The Interaction of Pesticides with Humin Fractions and Their Potential Impact on Non-Extractable Residue Formation.

The constant influx of pesticides into soils is a key environmental issue in terms of their potential retention in the soil, thus reducing their negative impact on the environment. Soil organic matter (SOM) is an important factor influencing the environmental fate of these substances. Therefore, the aim of this research was to assess the chemical behavior of pesticides (flufenacet, pendimethalin, α-cypermethrin, metazachlor, acetamiprid) toward stable soil humin fractions (HNs) as a main factor affecting the formation of non-extractable residues of agrochemicals in soil. This research was conducted as a batch experiment according to OECD Guideline 106. For this purpose, HNs were isolated from eight soils with different physicochemical properties (clay content = 16-47%, pHKCl = 5.6-7.7, TOC = 13.3-49.7 g·kg-1, TN = 1.06-2.90 g·kg-1, TOC/TN = 11.4-13.7) to reflect the various processes of their formation. The extraction was carried out through the sequential separation of humic acids with 0.1 M NaOH, and then the digestion of the remaining mineral fraction with 10% HF/HCl. The pesticide concentrations were detected using GC-MS/MS. The pesticides were characterized based on the different sorption rates to HNs, according to the overall trend: metazachlor (95% of absorbed compound) > acetamiprid (94% of absorbed compound) > cypermethrin (63% of partitioning compound) > flufenacet (39% of partitioning compound) > pendimethalin (28% of partitioning compound). Cypermethrin and metazachlor exhibited the highest saturation dynamic, while the other agrochemicals were much more slowly attracted by the HNs. The obtained sorption kinetic data were congruous to the pseudo-first-order and pseudo-second-order models related to the surface adsorption and interparticle diffusion isotherm. The conducted research showed that the processes of pesticide sorption, apart from physicochemical phenomena, are also affected by the properties of the pollutants themselves (polarity, KOC) and the soil properties (SOM content, clay content, and pHKCl).

Effects of Hydrologic Regime Changes on a Taxonomic and Functional Trait Structure of Earthworm Communities in Mountain Wetlands.

Disturbances, both natural and anthropogenic, influence the patterning of species and species traits. The shift in species composition and distribution pattern of functional traits can demonstrate if the community is resistant, sensitive or resilient to the disturbance. Based on species- and trait-based approaches, we examined the response of the earthworm community to changing hydrologic conditions caused by the artificial drainage of mountain fens, in which cumulative effects of disturbance events over space and time are much less dynamic than in riverine wetlands. We hypothesized that the drainage-related changes of mountain fen peat soils have an effect on the earthworm community composition and its functional structure. We assume that the shift in species composition and value of community-weighted functional traits reflect changes in the resilience or resistance of the earthworm community to environmental change. Our results demonstrate that the total density of earthworms was almost three times lower under drained conditions compared to natural ones. Artificial drainage of fens had a neutral effect on the species-based diversity indices. However, there were species-specific traits that responded to hydrologic changes and which led to the species' replacements and to the co-occurrence of eurytopic, surface-browsing and more drought- and low-pH-resistant earthworm species in the drained fens. Based on these results, we conclude that abiotic-based environmental filtering was the main process responsible for sorting earthworms according to species and traits in the disturbed hydrologic conditions. The greater earthworm functional trait variations in semi-natural hydrologic conditions emphasizes the impact of transient dynamics in an altered disturbance regime on the earthworm assembly. Results also showed that in the changing hydrologic conditions of mountain fens, the functional trait approach revealed only slightly more predictive power than the taxonomic one, but it proved better with processes responsible for earthworm species filtering.

Sorption of Organic Contaminants by Stable Organic Matter Fraction in Soil.

Soil organic matter (SOM) and its heterogeneous nature constitutes the main factor determining the fate and transformation of organic chemicals (OCs). Thus, the aim of thus research was to analyze the influence of the molecular chemodiversity of a stable SOM (S-SOM) on the sorption potential of different groups of OCs (organochloride pesticides­OCPs, and non-chlorinated pesticides­NCPs, polycyclic aromatic hydrocarbons­PAHs). The research was conducted as a batch experiment. For this purpose, a S-SOM was separated from six soils (TOC = 15.0−58.7 gkg−1; TN = 1.4−6.6 gkg−1, pH in KCl = 6.4−7.4 and WRB taxonomy: fluvisols, luviosols, leptosols) by alkaline urea and dimethylsulphoxide with sulfuric acid. Isolated S-SOM fraction was evaluated by UV−VIS, FT-IR and EEM spectroscopy to describe molecular diversity, which allowed the assessment of its potential sorption properties regarding OCs. In order to directly evaluate the sorption affinity of individual OCs to S-SOM, the mixture of the 3 deuterated contaminants: chrysene (PAHs), 4,4'DDT (OCPs) atrazine (NCPs) were applied. The sorption experiment was carried out according to the 106 OECD Guidelines. The OCs concentration was analyzed by gas chromatography triple mass spectrometry (GC-MS/MS). OCs were characterized by different sorption rates to S-SOM fractions according to the overall trend: atrazine (87.5−99.9%) > 4,4'DDT (64−81.6%) > chrysene (35.2−79.8%). Moreover, atrazine exhibited the highest saturation dynamic with fast bounding time amounting to 6 h of contact with S-SOM. Proportionally, the chrysene showed the slowest binding time achieving an average of 55% sorption after 78 h. Therefore, S-SOM isolated from different soils demonstrated varying binding capacity to OCs (CoV = 21%, 27% and 33% for atrazine, DDT and chrysene, respectively). Results indicate that each sample contains S-SOM with different degrees of transformation and sorption properties that affect the OCs availability in soil. Spectroscopic analyses have shown that the main component of S-SOM are biopolymers at various stages of transformation that contain numerous aromatic−aliphatic groups with mostly hydrophilic substituents.

Vascular plant and cryptogam abundance as well as soil chemical properties shape microbial communities in the successional gradient of glacier foreland soils.

In the glacier forelands, microbes play a fundamental role in soil development and shaping the vegetation structure. Such ecosystems represent various stages of soil development and are, therefore, an excellent place to study the interrelationship between soil, plants, and microorganisms. The aim of the study was to assess the effects of vegetation and soil physicochemical properties developing after glacier retreat on soil microbial communities. Specifically, abundance, species richness and the composition of arbuscular mycorrhizal fungi (AMF), as well as microbial biomass and community structure in soils were compared between plots established in 800-meter transects of three glacier forelands in northern Sweden. The cover of vascular plants and cryptogams, soil C content, AMF spore density and species richness, AMF biomass indicators, total microbial biomass, and bacterial phospholipid fatty acids (PLFA) were significantly and positively related to the distance from the glacier terminus. On the other hand, macronutrient concentrations and pH decreased along with increasing distance. No significant impact of the distance from the glacier terminus on the ratio fungal/bacterial PLFA was observed. Moreover, we found a significant effect of both glacier and the distance from the glacier terminus on the microbial community structure. AMF species richness and spore density in the glacier forelands were generally low, which is probably due to a limited supply of inoculum in primary successional ecosystems. Most microbial biochemical markers and AMF parameters were positively associated with the number of arbuscular mycorrhizal plant species and vascular plant and lichen cover as well as C content in soil, whereas negatively with soil macronutrients and pH. This could be related to an increase in plant cover and a decrease in soil nutrient levels as plant succession progresses. Our results showed that vegetation, soil C content, and microbial communities are interlinked and exhibit concordant patterns along successional gradients.

Optimized isolation method of humin fraction from mineral soil material.

Humic substances, including humin fraction, play a key role in the fate of organic and inorganic xenobiotics contaminating the environment. Humin is an important fraction of humic substances, which has been the least studied to date. This is due to the difficulties connected with its isolation that pose a number of methodological problems. Methods of humin fraction isolation can be divided into following main groups: (1) digestion of mineral soil components with HF/HCl followed by alkali extraction of HA and FA; (2) alkali extraction of HA and FA followed by extraction of humin by different organic solvents; and (3) alkali extraction of HA and FA followed by HF/HCl digestion of mineral soil components. Nevertheless, each of these methods has different limitations. We described in detail a useful procedure of humin isolation, in which this fraction was not extracted, but isolated from the soil by removing its soluble organic and mineral components. A modified method of HA and FA extraction with 0.1 M NaOH, according to the International Humic Substances Society, was used in the first step. Then, the mineral components in the residue were digested with the 10% HF/HCl. Unlike the procedures oriented to increase the concentration of organic matter, samples were treated several times with the HF/HCl mixture until the mineral fraction was almost completely digested. The main assumption of the method modification was to obtain the highest yield with the lowest possible ash content, but without affecting humin chemical structure. The results showed that the proposed procedure is characterized by a high efficiency and recovery and, therefore, it can be used to isolate high amounts of humin from soil.

The effects of humic substances on DNA isolation from soils.

BACKGROUND: Humic substances (HS) are compounds with a complicated structure, present in the humus soil layer, water, lake sediments, peat, brown coal and shales. Due to their similar physicochemical properties to DNA, they may have an adverse effect on the subsequent use of the isolated material. The main aim of this research was to examine the effect of HS on DNA isolation depending on the soil type and land use, taking into account the spectroscopic full characteristics of HS fractions. METHODS: The research was conducted on eight types of soil sample. Soils represented the most important Soil Reference Groups for temperate climates: Fluvisols, Regosols, Cambisols, Arenosols, Histosols and Luvisols. Soil samples were also collected from areas diversified in terms of use: arable land, grassland and forest. The extraction of HS fractions was performed using the procedure recommended by the International HS Society. The fractional composition of HS was characterized by UV-Vis and fluorescence methods. Soil DNA is extracted by direct cell lysis in the using a CTAB-based method with a commonly-used commercial soil DNA isolation kit. The basis for assessing the quantity and quality of extracted DNA was the Polymerase chain reaction (PCR) reaction since the analysis of soil DNA often relies on the use of PCR to study soil microorganisms. RESULTS: Based on the results, it can be concluded that in the presence of a high concentration of HS, the isolated DNA was low quality and the additional purification procedure was necessary. Despite the differentiation of the internal structure of HS fractions, the decisive factor in the efficiency of DNA isolation from soil samples was the total carbon content in HS. Reduced DNA yields can significantly constrain PCR detection limits to levels inadequate for metagenomic analysis, especially from humus-rich soils.

Photosensitizing properties of water-extractable organic matter from soils.

Water-extractable organic matter (WEOM) was extracted using pure water from two black soils and from the Elliott reference soil of the International Humic Substances Society (IHSS). WEOMs were characterized by chemical and spectroscopic methods. The apparent quantum yields of singlet oxygen, triplet excited states and hydroxyl radicals formation upon irradiation within the wavelength range 290-450 nm were determined using chemical probes and compared to those of standard Elliott humic substances. In general, the aromatic content, as measured by the SUVA value, was close in WEOMs and humic substances, while the E2/E3 was higher and the humification index lower in the former. Quantum yield values measured for WEOMs fell within the range of those found for basic medium extracted humic substances or were even higher in one case. Thus, water soluble aromatic moiety of the soil organic matter, especially those with low humification degree, is important for the photosensitizing properties. We also found that WEOMs sensitized the bisphenol A phototransformation with rates of the same order of magnitude for all the samples.