The humin structure of mucilage aggregates in the Adriatic and Tyrrhenian seas: hypothesis about the reasonable causes of mucilage formation

Sixteen mucilages sampled in the Adriatic and Tyrrhenian seas during 1999–2001 were characterised using spectroscopic [Fourier transform infrared spectroscopy (FTIR); colorimetric], chromatographic [thin-layer chromatography (TLC)], and elemental analysis techniques. Most samples contained comparable fractions of organic and inorganic compounds, with the exception of a few samples where the inorganic fraction was greater than the organic fraction. Carbohydrates were important in the samples rich in organic matter, while carbonate and silica (quartz and biogenic silica) were the most important constituents of the inorganic fraction. Carbonate and silica were the only important constituents of the samples with a very low organic content.According to chemical analyses, mucilage aggregates show the typical structure of humin—the insoluble fraction of the humic substance. Classification of mucilage samples as humin-like compounds, together with a reexamination of the factors involved in the formation of organic aggregates in marine environment, has led to the formulation of a reasonable hypothesis for mucilage formation.     

Nine thousand years of upper montane soil/vegetation dynamics from the summit of Caratuva Peak,Southern Brazil

Biodiversity loss, climate change, and increased freshwater consumption are some of the main environmental problems on Earth. Mountain ecosystems can reduce these threats by providing several positive influences, such as the maintenance of biodiversity, water regulation, and carbon storage, amongst others. The knowledge of the history of these environments and their response to climate change is very important for management, conservation, and environmental monitoring programs. The genesis of the soil organic matter of the current upper montane vegetation remains unclear and seems to be quite variable depending on location. Some upper montane sites in the very extensive coastal Sea Mountain Range present considerable organic matter from the late Pleistocene and other from only the Holocene. Our study was carried out on three soil profiles (two cores in grassland and one in forest) on the Caratuva Peak of the Serra do Ibitiraquire (a sub-range of Sea Mountain Range – Serra do Mar) in Southern Brazil. The δ¹³C isotopic analyses of organic matter in soil horizons were conducted to detect whether C₃ or C₄ plants dominated the past communities. Complementarily, we performed a pollen analysis and ¹⁴C dating of the humin fraction to obtain the age of the studied horizons. Except for a short and probably drier period (between 6000 and 4500 cal yr BP), C₃ plants, including ombrophilous grasses and trees, have dominated the highlands of the Caratuva Peak (Pico Caratuva), as well as the other uppermost summits of the Serra do Ibitiraquire, since around 9000 cal yr BP. The Caratuva region represents a landscape of high altitude grasslands (campos de altitude altomontanos or campos altomontanos) and upper montane rain/cloud forests with soils that most likely contain some organic matter from the late Pleistocene, as has been reported in Southern and Southeastern Brazil for other sites. However, our results indicate that the studied deposits (near the summit) are from the early to late Holocene, when somewhat wetter and warmer conditions (since around 9000 cal yr BP) enabled a stronger colonization of the ridge of Pico Caratuva by mainly C₃ plants, especially grassland species. However, at the same time, even near the summit, the soil core from the forest site already presented the current physiognomy (or a shrubby/elfin or successional forest), indicating that the colonization of the neighboring uppermost saddles and valleys were probably populated mainly by upper montane forest species.     

Spectroscopic Characterization of Organic Structures and Organic‐Inorganic Interactions in Paper Mill Sludge

The organic composition and organic‐inorganic interaction in paper mill sludge (PS) solvent extracts (hexane, ethyl acetate, acetone and ethanol) and humic fractions, humic acid (HA) and humin (HU) were studied by electron paramagnetic resonance spectroscopy (EPR), proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H NMR; ¹³C NMR), Fourier‐transformed infrared spectroscopy (FTIR), and ultraviolet‐visible spectroscopy (UV‐vis). The strategy of fractionating the PS, sequentially, with organic solvents of increasing polarity is a reliable analytical procedure for humic substance sample separation because it results in more purified fractions. FTIR, ¹H NMR and ¹³C NMR results showed that hexane extract consisted mainly of aliphatic hydrocarbon structures. Their contents in the extracts decreased as the polarity of the extracting solvent increased and the content of oxygen functional groups increased. Carboxylic and carboxylate functional groups were found in the acetone extract, and ester and ether functions were predominantly found in the ethanol extract. EPR spectra revealed some Fe³⁺ complexes with rhombic structure (g₁ = 4.3; g₂ = 9.0) in the humic fractions and in all solvent extracts, except hexane. Quasi‐octahedral Fe³⁺ complexes (g = 2.3; ΔH_pp ≤ 400 G) were found in the HU fraction and in the acetone extract. The organic free radical content in the HA fraction was higher than the non‐fractionated PS sample and HU fraction.     

Late Quaternary lake-level changes constrained by radiocarbon and stable isotope studies on sediment cores from Lake Titicaca, South America

We present and compare AMS-¹⁴C geochronologies for sediment cores recovered from Lake Titicaca, South America. Radiocarbon dates from three core sites constrain the timing of late Quaternary paleoenvironmental changes in the Central Andes and highlight the site-specific factors that limit the radiocarbon geochronometer. With the exception of mid-Holocene sediments, all cores are generally devoid of macrophyte fragments, thus bulk organic fractions are used to build core chronologies. Comparisons of radiocarbon results for chemically defined fractions (bulk decalcified, humate, humin) suggest that ages derived from all fractions are generally coherent in the post-13,500 yr BP time interval. In the pre-13,500 yr BP time interval, ages derived from humate extracts are significantly younger (300–7000 years) than ages from paired humin residues. Gross age incoherencies between paired humate and humin sub-fractions in pre-13,500 yr BP sediments from all core sites probably reflect the net downward migration of humates. Ages derived from bulk decalcified fractions at our shallow water (90 m) and deep water (230 m) core sites consistently fall between ages derived from humate and humin sub-fractions in the pre-13,500 yr BP interval, reflecting that the bulk decalcified fraction is predominantly a mixture of humate and humin sub-fractions. Bulk decalcified ages from the pre-13,500 yr BP interval at our intermediate depth core site (150 m) are consistently older than humate (youngest) and humin sub-fractions. This uniform, reproducible pattern can be explained by the mobilization of a relatively older organic sub-fraction during and after the re-acidification step following the alkaline treatment of the bulk sediment. The inferred existence of this ‘alkali-mobile, acid-soluble’ sub-fraction implies a different depositional/post-depositional history that is potentially associated with a difference in source material. While internally consistent geochronologies can be developed for the Lake Titicaca sequence using different organic fractions, mobile organic sub-fractions and fractions containing mobile sub-fractions should generally be avoided in geochronology studies. Consequently, we believe humin and/or bulk decalcified ages provide the most consistent chronologies for the post-13,500 yr BP interval, and humin ages provide the most representative ages for sedimentation prior to 13,500 yr BP interval.Using the age model derived from the deep water core site and a previously published isotope-based lake-level reconstruction, we present a qualitative record of lake level in the context of several ice-core records from the western hemisphere. We find the latest Pleistocene lake-level response to changing insolation began during or just prior to the Bølling/Allerød period. Using the isotope-based lake-level reconstruction, we also find the 85-m drop in lake level that occurred during the mid-Holocene was synchronous with an increase in the variability of ice-core δ¹⁸O from a nearby icecap, but was not reflected in any of the polar ice-core records recovered from the interior of Antarctica and Greenland.