Pyrolysis-GC-MS and NMR studies of dissolved seawater humic substances and isolates of a marine diatom

¹³C- and ¹H-NMR spectra were obtained for humic substances isolated from a coastal marine environment and also for the intracellular and extracellular extracts of a marine diatom. Phaeodactylum tricornutum Bohlin. Highly branched alkyl chains constitute a large proportion of the structure of the marine humic material, whereas aromatic components are less important. Carbohydrate-type materials, possibly uronic acids, are also present in appreciable amounts. Furans (derived from carbohydrates). pyrroles and nitriles (derived from proteins, nucleic acids and/or tetrapyrroles) and phenols and methylphenols (non-lignin derived) are pyrolysis products derived from pyrolysis-gas chromatography-mass spectrometry of the extracts. The results indicate the similarities in chemical structure of P. tricornutum exudate and dissolved marine humic material.     

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 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.     

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⁺.     

Investigation of marine and terrestrial humic substances by H and C, nuclear magnetic resonance and infrared spectroscopy

Humic acids were isolated from 5 sediments in which the origin nature of the organic matter are both typical and different. The humic acids were characterized on the basis of elemental compositions, infrared spectra and ¹H and ¹³C NMR. This last technique, especially ¹³C NMR, provides qualitative and semi-quantitative information regarding aromatic structure. Combined data from the three techniques permits differentiation of marine and terrestrial organic matter as well as identification of mixtures of humic acids from the two sources.     

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.     

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 origins of marine and non-marine boulder deposits: a brief review

Natural Hazards - We identify 14 mechanisms, marine and non-marine, one man made, that result and could result in the formation of boulder deposits after reviewing issues associated with clast...     

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...     

Analysis of the structure of dissolved marine humic substances and their phytoplanktonic precursors by H and C nuclear magnetic resonance

The structure of dissolved marine humic material and the intracellular and extracellular material from the diatom Phacodactylum tricornutum has been investigated by ¹H- and ¹³C-NMR spectroscopy. The results show that carbohydrates, highly-branched alkyl chains and to a lesser extent aromatic materials are important contributors to the structure of marine humic substances and aqueous extracts of P. tricornutum. There is a close relationship between the chemical structure of P. tricornutum exudate and dissolved marine humic material.     

The geochemistry of boron and its isotopes in groundwaters from marine and non-marine sandstone aquifers

The geological evolution of B in two UK sandstone aquifers is followed from precipitation chemistry through to groundwaters in both the unconfined and confined zones. Measurements have been made of major element geochemistry, B concentrations and B isotopic ratios. The isotopic measurements were carried out using ICP/MS following a simple preconcentration step. Isotopic measurements of rainfall show a bimodal distribution and it is suggested that enriched signatures are characteristic of Atlantic air over Britain and depleted signatures representative of continental air. In the marine Lower Greensand aquifer dissolution of glauconite results in the mobilisation of B and a correlation with SO₄ suggests that this dissolution is related to the oxidation of pyrite which appears to be the SO₄-forming reaction in the aquifer. In the non-marine Hastings beds isotopic ratios and a correlation with HCO₃ suggest that B is associated with the dissolution of ferroan carbonates. In both aquifers the geochemical evolution of B is complex and more information is needed on the behaviour of B isotopes during evapotranspiration and groundwater recharge.     

Arsenic redox transformation by humic substances and Fe minerals

The toxicity and mobility of the redox-active metalloid As strongly depends on its oxidation state, with As(III) (arsenite) being more toxic and mobile than As(V) (arsenate). It is, therefore, necessary to know the biogeochemical processes potentially influencing As redox state to understand and predict its environmental behavior. The first part of this presentation will discuss the quantification of As redox changes by pH-neutral mineral suspensions of goethite [α-Fe^IIIOOH] amended with Fe(II) using wet-chemical and synchrotron X-ray absorption (XANES) analysis (Amstaetter et al., 2010). First, it was found that goethite itself did not oxidize As(III). Second, in contrast to thermodynamic predictions, Fe(II)–goethite systems did not reduce As(V). However, surprisingly, rapid oxidation of As(III) to As(V) was observed in Fe(II)–goethite systems. Iron speciation and mineral analysis by Mössbauer spectroscopy showed rapid formation of ⁵⁷Fe–goethite after ⁵⁷Fe(II) addition and the formation of a so far unidentified additional Fe(II) phase. No other Fe(III) phase could be detected by Mössbauer spectroscopy, EXAFS, scanning electron microscopy, X-ray diffraction or high-resolution transmission electron microscopy. This suggests that reactive Fe(III) species form as an intermediate Fe(III) phase upon Fe(II) addition and electron transfer into bulk goethite but before crystallization of the newly formed Fe(III) as goethite.The second part of the presentation will show that semiquinone radicals produced during microbial or chemical reduction of a humic substance model quinone (AQDS, 9,10-anthraquinone-2,6-disulfonic acid) can react with As and change its redox state (Jiang et al., 2009). The results of these experiments showed that these semiquinone radicals are strong oxidants and oxidize arsenite to arsenate, thus decreasing As toxicity and mobility. The oxidation of As(III) depended strongly on pH. More arsenite (up to 67.3%) was oxidized at pH 11 compared to pH 7 (12.6% oxidation) and pH 3 (0.5% oxidation). In addition to As(III) oxidation by semiquinone radicals, hydroquinones that were also produced during quinone reduction, reduced As(V) to As(III) at neutral and acidic pH values (less than 12%) but not at alkaline pH. In an attempt to understand the observed redox reactions between As and reduced/oxidized quinones present in humic substances, the radical content in reduced AQDS solutions was quantified and Eh-pH diagrams were constructed. Both the radical quantification and the Eh-pH diagram allowed explaining the observed redox reactions between the reduced AQDS solutions and the As.In summary these studies indicate that in the simultaneous presence of Fe(III) oxyhydroxides, Fe(II), and humic substances as commonly observed in environments inhabited by Fe-reducing microorganisms, As(III) oxidation can occur. This potentially explains the presence of As(V) in reduced groundwater aquifers.     

Sedimentary humic acid and fulvic acid as surface active substances

Surface tension of sedimentary fulvic acid (FA) and humic acid (HA) with molecular weight from < 10,000 to > 300,000 was measured at 5°C and 25°C, over a wide range of concentrations (0.114-107.4 g/l) at pH 8. HA was in the form of sodium humate. Surface tension decreases with an increase in HA and FA concentration and both HA and FA were found to be surface active materials with FA exhibiting the lowest surface tension (31 dynes/cm).Plots of surface tension vs. log concentration gave two straight lines with a break at a certain concentration similar to surfactants. From the concentration at the break point, aggregation concentration (AGC) was determined. For HA with molecular weight above 10,000, the AGC decreased with an increase in molecular weight. The more hydrophobic the HA, the greater was the tendency to form aggregates. Surface excess (surface concentration) was determined (2.3 × 10^?10?5.5 × 10^?10mol/cn²) from the slope of the plot of surface tension vs. log concentration for concentrations lower than the AGC. Adsorption of HA into the surface layer increased with increasing molecular weight of HA.     

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.     

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.     

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.