protection and the accumulation of decomposing plant material, whereas more intense OM degradation seems to prevail in the land–water interface areas characterized by fluctuating water level. In addition, a well resolved series of organic sulfur compounds (OSCS) found in the submerged sediments of rehabilitated acid lakes, indicates the possible occurrence of particular mechanisms of C preservation in this extreme anoxic S rich environment, i.e. via sulphur “quenching” with plant derived lipids during early diagenesis.     

Effect of organic matter on DOM sorption on lake sediments

The effect of organic matter on the sorption of dissolved organic matter (DOM) on lake sediments is critical to understanding the fate and transport of contaminants at the sediment–water interface in lake ecosystems. Results indicate that DOM sorption on sediment is largely due to ligand exchange between the DOM and hydroxyl groups, and the amount of DOC sorbed is a linear function of added DOC. With increasing organic matter content the sediment has lower binding strength, higher releasing ability for DOM, and the higher amount of DOM sorbed by sediment naturally. There was no clear difference before and after the sediment was treated with H₂O₂, but the constant b implied that after the sediments were treated DOC release was promoted. Organic matter in the sediment tends to impede the sorption of DOC and results in a remarkable decrease in DOC sorption rates.     

Ligand extraction of rare earth elements from aquifer sediments: Implications for rare earth element complexation with organic matter in natural waters

The ability of organic matter as well as carbonate ions to extract rare earth elements (REEs) from sandy sediments of a Coastal Plain aquifer was investigated for unpurified organic matter from different sources (i.e., Mississippi River natural organic matter, Aldrich humic acid, Nordic aquatic fulvic acid, Suwannee River fulvic acid, and Suwannee River natural organic matter) and for extraction solutions containing weak (i.e., CH₃COO⁻) or strong (i.e., ) ligands. The experimental results indicate that, in the absence of strong REE complexing ligands in solution, the amount of REEs released from the sand is small and the fractionation pattern of the released REEs appears to be controlled by the surface stability constants for REE sorption with Fe(III) oxides/oxyhydroxides. In the presence of strong solution complexing ligands, however, the amount and the fractionation pattern of the released REEs reflect the strength and variation of the stability constants of the dominant aqueous REE species across the REE series. The varying amount of REEs extracted by the different organic matter employed in the experiments indicates that organic matter from different sources has different complexing capacity for REEs. However, the fractionation pattern of REEs extracted by the various organic matter used in our experiments is remarkable consistent, being independent of the source and the concentration of organic matter used, as well as solution pH. Because natural aquifer sand and unpurified organic matter were used in our experiments, our experimental conditions are more broadly similar to natural systems than many previous laboratory experiments of REE-humic complexation that employed purified humic substances. Our results suggest that the REE loading effect on REE-humic complexation is negligible in natural waters as more abundant metal cations (e.g., Fe, Al) out-compete REEs for strong binding sites on organic matter. More specifically, our results indicate that REE complexation with organic matter in natural waters is dominated by REE binding to weak sites on dissolved organic matter, which subsequently leads to a middle REE (MREE: Sm-Ho)-enriched fractionation pattern. The experiments also indicate that carbonate ions may effectively compete with fulvic acid in binding with dissolved REEs, but cannot out compete humic acids for REEs. Therefore, in natural waters where low molecular weight (LMW) dissolved organic carbon (DOC) is the predominant form of DOC (e.g., lower Mississippi River water), REEs occur as “truly” dissolved species by complexing with carbonate ions as well as FA, resulting in heavy REE (HREE: Er-Lu)-enriched shale-normalized fractionation patterns. Whereas, in natural terrestrial waters where REE speciation is dominated by organic complexes with high molecular weight DOC (e.g., “colloidal” HA), only MREE-enriched fractionation patterns will be observed because the more abundant, weak sites preferentially complex MREEs relative to HREEs and light REEs (LREEs: La-Nd).     

Thermochemolysis of organic matter preserved in stalagmites: A preliminary study

The analysis of organic matter (OM) preserved in stalagmites is a growing field, but there have been few studies of biomarker compounds such as lignin phenols that are widely used in other palaeoenvironmental contexts. Here we present a preliminary qualitative study of the OM in six stalagmite samples from contrasting environments, using thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH). The results indicate that a wide variety of products is preserved, including several potential lignin-derived compounds, but also that further research is needed to maximise compound recovery and allow the analysis of dissolved OM preserved in stalagmites to reach its full potential.     

沉积物不同提取态有机物特征及水文地球化学意义——以河套盆地典型研究区为例

地下水系统中有机物（OM）特征和活性对于地下水化学特征的形成和演化起着十分重要的作用。将内蒙古河套盆地表层湖相沉积物按10 cm间隔采集,并对沉积有机质的性质及来源进行重点分析。测量了不同深度上不同岩性沉积物的色度、水溶性有机物（WEOM）和盐溶性有机物（SEOM）含量及其光谱学特性。结果显示,沉积物的色度（R530-520）与TOC含量呈现相反的变化趋势:色度值较大时,TOC含量反而较小。相对于细砂层,黏土层的色度值较低,但TOC含量较高。相同的沉积物中,SEOM含量高于WEOM,但WEOM更易迁移至地下水中。有机物的光谱指数表明,WEOM以微生物来源为主,而SEOM以陆源为主。通过三维荧光光谱分析发现,荧光强度和沉积物有机碳（SOC）含量呈正相关;黏土层沉积有机物荧光强度更高;WEOM和SEOM均含类腐殖质成分和类蛋白成分,但SEOM中腐殖质成分较高;类腐殖质是所研究的沉积物中OM最主要的存在形式。     

The distribution and source of organic matter in reservoir sediments

The bottom sediments of two reservoirs, one with significant river sediment input and one without, were analyzed for organic matter content. Lake Texoma sediments average 1.0% organic carbon, of which 0.26% organic carbon is deposited by the river sediments of the Red and Washita River deltas. In Fort Gibson reservoir, where there is minimal river sediment input, the organic carbon averages 1.2% and is deposited with a strong correlation to water depth (+0.9). There is a significant difference between the C/N ratio of Lake Texoma sediments (11.5) and Fort Gibson sediments (9.6). The higher C/N ratio is suggested to be a result of the larger input of terrestrial plant debris (with a high original C/N ratio) by the rivers draining into Lake Texoma and the relatively high resistance of the lignin material in the plant debris to decomposition in the reservoir sediments.     

Rapid sampling of organic matter in flooded soils and sediments

Estuaries and Coasts - A coring system using a compressed air supply and a sediment shaking procedure using a soil dispersant are described which greatly simplify and shorten the task of...     

Thermodynamics and organic matter: constraints on neutralization processes in sediments of highly acidic waters

The controls on the internal neutralization of low productivity, highly acidified waters by sulfide accumulation in sediments are yet poorly understood. It is demonstrated that the neutralization process is constrained by organic matter quality and thermodynamic effects which control the relative rates of SO₄ and Fe reduction, and the fate of the reduced Fe and S in the sediments. The investigated sediments were rich in dissolved Fe(II) (0.005–12 mmol l⁻¹) and SO₄ (1.3–22 mmol l⁻¹). The pH ranged from 3.0 to 6.8. Contents of reduced inorganic S (0.1–9.5%), molar C/N ratios of the organic matter (12–80) and metabolic turnover rates (1–110 μeq cm⁻³ a⁻¹) varied strongly. Substantial amounts of Fe sulfides were only found at a simultaneous partial thermodynamic and solubility equilibrium of the involved biogeochemical processes. Sulfide oxidation was apparently inhibited, and SO₄ and Fe reduction coexisted. In this type of sediment increases in C availability cause enhanced neutralization rates. In the absence of a partial equilibrium, the sediments were in a sulfide oxidizing and Fe reducing state, and did not accumulate Fe sulfides. The latter type of sediment will increase neutralization rates in response to decreasing deposition of reactive Fe oxides but not necessarily in response to increases in lake productivity by e.g. fertilization measures.     

Trace metal behaviour in riverine sediments: Role of organic matter and sulfides

Three sediment cores were collected in the Scheldt, Lys and Spiere canals, which drain a highly populated and industrialized area in Western Europe. The speciation and the distribution of trace metals in pore waters and sediment particles were assessed through a combination of computational and experimental techniques. The concentrations of dissolved major and trace elements (anions, cations, sulfides, dissolved organic C, Cd, Co, Fe, Mn, Ni, Pb and Zn) were used to calculate the thermodynamic equilibrium speciation in pore waters and to evaluate the saturation of minerals (Visual Minteq software). A sequential extraction procedure was applied on anoxic sediment particles in order to assess the main host phases of trace elements. Manganese was the most labile metal in pore waters and was mainly associated with carbonates in particles. In contrast, a weak affinity of Cd, Co, Ni, Pb and Zn with carbonates was established because: (1) a systematic under-saturation was noticed in pore waters and (2) less than 10% of these elements were extracted in the exchangeable and carbonate sedimentary fraction. In the studied anoxic sediments, the mobility and the lability of trace metals, apart from Mn, seemed to be controlled through the competition between sulfidic and organic ligands. In particular, the necessity of taking into account organic matter in the modelling of thermodynamic equilibrium was demonstrated for Cd, Ni, Zn and Pb, the latter element exhibiting the strongest affinity with humic substances. Consequently, dissolved organic matter could favour the stabilization of trace metals in the liquid phase. Conversely, sulfide minerals played a key role in the scavenging of trace metals in sediment particles. Finally, similar trace metal lability rankings were obtained for the liquid and solid phases.     

Land-derived organic matter in surface sediments from the Gulf of Mexico

Lignin oxidation products and ¹³C/¹²C ratios were compared as indicators of land-derived organic matter in surface sediments from the western Gulf of Mexico. Whole sediments were reacted with cupric oxide to yield phenolic oxidation products that indicated the types and relative amounts of the lignins that were present.Measurements of lignin concentration and carbon isotope abundances both indicated a sharp offshore decrease of land-derived organic matter in most areas of the western Gulf. This decrease results primarily from mixing of terrestrial and marine organic matter. The terrestrially derived material in these sediments has a lignin content similar to that of grasses and tree leaves. Flowering plants contribute most of the sedimented lignin compounds. These lignins apparently occur in the form of well-mixed plant fragments that are transported to sea by rivers and deposited primarily on the inner continental shelf.     

Fate of organic matter during aquifer storage and recovery (ASR) of reclaimed water in a carbonate aquifer

Understanding the fate of injected organic matter and the consequences of subsequent redox processes is essential to assess the viability of using reclaimed water in aquifer storage and recovery (ASR). A full-scale field trial was undertaken at Bolivar, South Australia where two ASR cycles injected approximately 3.6 × 10⁵ m³ of reclaimed water into a carbonate aquifer over a 3-a period. Organic C within reclaimed water was predominantly in the dissolved fraction, ranging from 1 to 2 mmol L⁻¹ (10–20 mg L⁻¹), markedly higher than potable supply and stormwater previously reported as source waters for ASR. Between 20% and 24% of the injected dissolved organic C (DOC) was mineralised through reaction with injected O₂ and NO₃. Furthermore, this was achieved mainly within the first 4 m of aquifer passage. Despite the presence of residual DOC, SO₄ reduction was not induced within the bulk of the injected plume. It was only near the ASR well during an extended storage phase where deeply reduced (methanogenic) conditions developed, indicating variable redox zones within the injectant plume. The quality of water recovered from the ASR well indicated that the organic C content of reclaimed water does not restrict its application as a recharge source for ASR.     

Dissolved organic matter in pore water of carbonate sediments from Bermuda

Pore water samples from seven nearshore areas in Bermuda were obtained under in situ conditions and analyzed for dissolved organic carbon, dissolved carbohydrates, dissolved free amino acids and dissolved humic substances. The concentration of dissolved organic carbon is higher than in the overlying nearshore waters indicating significant diagenetic remobilization of carbon in these recently deposited carbonate sediments. Dissolved carbohydrates decrease with depth due to microbial utilization.     

Sulfate reduction and the nature of organic matter in estuarine sediments

The reduction of sulfate by sulfate reducing bacteria in the anoxic zone is an extremely important process during early diagenesis of marine sediments. Our data from Great Bay, NH reinforce the proposal that the rate of sulfate reduction is directly proportional to the reactivity of the organic matter or the amount of readily metabolizable organic matter present in the sediment and, hence, the source of the organic material in the anoxic zone. It appears that organic matter rich in marine organic remains is more easily degraded in the anoxic zone and that sulfate reduction rates can vary considerably in an estuarine system where many types of organic material may be deposited.     

Effects of organic matter heterogeneity on sorption and desorption of organic contaminants by soils and sediments

This review highlights the major progress over the last decade on characterization of geochemically heterogeneous soil/sediment organic matter (SOM) and the impacts of SOM heterogeneity on sorption and desorption of hydrophobic organic contaminants (HOCs) under equilibrium and rate limiting conditions. Sorption and desorption by soils and sediments are fundamental processes controlling fate and transport of less polar and nonpolar organic pollutants in surface aquatic and groundwater systems. Recent studies have shown that soils and sediments exhibit an array of HOC sorption phenomena that are inconsistent with an early partition model based on an assumption of homogeneous gel-like SOM. Increasing data have revealed that isotherm nonlinearity, varied sorption capacity, sorption–desorption hysteresis, and slow rates of sorption and desorption are characteristics for HOC sorption by soils and sediments. These phenomena have been shown to result from different types of condensed SOM that exhibit capacity limiting sorption processes. Recent findings of glass transition phenomena and the nonlinear HOC sorption by humic acids provide a scientific foundation for drawing an analogy between humic acids and synthetic organic polymers that supports a dual mode model for sorption by soils and sediments. Humic acid is glassy or rigid at temperatures lower than its glass transition temperature and exhibits relatively nonlinear sorption isotherms for HOCs. Fractionation and quantification of SOM indicate that soils and sediments contain significant amounts of black carbon and kerogen of different origins. These particulate organic materials have rigid 3-dimensional structures and are often less polar compared to humic substances. Limited studies show that black carbon and kerogen exhibit nonlinear sorption for HOCs and may dominate the overall nonlinear sorption by soils and sediments.     

Re–Os geochronology of organic rich sediments: an evaluation of organic matter analysis methods

Rhenium and osmium in organic-rich sedimentary rocks are dominantly hydrogenous, but any nonhydrogenous component will influence the accuracy and precision of the Re–Os date obtained. To minimize the influence of any nonhydrogenous Re and Os, we evaluate analysis of isolated organic matter from the whole rock, together with whole rock analysis using a CrO₃–H₂SO₄ digestion medium instead of inverse aqua regia, for a black shale unit of the Exshaw Formation, Canada. This unit previously returned a whole rock Re–Os date of 358±10 Ma (Model 3) [Geochim. Cosmochim. Acta (2002)] using inverse aqua regia dissolution. Organic matter isolated from the whole rock matrix using the HF–BF₃ technique [Org. Geochem. 20 (1993) 249] yields scattered data and a Re–Os date of 449±220 Ma (Model 3, MSWD=616). The organic matter analyses show similar ¹⁸⁷Os/¹⁸⁸Os values, but significantly lower ¹⁸⁷Re/¹⁸⁸Os values in comparison to the whole rock analyses. We show that the Re–Os systematics of organic matter are altered during chemical isolation, and as such we suggest that the HF–BF₃ method should not be used for Re–Os analysis of organic matter. Whole rock Re–Os analysis using a CrO₃–H₂SO₄ digestion medium yields significantly better regression analysis compared with the inverse aqua regia method, and the Re–Os data identify two distinct initial ¹⁸⁷Os/¹⁸⁸Os values for the sample set. Separate regressions of these data yield precise dates [366.1±9.6, MSWD=2.2 and 363.4±5.6 Ma, MSWD=1.6 (Model 3)], which are indistinguishable from the age constraints for this formation (363.4±0.4 Ma, U–Pb monazite). Comparison of the Re–Os dates obtained from aqua regia and CrO₃–H₂SO₄ methods suggests that the former may contain nonhydrogenous Re and Os, whereas the CrO₃–H₂SO₄ method dominantly liberates hydrogenous Re–Os from organic matter, allowing for better stratigraphic age determinations and evaluation of the Os isotope composition of seawater.