. A class of organic molecules extracted from atmospheric aerosol particles and isolated from fog and cloud water has been termed HUmic-LIke Substances (HULIS) due to a certain resemblance to terrestrial and aquatic humic and fulvic acids. In light of the interest that this class of atmospheric compounds currently attracts, we comprehensively review HULIS properties, as well as laboratory and field investigations concerning their formation and characterization in atmospheric samples. While sharing some important features such as polyacidic nature, accumulating evidence suggests that atmospheric HULIS differ substantially from terrestrial and aquatic humic substances. Major differences between HULIS and humic substances, including smaller average molecular weight, lower aromatic moiety content, greater surface activity, better droplet activation ability, as well as others, are highlighted. Several alternatives are proposed that may explain such differences: (1) the possibility that mono- and di-carboxylic acids and mineral acids abundant in the atmosphere prevent the formation of large humic "supramolecular associations"; (2) that large humic macromolecules are destroyed in the atmosphere by UV radiation, O3, and OH- radicals; (3) that "HULIS" actually consists of a complex, unresolved mixture of relatively small molecules rather than macromolecular entities; and (4) that HULIS formed via abiotic and short-lived oxidative reaction pathways differ substantially from humic substances formed over long time periods via biologically-mediated reactions. It should also be recalled that the vast majority of studies of HULIS relate to the water soluble fraction, which would include only the fulvic acid fraction of humic substances, and exclude the humic acid (base-soluble) and humin (insoluble) fractions of humic substances. A significant effort towards adopting standard extraction and characterization methods is required to develop a better and meaningful comparison between different HULIS samples.

/pdf/atmospheric-hulis-how-humic-like-are-they-a-comprehensive-4eo3w54c0b.pdf

Atmospheric HULIS: How humic-like are they? A comprehensive and critical review

Soil organic matter (SOM) as a solid or as a film at mineral surfaces affects wetting properties in unsaturated soil Soil organic matter mostly consists of a heterogeneous mixture of components with hydrophilic and hydrophobic functional groups This paper analyzes relations of SOM to soil wettability by considering functional group compositions of different soluble fractions Forest soil samples from two loamy sand Cambisol profiles (locations Chorin and Steigerwald) and from a Podzol (Waldstein) were used to obtain water [SOM(W)] and sodium pyrophosphate [SOM(PY)] soluble SOM fractions The hydrophobic (A) and hydrophilic (B) functional groups of bulk soil SOM and of the soluble fractions were evaluated using transmission Fourier-transform infrared (FT-IR) spectroscopy Advancing liquid-solid contact angles (CA) were determined by using the capillary rise method For soil organic carbon (SOC) contents 10 g kg -1  Although hydrophilic groups in FT-IR spectra of SOM(W), SOM(PY), and bulk soil dominated (ie, A/B ratios between 008 and 05), soil wettability was reduced (ie, CA between 88 and 52°) Soil specific relations between CA and A/B ratios could be obtained after introducing relatively soil type independent factors, G As exponential functions of the SOC/clay relation, the G-factors imitate the effectiveness of functional groups with respect to wettability The results suggest that in addition to SOC content, the SOM composition may improve explanations of soil wettability if the spatial orientation of SOM functional groups at the SOM-mineral surface in the presence of sorption sites and polyvalent cations is considered

Composition of Organic Matter Fractions for Explaining Wettability of Three Forest Soils

The protective impact of aggregation on microbial degradation through separation has been described frequently, especially for biotically formed aggregates. However, to date little information exists on the effects of organic-matter (OM) quantity and OM quality on physical protection, i.e., reduced degradability by microorganisms caused by physical factors. In the present paper, we hypothesize that soil wettability, which is significantly influenced by OM, may act as a key factor for OM stabilization as it controls the microbial accessibility for water, nutrients, and oxygen in three-phase systems like soil. Based on this hypothesis, the first objective is to evaluate new findings on the organization of organo-mineral complexes at the nanoscale as one of the processes creating water-repellent coatings on mineral surfaces. The second objective is to quantify the degree of alteration of coated surfaces with regard to water repellence. We introduce a recently developed trial that combines FTIR spectra with contact-angle data as the link between chemical composition of OM and the physical wetting behavior of soil particles. In addition to characterizing the wetting properties of OM coatings, we discuss the implications of water-repellent surfaces for different physical protection mechanisms of OM. For typical minerals, the OM loading on mineral surfaces is patchy, whereas OM forms nanoscaled micro-aggregates together with metal oxides and hydroxides and with layered clay minerals. Such small aggregates may efficiently stabilize OM against microbial decomposition. However, despite the patchy structure of OM coating, we observed a relation between the chemical composition of OM and wettability. A higher hydrophobicity of the OM appears to stabilize the organic C in soil, either caused by a specific reduced biodegradability of OM or indirectly caused by increased aggregate stability. In partly saturated nonaggregated soil, the specific distribution of the pore water appears to further affect the mineralization of OM as a function of wettability. We conclude that the wettability of OM, quantified by the contact angle, links the chemical structure of OM with a bundle of physical soil properties and that reduced wettability results in the stabilization of OM in soils.

Physical carbon-sequestration mechanisms under special consideration of soil wettability

[1] Humic-like substances (HULIS) were isolated by a solid-phase extraction procedure from PM2.5 fraction urban-type atmospheric aerosol samples collected in downtown Budapest, Hungary, in the nonheating season. Their amount was derived, and the surface tension properties of their pure solutions were investigated. Carbon content of HULIS accounted for 54% of the water-soluble organic carbon and for 19% of organic carbon in the aerosol. Solution of pure HULIS in concentrations corresponding to real incipient cloud droplets decreased the surface tension of water by about 30%, and the major decrease occurred within several tens of seconds. In diluted solutions, however, the thermodynamic equilibrium in surface tension was only reached after several hours, but the equilibrium depression value was still remarkable, about 18%. Detailed analysis of the relaxation curves implied that the kinetics of the surface tension depression should be regarded as and described by a diffusion-controlled process. The surface tension curves as a function of the HULIS concentration after an elapsed time of up to about 100 s resembled the curves observed earlier, but the shape of and tendency in the equilibrium curve (the isotherm) was rather different. The deviations were linked to physicochemical properties of certain classes of compounds within the HULIS. The surface tension depended on the solution pH as well; the smallest depression was observed at about pH = 5, and it was increased by an additional 13% for strong acidic or basic conditions; hence the role of surface tension in cloud droplet formation under acid rain conditions is further amplified.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2005JD007015

Surface tension of atmospheric humic-like substances in connection with relaxation, dilution, and solution pH

In structured soils, interaction of percolating water and reactive solutes with the soil matrix is often restricted to the outer surfaces of the preferential flow paths. Such surfaces of soil aggregates and biopores are mostly covered by organic matter (OM) that finally controls wettability, sorption, and transfer properties of the flow pathways. However, the local OM properties along such surfaces are largely unknown to date because the coatings are relatively thin and vulnerable. The objective of this study was to determine and compare the local two-dimensional distribution of soil OM composition at intact aggregate surfaces that serve as preferential flow paths. The Fourier transformed infrared spectroscopy in diffuse reflectance mode (diffuse reflectance infrared Fourier transform, DRIFT) was applied to determine transects and grids of OM functional group data (i.e., CH/CO ratios) on undisturbed and intact surfaces of soil aggregate samples using a DRIFT mapping procedure in 1-mm steps. The aggregate sample surfaces could be distinguished by DRIFT mapping in areas from earthworm burrows, root channels, and aggregate coatings. The water drop infiltration time of these structural surfaces appeared to correspond with CH/CO ratios for uncoated crack surfaces but less so for earthworm burrows. The results show that coatings at preferential flow-path surfaces differed locally in terms of OM composition, distribution, and possibly also in wettability, indicating yet unknown implications for preferential movement of water and reactive solutes.

DRIFT mapping of organic matter composition at intact soil aggregate surfaces.

Humic acids were extracted from two histosols, an andosol, an inceptisol, a rice field soil, and a sludge-amended cambisol and characterized by elemental analysis, acidic groups titration, E4/E6 determination, Fourier transform infrared (FTIR) and 13C nuclear magnetic resonance (13C NMR) spectroscop

Effect of the Chemical Composition of Soil Humic Acids on Their Viscosity, Surface Pressure, and Morphology

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Effect of the Chemical Composition of Soil Humic Acids on Their Viscosity, Surface Pressure, and Morphology