Concentration of Potentially Toxic Elements in Farmed Fallow Deer Antlers Depending on Diet and Age.

Deer antlers, usually harvested annually on a farm, are an accessible material used to determine the exposition to potentially toxic elements, PTEs, during growth. Moreover, the study of antlers from animals of different ages allows the assessment of long-term exposition to these elements. The aim of the study was to analyze the concentration of eight potentially toxic elements (Cd, Pb, As, Ba, Ni, Sr, La, Ce) in individual positions of the antlers (first, second, and third position, corresponding to the stages of development and life of these animals) and in the food that the animals consumed during the growth of individual antler fragments, depending on the age of the farmed fallow deer (Dama dama). The mineral composition of samples was analyzed using inductively coupled plasma mass spectrometry (ICP-MS). The analysis included 31 male deer aged 2-8 years old. The average concentration of Pb, Ba, and Ni was higher in the second position of the antler, and As, La, and Ce in the third position. In addition, the oldest individuals showed a higher Cd, Pb, and As concentration in the third position. A significant positive relationship was found between the age of animals and accumulation of As (r = 0.582, p < 0.05), as well as Ba and Sr (r = -0.534, r = -0.644 at p < 0.05, respectively). The average content of Ba and Sr also significantly negatively depended on body mass and antler mass stags (r = -0.436, r = -0.515 at p < 0.05, respectively). Cd concentration in feed was significantly higher in June compared to winter, spring, and later summer (p < 0.05). On the other hand, the concentration of Ba in food was significantly higher in spring and winter than in early and later summer (p < 0.05). An increase in the PTEs in the pasture determined the concentration of these components in fallow deer antlers.

Microbial Community Response to Various Types of Exogenous Organic Matter Applied to Soil.

Recycling of solid biowaste and manure would reduce the dependence of agriculture on synthetic products. Most of the available studies on the effects of exogenous organic matter (EOM) application to soil were focused on nutrients and crop yield, with much less attention to microbiological processes in soil, especially using modern molecular methods. The aim of this study was to evaluate the effects of various types of manure, sewage sludge and bottom sediment on the biochemical activity and biodiversity of soil and plant yield in a pot experiment. The soil was treated with a range of EOM types: six types of manure (cattle, pig, goat, poultry, rabbit and horse manure; two bottom sediments (from urban and rural systems); and two types of municipal sewage sludge. All EOMs stimulated dehydrogenases activity at a rate of 20 t ha-1. Alkaline phosphatase was mostly stimulated by poultry manure and one of the sludges. In general, the two-fold greater rate of EOMs did not further accelerate the soil enzymes. The functional diversity of the soil microbiome was stimulated the most by cattle and goat manure. EOMs produce a shift in distribution of the most abundant bacterial phyla and additionally introduce exogenous bacterial genera to soil. Poultry and horse manure introduced the greatest number of new genera that were able to survive the strong competition in soil. EOMs differentiated plant growth in our study, which was correlated to the rate of nitrate release to soil. The detailed impacts of particular amendments were EOM-specific, but in general, no harm for microbial parameters was observed for manure and sludge application, regardless of their type. There was also no proof that the PAH and pesticide contents measured in manure or sludge had any effect on microbial activity and diversity.

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).

The screening method for use of wild pheasant feathers in the monitoring of environmental pollution with heavy metals.

It has been shown that some species of birds, especially herbivorous and territorial ones, are more sensitive to the effects of toxic substances compared to mammals. This allows for taking integrated actions in the area of environmental protection and monitoring in a holistic sense (at various trophic levels). Therefore, this study aimed to assess the possibility of using pheasant feathers (Phasianus colchicus) as a potential bioindicator ofenvironmental contamination, and thus to determine the concentration of heavy metals (lead-Pb, arsenic-As, cadmium-Cd, chromium-Cr, nickel-Ni, and zinc-Zn) in the analyzed tissue of animals inhabiting the forest districts of the Lubartów, Tomaszów, Skierniewice, and Ostrowiec Swietokrzyski areas. The chemical analysis used to determine the concentration of toxic elements in pheasant feathers was carried out by inductively coupled plasma mass spectrometry. The highest concentrations of Cr and Zn were found in birds from the Lubartów Forest District (1.93 mg/kg and 120.63 mg/kg, respectively), As and Ni in the Tomaszów Forest District (0.55 mg/kg and 1.60 mg/kg, respectively), Cd in the Lubartów Forest District and Skierniewice (0.04 mg/kg), and Pb in the Skierniewice Forest Distict (6.79 mg/kg). The observed results were strongly related to soil contamination and urbanization index, as key environmental factors which significantly determine the metal content in pheasant feathers. Therefore, proposed non-invasive measurements of the elemental composition of feathers of birds living in specific areas may be an important indicator of environmental pollution in relation to the high impact of anthropopressure.

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.

Effect of sorption properties on the content, ecotoxicity, and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in bottom sediments.

Polycyclic aromatic hydrocarbons (PAHs) tend to accumulate in the sediment due to their high hydrophobicity. Despite PAHs have been the subject of several reviews, PAH sorption processes in bottom sediments has not been comprehensively discucorrelation coefficients between sorption parameters and contessed. Understanding the dependencies governing PAH sorption processes will allow to predict, monitor, and mitigate the ecological effects of PAH contamination and the associated risks to humans or wildlife. The objectives of the study were to assess the relationship between the sorption properties and the content of PAHs in bottom sediments and mussels. The PAH profile was dominated by higher-molecular hydrocarbons, which accounted for 73% of the total concentration of PAHs. Potentiometric studies revealed the steric-based PAH sorption mechanism that strongly depended on the presence of negatively dissociating structures such as carboxylic or phenolic functional groups. Based on the changes in Q8 values, the size-exclusion effect was more likely for 5- and 6-ring compounds. Pores < 5 µm, which had the largest share in the specific surface area, were the preferred sites for PAH sequestration and stabilization in bottom sediments. The availability of PAHs was reduced in sediments with high organic matter content. The PAH bioaccumulation factor significantly decreased with increasing TOC content in sediments. Higher mortality and growth inhibition of H. incongruens were observed in samples with high and medium TOC contents than in those with low TOC content.

Concentration of Macroelements and Trace Elements in Farmed Fallow Deer Antlers Depending on Age.

The mineral content of the antlers reflects the nutritional status and specific stage of bone growth in cervid males. Therefore, this research aimed to analyze the concentration of Ca, P, Mg, K, Na, Li, V, Cr, Mn, Co, Cu, Zn, Se and Mo in three characteristic antler positions selected based on the observation of fights between males. These were compared between farmed fallow deer (Dama dama) of different ages. The mineral compositions of tissues were analyzed using inductively coupled plasma mass spectrometry. The highest mean concentrations of macroelements (except K) were recorded in the youngest animals aged 2 or 3 years in the proximal position of the antlers. With age and distance from the skull, Ca, P, Mg and Na contents decreased, while K increased. Higher mean concentrations of most trace elements (Cr, Mn, Co, Cu, Zn) were recorded in 3-year-old animals in antler distal positions. With an increase in the age, body mass and antler mass of fallow deer, the concentration of Ca, P, Mg, K, Mn, Cu and Zn decreased (−0.414 ≤ R ≤ −0.737, p < 0.05) in the studied tissue, whereas Li increased (0.470 ≤ R ≤ 0.681, p < 0.05). The obtained results confirm that the antlers' chemical composition changes with age, also changing the Ca:P ratio.

Diffuse Reflectance Spectroscopy for Black Carbon Screening of Agricultural Soils under Industrial Anthropopressure.

Visible and near-infrared spectroscopy (VIS-NIRS) is a fast and simple method increasingly used in soil science. This study aimed to investigate VIS-NIRS applicability to predict soil black carbon (BC) content and the method's suitability for rapid BC-level screening. Forty-three soil samples were collected in an agricultural area remaining under strong industrial impact. Soil texture, pH, total nitrogen (Ntot) and total carbon (Ctot), soil organic carbon (SOC), soil organic matter (SOM), and BC were analyzed. Samples were divided into three classes according to BC content (low, medium, and high BC content) and scanned in the 350-2500 nm range. A support vector machine (SVM) was used to develop prediction models of soil properties. Partial least-square with SVM (PLS-SVM) was used to classify samples for screening purposes. Prediction models of soil properties were at best satisfactory (Ntot: R2 = 0.76, RMSECV = 0.59 g kg-1, RPIQ = 0.65), due to large kurtosis and data skewness. The RMSECV were large (16.86 g kg-1 for SOC), presumably due to the limited number of samples available and the wide data spread. Given our results, the VIS-NIRS method seems efficient for classifying soil samples from an industrialized area according to BC content level (training accuracy of 77% and validation accuracy of 81%).

The Mineral Composition of Bone Marrow, Plasma, Bones and the First Antlers of Farmed Fallow Deer.

An adequate supply of essential nutrients is particularly important during the skeletal growth and development of young deer, especially in males, who build new antlers each year. The aim of the research was to analyze the levels of 21 mineral elements (including the bulk elements: Ca, P, Mg, K, Na; trace elements: Li, Cr, Mn, Co, Cu, Zn, Se, Mo; and toxic elements: Be, Al, As, Cd, Sb, Ba, Pb, Ni) in the bone marrow, plasma, bones, and first antlers of farmed fallow deer (Dama dama). The mineral compositions of tissues were analyzed using inductively coupled plasma mass spectrometry. Higher concentrations of Ca, P, Mg, Cr, Zn, Se, Al, Ba and Ni were found in bone marrow than in plasma. The highest concentrations of Ca, P and Ba were recorded in fallow deer bone, while the highest concentrations of Mg, K, Na, Li, Cr, Mn, Co, Cu, Zn, Se, Mo, Be, Al, As, Sb, Pb and Ni were found in the antlers. Moreover, the research showed a significant negative relationship between Ca and Cd, and between Ca and Pb, and P and Pb (rS = −0.70, rS = −0.80, and rS = −0.66, respectively; p < 0.05) in the tissues.

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.

Comparison of the accumulation of macro- and microelements in the bone marrow and bone of wild and farmed red deer (Cervus elaphus).

BACKGROUND: The cells of the entire body, including the skeletal system, especially of young animals, may derive from the bone marrow in which they multiply. Therefore, it is important to assess whether the diet and quality of life of deer have a significant impact on the elemental composition of bone and bone marrow, which can directly affect their health and growth. The aim of this study was to determine the concentrations of macro- (Ca, calcium, P, phosphorus, Mg, magnesium, K, potassium, Na, sodium) and microelements (Li, lithium, Cr, chromium, Mn, manganese, Co, cobalt, Cu, copper, Zn, zinc, Se, selenium, Mo, molybdenum, and Sn, tin) accumulated in the bone marrow and bones of deer (Cervus elaphus). The study was carried out on 15 young stags divided into two groups: farmed and wild animals. The concentrations of macro- and microelements were analysed using the inductively coupled plasma mass spectrometry technique. This research expands our knowledge on this topic, which so far has not been extensively studied. RESULTS: The mean content of K, Na, Zn and Se in the bone marrow of farmed animals was significantly higher than in wild deer, whereas the mean content of Ca, P, Mg, K, Na and Li in the bones was higher in wild animals than in farmed individuals (p < 0.05). In addition, the mean concentration of Cr, Mn, Cu, Se and Mo in the bones of the analysed animals differed significantly (p < 0.05) and was higher in the farmed deer. The mean concentration of Se in the bone marrow of wild deer decreased with the increase of the body weight (p < 0.05). In turn, the mean content of Mn in the bone marrow and of Mo in the bones of the animals was significantly positively correlated with the animals' body weight (p < 0.05). CONCLUSIONS: The obtained results indicated different levels of micro- and macro-components in the body of farmed and wild deer, though without clear and strong variations. Generally, the higher level of macronutrients in the bones of wild deer may be related to the higher physiological importance of these minerals for life activities in the natural environment and to the limited supply of balanced food. On the other hand, the higher levels of microelements in the tissues of farmed animals may result from their significantly better nutritional status in the first year of life, achieved through appropriate nutrition as well as diet supplementation of adult females.

Accumulation of Toxic Elements in Bone and Bone Marrow of Deer Living in Various Ecosystems. A Case Study of Farmed and Wild-Living Deer.

The aim of the study was to determine the concentrations of toxic elements accumulated in the bone marrow and bones (Cervus elaphus). The studies were carried out on two groups of young stags: farmed (n = 6) and wild (n = 9). Their body weights were measured and bone and bone marrow samples were collected. The concentrations of toxic elements were analyzed using the inductively coupled plasma mass spectrometry technique. The mean aluminum content in the bone marrow and bones of the farmed animals was significantly higher than in the wild group (p < 0.05). The mean concentration of arsenic, barium and lead in the bones of the wild red deer was significantly higher than in the bones of the farmed animals (p < 0.05), while the cadmium concentration in the bones of the farmed red deer exceeded the value determined in the wild animals. A significant difference was found between the mean concentrations of aluminum, arsenic, barium, lead, vanadium and nickel in the bone marrow and bones of both red deer groups (p < 0.05). Although the study involved animals living in an uncontaminated area, the concentrations of some heavy metals were higher than values reported from industrial regions.

Fungal Community, Metabolic Diversity, and Glomalin-Related Soil Proteins (GRSP) Content in Soil Contaminated With Crude Oil After Long-Term Natural Bioremediation.

Fungi have increased tolerance to environmental stress (also related to the access of pollutants, e.g., trace elements and polycyclic aromatic hydrocarbons PAHs). The aim of the study was to evaluate the mycobiome and functional diversity of fungi in long-term crude-oil contaminated soils as the potential bioremediators of oil contaminated sites. Samples were taken from three historical oil wells (over a century old) at two distances: within a 0.5 m radius of the oil wells (OWP1, OWP2, and OWP3) and within a 3 m radius from the oil wells as the controls (OW1, OW2, and OW3). Next generation sequencing (for the ITS region) was accompanied with determination of the functional fungal community based on Biolog FFPlates, glomalin related soil protein (GRSP) content, trace element and PAHs concentration. The research hypothesis assumed that long-term natural bioremediation of crude oil contaminated soils can contribute to intensive development of a unique fungal community adapted to the contamination conditions. The identification of such fungi can be of particular importance in soil bioremediation. There were significant differences in the fungal community and functional diversity between the soil samples. The soils collected directly from the oil wells were characterized by higher biological activity and higher diversity of PAH-degrading fungal candidates compared to the soils collected within 3 m of the oil wells. The total glomalin-related soil proteins (T-GRSP) and easily-extractable glomalin-related soil proteins (EE-GRSP) contents were lower in soil samples taken directly from the crude oil well. The control soil (OW) subjected to a long-term natural remediation may already have sufficient conditions for the growth and development of mycorrhizal fungi. The mycobiome of the soils collected directly from the oil wells (OWP1, OWP2, and OWP3) was characterized by a 35% share of PAH-degrading candidates, compared to the soil collected at the 3 m distance from the oil wells (OW1, OW2, and OW3) at < 5%. The main PAH-degrading fungal candidates belong to genera Ilyonectria, Chaetomium, Gibberella, Paraphoma, Schizothecium, Pseudorobillarda, Tetracladium, Ganoderma, Cadophora, Exophiala, Knufia, Mycoleptodiscus, Cyphellophora, Fusicolla, Devriesia, Didymella, Plenodomus, Pyrenochaetopsis, Symbiotaphrina, Phallus, Coprinellus, Plectosphaerella, Septoriella, and Hypholoma. The share of three- and four-ringed PAHs in soil was higher as the distance from the oil well increased. These results may indicate that more effective degradation processes occur closer to the oil wells.

The Impact of Organic Matter on Polycyclic Aromatic Hydrocarbon (PAH) Availability and Persistence in Soils.

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 ß-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.

Residues of Persistent Organic Pollutants (POPs) in Agricultural Soils Adjacent to Historical Sources of Their Storage and Distribution-The Case Study of Azerbaijan.

The aim of this study was to identify and examine the levels of organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) in soil collected from the surroundings of historical pesticide storage facilities on former agricultural aerodromes, warehouses, and pesticide distribution sites located in the most important agricultural regions in Azerbaijan. The conducted research included determination of three groups of POPs (occurring together), in the natural soil environment influenced for many years by abiotic and biotic factors that could have caused their transformations or decomposition. In this study, soil samples were collected in 21 georeferenced points located in the administrative area of Bilasuvar, Saatly, Sabirabad, Salyan and Jalilabad districts of Azerbaijan. Soil chemical analysis involved determination of organochlorine compounds (OCP): hexachlorocyclohexanes (HCHs) (three isomers α-HCH, ß-HCH and γ-HCH) and dichlorodiphenyltrichloroethanes (DDTs) (six congeners 2,4'DDT; 4,4'DDT; 2,4'DDE; 4,4'DDE; 2,4'DDE; and 4,4'DDE); polycyclic aromatic hydrocarbons (PAHs): 16 compounds from the United States Environmental Protection Agency US EPA list and, PCBs (seven congeners identified with the following IUPAC numbers: 28, 52, 101, 118, 138, 153, and 180). Our research showed that OCPs reached the highest concentration in the studied areas. The total concentrations of OCPs ranged from 0.01 to 21,888 mg∙kg-1 with significantly higher concentrations of Σ6DDTs (0.01 µg kg-1 to 21880 mg kg-1) compared to ΣHCH (0.14 ng kg-1 to 166.72 µg kg-1). The total concentrations of PCBs in the studied soils was varied from 0.02 to 147.30 µg·kg-1 but only PCB138 and PCB180 were detected in all analyzed samples. The concentrations of Σ16 PAHs were also strongly diversified throughout the sampling areas and ranged from 0.15 to 16,026 mg kg-1. The obtained results confirmed that the agricultural soils of Azerbaijan contained much lower (up to by three orders of magnitude) concentrations of PCBs and PAHs than DDT. It is supported by the fact that PCBs and PAHs were not directly used by agriculture sector and their content results from secondary sources, such as combustion and various industrial processes. Moreover, the high concentrations of PAHs in studied soils were associated with their location in direct neighborhood of the airport, as well as with accumulation of contaminants from dispersed sources and long range transport. The high concentrations of pesticides confirm that deposition of parent OCPs have occurred from obsolete pesticide landfills.

Assessment of Pesticide Residue Content in Polish Agricultural Soils.

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, ß-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 (ß-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.

Genetic and Functional Diversity of Bacterial Microbiome in Soils With Long Term Impacts of Petroleum Hydrocarbons.

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 Weglówka, 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.

The impact of selected soil organic matter fractions on the PAH accumulation in the agricultural soils from areas of different anthropopressure.

The level of 16PAH accumulation was determined in 75 soil samples collected from two agricultural regions of Poland corresponding to the smallest Polish administrative unit at the LAU 2 level. Both regions are characterised by similar territory and soil cover but different history of pollution and different pressure of anthropogenic factors. Overall accumulation of Σ16PAHs in the upper soil layer was within a wide range with the median value of 291 and 1253 µg kg-1 for a non-contaminated and high anthropopressure region, respectively. Nearly 75 % of the total polycyclic aromatic hydrocarbon (PAH) pool was represented by high molecular four-to-six-ring compounds, deriving mainly from combustion sources. The total organic carbon (Corg) and black carbon (BC) contents were the main parameters associated with the PAH accumulation in soils, and the level of the regional anthropopressure was considered a significant factor. The strongest links of PAHs/BC (r = 0.70, p ≤ 0.05) were found in the region of high anthropopressure, characterized by a relatively high content of BC (up to 45.3 g kg-1), which tends to heavily adsorb hydrocarbons. In a region of low influence exerted by anthropopressure, the PAH/Corg or PAH/BC relationships were not observed, which may suggest different diffuse sources of PAH origin and a dominant role of other organic matter fractions in retention of PAHs in soils.