Purpose The objective of this study was to evaluate the mutual relations between the soil organic matter (SOM) fractions: fulvic acids (FA), humic acids (HA), humins (HN), black carbon (BC) and the polycyclic aromatic hydrocarbons (PAH) accumulation level in agricultural soils influenced by historical and actual anthropopressure. The research allowed to indicate which fractions of SOM are the major sequestration sinks for PAHs after they are naturally introduced into the soil. Materials and methods Soil samples were collected from the upper layer of agricultural soils (n = 41), and basic physicochemical properties (pH_KCl, total carbon, total nitrogen and clay content) were determined. The SOM was characterised by the total organic carbon content and humic substances, including HA, FA and HN, determined by an adapted method recommended by the International Humic Substances Society. The extracts of HA and FA were analysed for carbon content using a liquid CN analyser, while HN constituted the soil carbon in the residue after FA and HA extraction. The content of BC was analysed by dry combustion at 375 °C for 24 h (CTO375); the remaining carbon was determined via combustion in an elemental analyser. Results and discussion In all soils, significant positive relations between PAH concentrations and TOC content (r = 0.73, p < 0.001) as well as HN (r = 0.71, p < 0.001) and BC (r = 0.86, p < 0.001) were noted. Relations among PAHs, HN and BC were statistically significant only in soils with TOC content ≥ 12 g kg⁻¹, while they were not observed for soils with TOC content < 12 g kg⁻¹. The links between HN and PAHs were stronger for low-molecular (two and three rings)-weight PAHs (r = 0.77, p < 0.05) than for high-molecular (≥ four rings) PAHs (r = 0.68, p < 0.05). Contrary to HN, the BC faction showed higher correlations with high-molecular-weight PAHs (r = 0.92, p < 0.001). FA and HA showed no significant relationship with hydrocarbons. Conclusions Different SOM fractions might possess divergent binding capabilities and dissimilar binding strengths to PAHs. The different proportions and sorption capacities of BC and HN in relation to PAHs of different molecular weight are the result of varying structure, i.e. polar and non-polar functionalities in sorption domains and pore-size structures of these fractions. The high correlation between BC and higher-molecular PAHs may be a result of their co-emission, while the stronger relationships between HN and lower-molecular PAHs are directly related to their higher mobility and easier diffusion to stable SOM fractions.

The objective of this paper was to investigate the molecular characterization of soil organic matter fractions (humic substances (HS): fulvic acids-FAs, humic acids-HAs, and humins-HNs), which are the most reactive soil components. A wide spectrum of spectroscopic (UV–VIS and VIS–nearIR), as well as electrochemical (zeta potential, particle size diameter, and polydispersity index), methods were applied to find the relevant differences in the behavior, formation, composition, and sorption properties of HS fractions derived from various soils. Soil material (n = 30) used for the study were sampled from the surface layer (0–30 cm) of agricultural soils. FAs and HAs were isolated by sequential extraction in alkaline and acidic solutions, according to the International Humic Substances Society method, while HNs was determined in the soil residue (after FAs and HAs extraction) by mineral fraction digestion using a 0.1M HCL/0.3M HF mixture and DMSO. Our study showed that significant differences in the molecular structures of FAs, Has, and HNs occurred. Optical analysis confirmed the lower molecular weight of FAs with high amount of lignin-like compounds and the higher weighted aliphatic–aromatic structure of HAs. The HNs were characterized by a very pronounced and strong condensed structure associated with the highest molecular weight. HAs and HNs molecules exhibited an abundance of acidic, phenolic, and amine functional groups at the aromatic ring and aliphatic chains, while FAs mainly showed the presence of methyl, methylene, ethenyl, and carboxyl reactive groups. HS was characterized by high polydispersity related with their structure. FAs were characterized by ellipsoidal shape as being associated to the long aliphatic chains, while HAs and HNs revealed a smaller particle diameter and a more spherical shape caused by the higher intermolecular forcing between the particles. The observed trends directly indicate that individual HS fractions differ in behavior, formation, composition, and sorption properties, which reflects their binding potential to other molecules depending on soil properties resulting from their type. The determined properties of individual HS fractions are presented as averaged characteristics over the examined soils with different physico-chemical properties.

Soil contamination with petroleum, especially in the area of oil wells, is a serious environmental problem. Restoring soil subjected to long-term pollution to its original state is very difficult. Under such conditions, unique bacterial communities develop in the soil that are adapted to the contaminated conditions. Analysis of the structure and function of these microorganisms can be a source of valuable information with regard to bioremediation. The aim of this study was to evaluate structural and functional diversity of the bacterial communities in soils with long-term impacts from petroleum. Samples were taken from the three oldest oil wells at the Crude Oil Mine site in Węglówka, Poland; the oldest was established in 1888. They were collected at 2 distances: (1) within a radius of 0.5 m from the oil wells, representing soil strongly contaminated with petroleum; and (2) 3 m from the oil wells as the controls. The samples were analyzed by 16S rRNA sequencing and the community level physiological profiling (CLPP) method in order to better understand both the genetic and functional structure of soil collected from under oil wells. Significant differences were found in the soil samples with regard to bacterial communities. The soils taken within 0.5 m of the oil wells were characterized by the highest biodiversity indexes. Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria were strongly correlated with biological activity in these soils. Families of Alphaproteobacteria were also dominant, including: Bradyrhizobiaceae, Rhizobiaceae, Rhodobacteraceae, Acetobacteraceae, Hyphomicrobiaceae, and Sphingomonadaceae. The study showed that the long term contamination of soil changes bacterial communities and their metabolic activity. Even so, natural bioremediation leads to the formation of specific groups of bacteria that actively grow at the site of contamination in the soil.

Polycyclic aromatic hydrocarbons (PAHs) exhibit persistence in soils, and most of them are potentially mutagenic/carcinogenic and teratogenic for human beings but also influence the growth and development of soil organisms. The PAHs emitted into the atmosphere are ultimately deposited (by dry or wet deposition processes) onto the soil surface where they tend to accumulate. Soil organic matter (SOM) plays an important role in the fate and transformation processes of PAHs, affecting their mobility, availability, and persistence. Therefore, the aim of this research was to investigate the influence of SOM fractional diversification (fulvic acids—FA, humic acids—HA, and humins—HN) on PAH availability and persistence in soils. Twenty soil samples (n = 20) were collected from upper horizons (0–30 cm) of agricultural soils exposed to anthropogenic emissions from industrial and domestic sources. The assessment of PAH concentrations included the determination of medium-molecular-weight compounds from the US EPA list: fluoranthene—FLA, pyrene—PYR, benz(a)anthracene—BaA, and chrysene—CHR. The assessment was conducted using the GC-MS/MS technique. Three operationally defined fractions were investigated: total extractable PAHs (TE-PAHs) fraction, available/bioavailable PAHs (PB-PAHs) fraction, and nonavailable/residual PAHs (RE-PAHs) fraction, which was calculated as the difference between total and available PAHs. TE-PAHs were analyzed by dichloromethane extraction, while PB-PAHs were analyzed with a hydrophobic β-cyclodextrin solution. SOM was characterized by total organic carbon content (Turin method) and organic carbon of humic substances including FA, HA, HN (IHSS method). Concentrations of PAHs differed between soils from 193.5 to 3169.5 µg kg⁻¹, 4.3 to 226.4 µg kg⁻¹, and 148.6 to 3164.7 µg kg⁻¹ for ∑4 TE-PAHs, ∑4 PB-PAHs, and ∑4 RE-PAHs, respectively. The ∑4 PB-PAHs fraction did not exceed 30% of ∑4 TE-PAHs. FLA was the most strongly bound in soil (highest content of RE-FLA), whereas PYR was the most available (highest content of PB-PYR). The soils were characterized by diversified total organic carbon (TOC) concentration (8.0–130.0 g kg⁻¹) and individual SOM fractions (FA = 0.4–7.5 g kg⁻¹, HA = 0.6–13.0 g kg⁻¹, HN = 0.9–122.9 g kg⁻¹). FA and HA as the labile fraction of SOM with short turnover time strongly positively influenced the potential ∑4 PAH availability (r = 0.56 and r = 0.52 for FA and HA, respectively). HN, which constitutes a stable fraction of organic matter with high hydrophobicity and poor degradability, was strongly correlated with ∑4 RE-PAHs (r = 0.75), affecting their persistence in soil.

Pesticides belong to a group of xenobiotics harmful to humans and wildlife, whose fate and activity depends on their susceptibility to degradation. Therefore, the monitoring of their residue level in agricultural soils is very important because it provides very valuable information on the actual level of soil contamination and environmental risk resulting from their application. The aim of this study was to evaluate contemporary concentrations of organochlorine (OCPs) and non-chlorinated pesticides (NCPs) in arable soils of Poland as an example of Central and Eastern European countries. The results were assessed in relation to Polish regulations, which are more restrictive compared to those of other European countries. The sampling area covered the territory of arable lands in Poland (216 sampling points). The distribution of sampling points aimed to reflect different geographical districts, conditions of agricultural production, and various soil properties. The collected soil samples were extracted with organic solvents in an accelerated solvent extractor (ASE 2000). The OCPs, including α-HCH, β-HCH, γ-HCH, and p,p’DDT, p,p’DDE, and p,p’DDD, were extracted with a hexane/acetone mixture (70:30 v/v) and determined by gas chromatography with an electron capture detector (GC-μECD). NCPs included atrazine, carbaryl, and carbofuran were extracted with a dichloromethane/acetone mixture (50:50 v/v), while maneb was extracted by intensive shaking the sample with acetone (1:1 v/v) and ethylenediamine-tertraacetic acid. The NCPs were identified by a dual mass- spectrometry (GC-MS/MS). The total content of individual OCPs ranged from 0.61 to 1031.64 µg kg⁻¹, while the NCP concentrations were significantly lower, from 0.01 to 43.92 µg kg⁻¹. DDTs were detected in all soils samples (p,p’DDD (23.60 µg kg⁻¹) > p,p’DDT (18.23 µg kg⁻¹) > p,p’DDE (4.06 µg kg⁻¹), while HCHs were only in 4% of the analyzed samples (β-HCH (339.55 µg kg⁻¹) > α-HCH (96.96 µg kg⁻¹) > γ-HCH (3.04 µg kg⁻¹)), but in higher values than DDTs. Among NCPs, higher concentration was observed for carbaryl (<0.01–28.07 µg kg⁻¹) and atrazine (<0.01–15.85 µg kg⁻¹), while the lower for carbofuran (<0.01–0.54 µg kg⁻¹). Maneb was not detected in analyzed soils. Assessment of the level of soil pollution based on Polish regulations indicated that several percentages of the samples exceeded the criterion for OCPs, such as ∑3DDTs (14 samples; 6.5% of soils) and HCH congeners (α-HCH in one sample; 0.5% of soils), while NCP concentration, such as for atrazine, carbaryl and carbofuran were below the permissible levels or were not detected in the analyzed soils, e.g., maneb. The obtained results indicated that residues of the analyzed pesticides originate from historical agricultural deposition and potentially do not pose a direct threat to human and animal health. The behavior and persistence of pesticides in the soils depend on their properties. Significantly lower NCP concentration in the soils resulted from their lower hydrophobicity and higher susceptibility to leaching into the soil profile. OCPs are characterized by a high half-life time, which affect their significantly higher persistence in soils resulting from affinity to the soil organic phase.