This study focuses on geochemical research into humic acids and humification processes in lakes of West Antarctica, specifically King George Island and Marie Byrd Land. Humic acids were extracted from recent sediments of Antarctic lakes and analysed using high-precision laboratory methods. The experiments included examining the elemental composition and molecular structure of the humic acids. The results show that the organic matter in sediments of the studied lakes has undergone complete humification processes. However, the molecular structure of humic acids is characterized by a predominance of aliphatic fragments and a significant amount of polysaccharides, which is typical of humic substances in the cold climates of Arctic and Antarctic regions. Thus, the humic substances of Antarctic lakes were found to have a very low degree of maturity and were non-resistant to mineralization. These findings are valuable for understanding the full chain of organic matter transformation processes in Antarctic ecosystems and the global carbon cycle on Earth.

The polyphenol theory of humic-substance formation has been studied extensively; however, an alternative theory, that humic substances are formed through the condensation of amino acids and reducing sugars (Maillard reaction), has not been explored to the same extent. The general objectives of this study were to determine whether smectites and goethites catalyze the abiotic polymerization of arginine and glucose to form humic-like compounds. The effects of smectite type, saturating cation, and the degree of Al substitution in goethites on the polymerization reaction were also studied. Four cation-saturated smectites and four Al-substituted goethites were incubated abiotically with solutions containing a mixture of arginine + glucose for 21 days at 37°C. After the incubations, total C recovered ranged from 80.6 to 123.8% and from 100.5 to 105.1% for the smectite and goethite systems, respectively. At the end of the incubations, 21.4–50.3% of the added C and 16.5–90% of the added N were sorbed on the various smectites, and 6.2–9.0% of the added C and 2.3–4.6% of added N was sorbed on the goethites in a form that could not be desorbed by washing with 100 mM CaCl2. X-ray diffraction analysis indicated that some of the sorbed C was intercalated in the smectites and FTIR analysis provided evidence of new absorption bands at 1650 and 1668 cm−1, which are consistent with Maillard reaction products. Thus, it is concluded that smectites catalyze the condensation of arginine and glucose to form humic-like products. Goethites, however, have little or no ability to catalyze this reaction.

Mineral–organic matter (OM) associations play an important role in determining the long-term retention of OM in soils. However, the retention mechanisms of OM in cation–mineral–OM systems remain unclear. Taking into account the dominance of montmorillonite (Mnt) in the soil of the temperate zone, we investigated the stability of humic substances (HSs) in the Fe(III)–Mnt–HS system using thermal analysis. The HS degradation started at ~387°C in the Fe(III)–Mnt–HS system, which was higher than that of the Fe(III)–HS system (290°C). The formed ferrihydrite (Fhy) mainly contributed to the enhanced labile OM retention through adsorption and/or co-precipitation, whereas Mnt inhibited the initial formation and subsequent transformation of Fhy, thus improving the stability of OM. These results suggest that the HS stability in Fe(III)–clay–HS systems depends on the Fe speciation affected by clay minerals, and this finding provides insights into OM–mineral interactions in temperate-zone soils.

This work deals with the formation of humic-like compounds, products of the Maillard reaction between glycine and D-glucose, on clay (K+, Ca2+ and Al3+-saturated montmorillonite and kaolinite) and quartz systems in the presence of the same cations. Natural quartz was used as the control while the effect of cation type, mineral substrate and CEC was evaluated. All the systems form humic-like substances that are probably responsible for the decrease in the pH (H2O) after 30 d. The type of cation does not influence the overall production of humic substances, while the amount of cations controls the formation of humic-like material especially in the presence of clays. A mineral surface is necessary to synthesize molecules with this high degree of complexity.

Fulvic-like compounds are produced in great amounts on natural quartz and their formation is hampered by the presence of ‘free’ cations, regardless of their amount. Humic substances do not penetrate the interlayer of montmorillonite.

Iron oxides and oxyhydroxides are commonly of considerable importance in the sorption of ions onto rocks, soils and sediments. They can be the controlling sorptive phases even if they are present in relatively small quantities. In common with other oxides and clay minerals, the sorptionpH-edge of metals is directly linked to their hydrolysis: the higher the residual charge on the metal ion, the lower the pH-edge. Modelling of this process has been successfully carried out using different microscopic or macroscopic definitions of the interface (e.g. surface complexation orion exchange models that may or may not include mineralogical descriptions). The influence of organic material on the sorption of many metals is of significant. This organic material includes simple organic molecules and more complex exopolymeric substances (e.g. humic substances) producedby the decay of natural organic matter. Sorption of this organic material to mineral surfaces has been the subject of a large body of work. The various types of organic substances do not share the same affinities for mineral surfaces in general, and for iron oxides and oxyhydroxides in particular.In those cases in which successful models of the component binary systems (i.e. metal–surface, metal–organic, organic–surface) have been developed, the formation of mixed surface complexes, the evolution of the surface itself, the addition order in laboratory systems, andthe evolution of natural organic matter fractions during sorption, have often precluded a satisfactory description of metal–surface–organic ternary systems over a sufficiently wide range of parameter values (i.e. pH, ionic strength, concentration of humic substances). This manuscriptdescribes the reasons for some successes and failures in the modelling of the ternary systems. Promising recent advances and possible methods of providing more complete descriptions of these intricate systems are also discussed.

Previously, it has been suggested that metal ions complexed to humic acid in the environment might show slower dissociation than those added to humic substances in the laboratory, which has serious implications for the transport of radionuclides in the environment. The dissociation of lanthanide and anthropogenic actinide ions from humic substance complexes has been studied as a function of humic concentration and metal ion:humic concentration ratio. The results suggest that the apparently slower kinetics observed for metal ions complexed in the environment are probably due to the large humic concentrations that are used in those studies. Further, there is no evidence that the dissociation rate constant varies at very low metal ion concentrations. Although humic samples size-fractionated by ultrafiltration showed that more metal may be bound non-exchangeably, there was no evidence for different rate constants. Ultrafiltration of Eu(III)/humic acid mixtures did show a shift in Eu from smaller to larger fractions over a period of two days. Therefore, the results suggest that dissociation rate constants determined in the laboratory at metal ion concentrations higher than those expected in the environment may be used in predicting radionuclide mobility, provided that the humic acid concentration is in the range expected at the site.

Due to the input of humic substances from freshwater run-off into the marine habitat, the influences of such substances on marine organisms should not be neglected. We here investigate the effect of a humic acid (HA) extract from the North Sea, characterized by spectroscopic techniques and carboxylic and phenolic group content, on the growth of different algae. Two benthic pennate diatoms isolated from the Baltic Sea, Navicula ramosissima (C. Agardh) Cleve, 1895 and Entomoneis paludosa (W. Smith) Reimer, 1975, as well as two tychopelagic centric diatoms isolated from the North Sea, Melosira nummuloides C. Agardh, 1824 and Paralia sulcata (Ehrenberg) Cleve, 1873, were employed. The concentrations of pigments (fucoxanthin, diadinoxanthin, chlorophyll-a and β-carotene) and nutrients were also measured. Adding low concentrations of naturally humic substances (5.5 mg of C l−1) to the algae cultures resulted in enhanced growth rates compared to the control experiments, possibly due to the increase in the bioavailability of trace metals or other nutrients.

This study concerned the fragility of maritime Antarctic soils under increasing temperature, using the C dynamics and structural characteristics of humic substances as indicators. Working with four representative soils from King George Island (Lithic Thiomorphic Cryosol (LTC1 and LTC2), Ornithogenic Cryosol (OG) and Gelic Organosol (ORG)) we evaluated the total organic C and nitrogen contents, the oxidizable C and humic substances. Soil samples were incubated to assess the amount of C potentially mineralizable at temperatures typical of an Antarctic summer (5–14°C). Humic acids showed a higher aliphatic character and a smaller number of condensed aromatic groups, which suggests that these molecules from Antarctic soils are generally less resistant to microbial degradation than humic acids molecules from other regions. Based on 13C NMR spectra of MAS and CP/MAS, samples of soil humic acids of mineral soils (LTC1 and LTC2) have a higher content of aliphatic C, and heteroatom C, with lower levels of carbonyl and aromatic C, when compared with organic matter-rich soils (OG and ORG). Increasing incubation temperature led to a higher rate of mineralizable C in all soils. A sequence of soil fragility was suggested - LTC1 and LTC2 > OG > ORG - which showed a correlation with the Q10 coefficient and the ratio of labile and recalcitrant C fractions of soil organic matter (R2 = 0.83).

Iodine intake is important for thyroid function. Iodine content of natural waters is high in some areas and occurs bound in humic substances. Tap water is a major dietary source but bioavailability of organically bound iodine may be impaired. The objective was to assess if naturally occurring iodine bound in humic substances is bioavailable. Tap water was collected at Randers and Skagen waterworks and spot urine samples were collected from 430 long-term Randers and Skagen dwellers, who filled in a questionnaire. Tap water contained 2 μg/l elemental iodine in Randers and 140 μg/l iodine bound in humic substances in Skagen. Median (25; 75 percentile) urinary iodine excretion among Randers and Skagen dwellers not using iodine-containing supplements was 50 (37; 83) μg/24 h and 177 (137; 219) μg/24 h respectively (P < 0·001). The fraction of samples with iodine below 100 μg/24 h was 85·0 % in Randers and 6·5 % in Skagen (P < 0·001). Use of iodine-containing supplements increased urinary iodine by 60 μg/24 h (P < 0·001). This decreased the number of samples with iodine below 100 μg/24 h to 67·3 % and 5·0 % respectively, but increased the number of samples with iodine above 300 μg/24 h to 2·4 % and 16·1 %. Bioavailability of iodine in humic substances in Skagen tap water was about 85 %. Iodine in natural waters may be elemental or found in humic substances. The fraction available suggests an importance of drinking water supply for population iodine intake, although this may not be adequate to estimate population iodine intake.