Organic geochemistry of Recent equatorial deltaic sediments

The organic matter of recent deltaic sediments cored in the Mahakam delta, East Kalimantan, has been studied before and after physical fractionation into sands >50 μm, silts 5–50 μm and clays <5 μm. Both the lipid and non-lipid components have been investigated.Weight, carbon and nitrogen fractionation budgets were used to define three types of samples, depending on coarse particle contributions to the total amount of organic matter: a = a first type with more than 50% of the O.M. in the coarse particles, high C/N ratios and O.M. content, b = an intermediary type with medium C/N ratios and O.M. content, each fraction having quite the same O.M. content, c = a third type with less than 5% of the whole O.M. in the sands and the lowest C/N ratios and O.M. content.Concerning the global organic characteristics of the fractions, a systematic increase of C/N ratios occurs when going from clays to sands; the finer the fraction is, the more nitrogenous the compounds are. This enrichment in nitrogen is related to a persistent high rate of hydrolysable material either for argillaceous organic matter-poor sediments or for the clay fractions of all types of samples. Conversely, the type (a) coarse sediments, in particular the sandy components were resistant to acid hydrolysis with burial.Concerning the geochemical markers signatures of granulometric fractions, the distribution patterns of n-alkanes and n-fatty acids are characterized by the predominance of high molecular weight compounds >C₂₂. Carbon preference index (CPI) values are higher in the sands and silts, reflecting their enrichment in continentally-derived vegetation debris. For type (c), the fractionation revealed markers of microbial activity within the clay fractions. For all types of samples, we observed an increase with burial of the n-alkane and n-fatty acid concentrations, particularly in the clay fractions, suggesting possibly a better preservation and/or affinity of lipids with the finest fractions.     

The influence of humic substances on the geochemistry of iodine in nearshore and hemipelagic marine sediments

Iodine is characteristically enriched at the surface of hemipelagic and nearshore sediments deposited under oxygenated conditions. In such sediments, bulk I/C_org ratios usually decrease with depth to values which are characteristic of anoxic sediments, reflecting a preferential release of I during early diagenesis. There is some debate as to whether sedimentary I is associated with the iron oxyhydroxide phase or with the organic fraction, and whether the decrease in I/C_org with depth is due to the dissolution of the iron oxyhydroxides or the decomposition of labile organic matter.It is shown that in a surficial hemipelagic sediment sample and in a nearshore sediment core I is mainly associated with the organic fraction and, moreover, that humic substances are involved in the surficial iodine enrichment. Laboratory experiments on the uptake and release of I by and from sedimentary humic substances also suggest a mechanism whereby humic materials reduce iodate at the sediment/water interface to an electrophilic I species which further reacts with the organic matter to produce iodinated organic molecules. During burial, this excess I could be displaced from the organic matrix by nucleophiles such as sulphide ions or thiosulphate, thus providing a possible explanation for the decrease in I/C_org ratio with depth observed in many nearshore and hemipelagic sediments.     

The role of humic substances in the formation of marble patinas under soil burial conditions

The present work aim to study the effect of burial on the photoluminescnece (PL) spectra of white, crystalline marble surfaces and the physicochemical processes that take place at the marble—soil interface. The PL was studied by an argon ion laser beam, focused through a microscope objective onto the sample, offering a spatial resolution of 3 μm. Long-buried (time scale of 1,000 years) surfaces show a red (at 610 nm) emission due to Mn²⁺, which is also shown on fresh marble spectra and an additional broadband blue-green (380–530 nm) one. Electron paramagnetic resonance (EPR) spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) indicate that the latter emission originates from humate complexes. The complexes are most probably Ca-humates, the humic substances found in the soil and the divalent calcium cations released by the dissolution of marble calcite. Finally, the examination of recently (time scale of 50 years) buried surfaces shows that the blue-green emission and consequently the presence of humates in marble patinas are not affected by the soil organic matter content. Soil acidity however, is a critical factor, with a total absence of the blue-green emission at pH values lower than 6.     

Aggregation of aquatic humic substances

Humic substances (HS) were isolated from Penwhirn Reservoir (PR) and Esthwaite Water (EW) and their removal from solution by centrifugation was studied as a function of pH, humic concentration and molecular weight, and CaCl₂ concentration. Large amounts (up to 50%) of PR HS could be removed but only small amounts (? 3%) of EW HS. At pH ? 5 removal of PR HS by Ca²⁺ can be explained satisfactorily in terms of decreases in humic solubilities induced by complexation with the cation. However, removal induced by protonation of the PR HS is unusual in that it decreases with increasing humic concentration.The results suggest that PR HS comprise a range of molecules differing in solubility, with the high-molecular-weight (40,000) components being the least soluble. The EW HS consist of molecules of weight-average molecular weight 5000 and resemble similarly sized PR HS in that they remain unaggregated in solution even when highly complexed with Ca²⁺.     

The luminescent humic substances in speleothems

Calcite speleothems deposited in caves by seepage waters derived from the overlying soils of the epikarst are typically coarsely crystalline, colored various shades of brown through orange and white, and strongly luminescent. For most speleothems, the color and luminescence is due to humic substances incorporated in the calcite crystals. For a quantitative assessment of the luminescent properties of these materials, the organic content of the dissolved speleothems was separated by gel chromatography and spectra measured as a function of molecular weight. The most intense luminescence was obtained from molecular weight fractions in the range of 4000–6000 daltons, a range characteristic of fulvic acids. In addition, there was considerable variation in detail from sample to sample that would merit further investigation.     

Organic fades in Recent sediments of carbonate platforms: Southwestern Puerto Rico and Northern Belize

Our organic facies model of a platform environment is based on the analysis of (1) total organic carbon, (2) visual protokerogen types and hydrogen indices of the sediments, (3) sediment mineralogy and grain size, and (4) reef patterns, water circulation, and relief of the adjacent land.TOC values are lowest on reefs and outer platforms (0.2%); intermediate in sediments fringing carbonate islands (0.5–2.0%), on sea-grass meadows (0.5–0.7%), and in forereef lagoons (0.1–0.7%); highest in inner platform lagoons (0.5–5.0%) and mangrove swamps (2.7–3.5%). Paniculate organic matter comprises structured terrestrial, marine, and amorphous types. On average, terrestrial material accounts for 28% of OM in Puerto Rico and 12% in Belize. The mean hydrogen index of the sediment is 355 (mg hydrocarbons/g TOC) in Puerto Rico and 719 in Belize.This study indicates that TOC values are mainly related to platform subenvironment, while OM types are controlled by distance from the shoreline. Organic facies dominated by structural terrestrial OM occur closer to the shore, whereas toward the shelf margin marine and amorphous OM contents increase.     

The effects of humic substances on the transport of radionuclides: Recent improvements in the prediction of behaviour and the understanding of mechanisms

Some recent developments made during the European Union 6th Framework Integrated Project FUNMIG in the understanding and prediction of behaviour in ternary systems of radionuclides, humic substances and mineral surfaces are described. These developments are placed in the context of the existing literature. The aim is to describe the current understanding of humic substance mediated radionuclide transport as it may be applied to calculations in support of Radiological Performance Assessment. Some improvements in experimental techniques that provide the raw data to calibrate metal ion binding models are explained. The various metal ion binding models that are available are described and contrasted, before the recent development of ternary system models, in particular the Ligand Charge Distribution model that can predict metal ion and humic substance behaviour in ternary systems. The kinetic effects in ternary systems are described along with the models that are used to describe them. Finally, the remaining challenges in making predictions of radionuclide transport for the Radiological Performance Assessment of radioactive waste repositories are discussed.     

Sources of sedimentary humic substances: vascular plant debris

A modern Washington continental shelf sediment was fractionated densimetrically using either an organic solvent, CBrCl₃, or aqueous ZnCl₂. The resulting low density materials (<2.06 g/ml) account for only 1% of the sediment mass but contain 25% of the sedimentary organic carbon and 53% of the lignin. The C/N ratios (30–40) and lignin phenol yields ($\text{Λ = 8}$) and compositions indicate that the low density materials are essentially pure vascular plant debris which is slightly enriched in woody (versus nonwoody) tissues compared to the bulk sediment. The low density materials yield approximately one-third of their organic carbon as humic substances and contribute 23% and 14% of the total sedimentary humic and fulvic acids, respectively. Assuming that the lignin remaining in the sedimentary fraction is also contained in plant fragments that yield similar levels of humic substances, then 50% and 30% of the total humic and fulvic acids, respectively, arise directly from plant debris.Base-extraction of fresh and naturally degraded vascular plant materials reveals that significant levels of humic and fulvic acids are obtained using classical extraction techniques. Approximately 1–2% of the carbon from fresh woods and 10–25% from leaves and bark were isolated as humic acids and 2–4 times those levels as fulvic acids. A highly degraded hardwood yielded up to 44% of its carbon as humic and fulvic acids. The humic acids from fresh plants are generally enriched in lignin components relative to carbohydrates and recognizable biochemicals account for up to 50% of the total carbon. Humic and fulvic acids extracted directly from sedimentary plant debris could be responsible for a major fraction of the biochemical component of humic substances.     

Molecular size of aquatic humic substances

Aquatic humic substances, which account for 30 to 50% of the organic carbon in water, are a principal component of aquatic organic matter. The molecular size of aquatic humic substances, determined by small-angle X-ray scattering, varies from 4.7 to 33 Å in their radius of gyration, corresponding to a molecular weight range of 500 to greater than 10,000. The aquatic fulvic acid fraction contains substances with molecular weights ranging from 500 to 2000 and is monodisperse, whereas the aquatic humic acid fraction contains substances with molecular weights ranging from 1000 to greater than 10,000 and is generally polydisperse.     

Phosphorus in marine and non-marine humic substances

The phosphorus content of marine humic acids (HA) is in the range of 0.1–0.2%. The C/P ratios of the HA are 300 to 400. Marine fulvic acids (FA) contain 0.4–0.8% P and have C/P ratios of 80 to 100. High molecular weight organic matter dissolved in pore waters (DOM) contains 0.5% P and has C/P of 90. The data suggest that during the formation sequence: Plankton → DOM → FA → HA → Kerogen, phosphorus is lost, mainly in the FA → HA (and possibly also in the HA → Kerogen) step. Diagenesis of sedimentary humic acids is accompanied by loss of phosphorus (as well as of nitrogen) to form HA with C/P ratios of 1000.Soil humic substances resemble marine humates in P content (0.3%) and soil FA's are about three to fivefold enriched in P relative to HA. C/P ratios are lower in soil HA (ca. 200) as compared with marine HA. Humic acids from diagenetic products such as peat and lignite are highly depleted in P. Rough calculations indicate that humate bound P may account for 20–50% of the organic phosphorus reservoir in sediments. The chemical speciation of this P is unknown, but lack of correlation with ash, Fe, Ca or Al content (in marine humates, at least) indicates that it is organically bound.     

Modelling the interactions of Hg(II) and methylmercury with humic substances using WHAM/Model VI

WHAM, incorporating Humic Ion Binding Model VI, was used to analyse published data describing the binding of Hg(II) and methylmercury (CH₃Hg) by isolated humic substances. For Hg(II), the data covered wide ranges of pH and levels of metal binding, whereas for CH₃Hg the range of metal binding was relatively narrow. Data were fitted by adjustment of a single model parameter, log K_MA, the intrinsic equilibrium constant characterising, in the standard version of the model, the binding of metal ions and their first hydrolysis products to humic carboxylic acid groups. Other model parameters, including those characterising the tendency of metal ions to interact with “softer” ligand atoms (N and S), were held at their default values. The importance of the first hydrolysis products in binding was considered, and also the possible influence of competition by residual Fe(III), bound to the humic matter.     

Assessing redox properties of standard humic substances

Redox properties of humic substances (HS) control important biogeochemical processes. Thus, accurate estimation of redox properties of HS is essential. However, there is no general consensus regarding the best available measurement method of HS redox properties. In this study, we compared several common HS redox property measurement methods using anthraquinone-2,6-disulfonate (AQDS) as model compound, and standard Elliot soil humic acid (1S102H, ESHA), reference Pahokee peat (1R103H, PPHA), and Suwannee River natural organic matter (1R101N, SRNOM) as representative HS. We found that the H₂/Pd reduction method followed by incubation with ferric citrate (FeCit) reagent was incomplete, and the H₂/Pd reduction method followed by incubation with potassium ferricyanide (K₃Fe(CN)₆) was insensitive. Stannous chloride (SnCl₂) reduction followed by titration of excess stannous (Sn²⁺) by potassium dichromate (K₂Cr₂O₇) was found to be most accurate. These findings will help in future investigations on detailed characterizations of functional groups of HS responsible for oxidation/reduction reactions.     

Unique properties of humic substances from sapropel

Doklady Earth Sciences - Sapropel from inland Russian water reservoirs is becoming a popular raw material for medicinal purposes, production of sorbents, organomineral fertilizers, and food...     

Analytical constraints on the structural features of humic substances

A rigorous calculation of the maximum fraction of aromatic carbon in humus or any other complex mixture of organic compounds is described. Input parameters include elemental composition, carboxyl content, carbonyl content, and an estimate of number-average molecular weight. The calculated upper limit constrains structural models that are based on interpretations of ¹³C-NMR spectra or on the products of degradation reactions and also directly limits the phenolic content of a sample.Another computational method is described that yields good estimates of the actual levels of aromatic (and aliphatic) carbon in a humus sample. Even though the method is capable of estimating only the most probable level of aromatic carbon, the predicted values are surprisingly close to the experimental values that have been determined by ¹³C-NMR spectroscopy.     

Characterization of groundwater humic substances: influence of sedimentary organic carbon

A total of 35 groundwaters from 4 different aquifer systems in Germany are investigated for their physico-chemical properties, dissolved organic C (DOC) and humic and fulvic acids. Humic substances are isolated and characterized for their elemental composition, UV/Vis and fluorescence spectroscopic properties, size distribution by gel permeation chromatography (GPC) and ¹⁴C content. For isolation of sufficient quantities of humic substances a mobile sampling system is developed based on a combination of reverse osmosis (RO) and XAD–8 adsorption chromatography. One of the aquifer systems (Gorleben) covers a wide range of hydrogeochemical conditions, whereas the other 3 aquifer systems (Munich, Franconian Albvorland and Fuhrberg) have less diverse properties. One specific feature of the Gorleben aquifer system is the presence of a very high DOC, which, in contrast to other aquifer systems, contains considerable amounts of aquatic humic acid. This is attributed to the release of aquatic humic substances originating from sedimentary organic C (SOC) that is abundant in Gorleben sediments. The results show that aquatic humic substances from different aquifer systems have dissimilar properties which differ from one another. Systematic differences are found among humic substances from different regions of the Gorleben aquifer system. Such differences are considered to be caused by the mixing of humic substances from the SOC. However, exact quantification of such mixing appears difficult because overlapping effects of different geochemical processes feigning a dissolution of SOC cannot be excluded.     

Thermal characterization of natural and synthetic humic substances

Thermogravimetric technique was used for the characterization of natural (humic) and synthetic (melanoidins) substances. The influence of pH on the thermal stability of humic substances was studied. A similarity in thermal behaviour of natural humic substances and of melanoidins (prepared from an excess of sugar) and the unique thermal properties of melanoidins (prepared from basic amino acids) was observed. Thermal behavior of natural and synthetic substances was compared with model compounds of sugar, peptide and kerogen types.     

The adsorption of aquatic humic substances by iron oxides

The interactions of humic substances from Esthwaite Water with hydrous iron oxides (α-FeOOH, α-Fe₂O₃, amorphous Fe-gel) have been examined by measuring adsorption isotherms and by microelectrophoresis. In Na⁺-Cl^?-HCO₃^?at I = 0.002 M (medium I) the extent of adsorption decreases with increasing pH. The results are consistent with a mechanism involving ligand exchange of humic anionic groups with H₂O and OH^?of surface Fe-OH₂⁺and Fe-OH groups respectively, with an increasing degree of protonation of the adsorbed humics as the adsorption density increases at constant pH.At pH 7 in a medium containing Mg²⁺, Ca²⁺ and SO₄^2?, at their Esthwaite Water concentrations and at I= 0.002 M (medium II) the adsorption capacity of goethite (α-FeOOH) is approximately twice that in medium I. Electrophoresis experiments show that the extra capacity is associated with coadsorption of Mg²⁺ and/or Ca²⁺ ions.When the iron oxides are added to samples of Esthwaite Water itself they become negatively charged and plots of electrophoretic mobility against pH for the natural water are identical to those in medium II plus humics.     

An application of soil humic substances to geochemical exploration

The wet temperate climate of Tasmania causes strong leaching of soils and conventional “B” horizon soil geochemistry yields unreliable results. For this reason, most surveys of recent times have been based on “C” horizon sampling which is expensive and often difficult to accomplish in the strongly dissected, heavily vegetated terrain of western Tasmania.A system has been developed based on sampling of the “A” soil horizon, extraction of the humic substances with 0.5 M NH₄OH and determination of the associated metals by atomic absorption spectrometry. The humic substances content of the extract is obtained from quantitative wet oxidation of an aliquot of the sample with 0.4N K₂ Cr₂ O₇.In trials to date this system has yielded results compatible with those obtained from the “C” horizon. It offers a cost effective method of exploration by soil geochemistry and can be carried out with minimal disturbance to the environment.     

Organic geochemistry of the Vindhyan sediments: Implications for hydrocarbons

The organic geochemical methods of hydrocarbon prospecting involve the characterization of sedimentary organic matter in terms of its abundance, source and thermal maturity, which are essential prerequisites for a hydrocarbon source rock. In the present study, evaluation of organic matter in the outcrop shale samples from the Semri and Kaimur Groups of Vindhyan basin was carried out using Rock Eval pyrolysis. Also, the adsorbed low molecular weight hydrocarbons, methane, ethane, propane and butane, were investigated in the near surface soils to infer the generation of hydrocarbons in the Vindhyan basin. The Total Organic Carbon (TOC) content in shales ranges between 0.04% and 1.43%. The S₁ (thermally liberated free hydrocarbons) values range between 0.01–0.09 mgHC/gRock (milligram hydrocarbon per gram of rock sample), whereas the S₂ (hydrocarbons from cracking of kerogen) show the values between 0.01 and 0.14 mgHC/gRock. Based on the T_max (temperature at highest yield of S₂) and the hydrogen index (HI) correlations, the organic matter is characterized by Type III kerogen. The adsorbed soil gas, CH₄ (C₁), C₂H₆ (C₂), C₃H₈ (C₃) and nC₄H₁₀, (nC4), concentrations measured in the soil samples from the eastern part of Vindhyan basin (Son Valley) vary from 0 to 186 ppb, 0 to 4 ppb, 0 to 5 ppb, and 0 to 1 ppb, respectively. The stable carbon isotope values for the desorbed methane (δ¹³C₁) and ethane (δ¹³C₂) range between −45.7‰ to −25.2‰ and −35.3‰ to −20.19‰ (VPDB), respectively suggesting a thermogenic source for these hydrocarbons. High concentrations of thermogenic hydrocarbons are characteristic of areas around Sagar, Narsinghpur, Katni and Satna in the Son Valley. The light hydrocarbon concentrations (C₁–C₄) in near surface soils of the western Vindhyan basin around Chambal Valley have been reported to vary between 1–2547 ppb, 1–558 ppb, 1–181 ppb, 1–37 ppb and 1–32 ppb, respectively with high concentrations around Baran-Jhalawar-Bhanpur-Garot regions (Kumar et al., 2006). The light gaseous hydrocarbon anomalies are coincident with the wrench faults (Kota – Dholpur, Ratlam – Shivpuri, Kannod – Damoh, Son Banspur – Rewa wrench) in the Vindhyan basin, which may provide conducive pathways for the migration of the hydrocarbons towards the near surface soils.