Polycyclic Aromatic Hydrocarbons In Soils Research Articles

Toxicological Risk Evaluation of Polycyclic Aromatic Hydrocarbons in Soils from a Petroleum Spillage Site at Kokori in the Niger Delta Region of Nigeria

Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants that are produced by the incomplete combustion of organic sources and are widely found in soils. This present research was carried out to evaluate the concentrations and toxicological risk assessment of the United States Environmental Protection Agency's sixteen priority polycyclic aromatic hydrocarbons (16 priority PAHs) in soils from the vicinity of an oil spillage site in Delta State of Nigeria. The level of pollution and potential toxicological health hazards of the PAHs were assessed in surface soil samples using soxhlet extraction of and Gas Chromatography-Mass Spectrometry (GC-MS). Thirteen out of the sixteen USEPA priority PAHs were detected in the soil sample. The concentrations of PAHs in the petroleum-contaminated soils in this investigation ranged from 0.01181 ppm to 1.16054 ppm, with the total estimated concentration of the 16 priority PAHs being 5.6713 ppm. Furthermore, the distribution of the PAHs in the study area was predominated by LMW PAHs (62%) over HMW PAHs (38%). Additionally, the total toxicity equivalency quotients TEQ (B[a]Peq) result of the carcinogenic potency of the USEPA priority PAHs was calculated as 0.08689 ppm (8.689%) and was discovered to be within the Canadian TEQ (B[a]Peq) threshold of 0.6 ppm. This suggests that the soil in the study area is safe based on the Canadian TEQ (B[a]Peq) standard and does not constitute a carcinogenic risk. However, the long-term bioaccumulation of these low quantities of PAHs in human has been found to constitute a potential health concern due to bioaccumulation in living systems.

Enhancing Anaerobic Biodegradation of Phenanthrene in Polluted Soil by Bioaugmentation and Biostimulation: Focus on the Distribution of Phenanthrene and Microbial Community Analysis

The remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils has received much attention in recent years, and most of the contaminated sites are in anaerobic environments, such as deep soils and flooded soils. We simulated the natural flooded soil environment, selected phenanthrene (PHE) as a model PAH contaminant, and designed batch experiments run for 63 days to comprehensively investigate the effects of the combined addition of anaerobic sludge and granular biochar on microbial community and function and the anaerobic biodegradation of PHE. Firstly, the residue, distribution, and removal of PHE in the flooded soil environment were quantified for each group. Secondly, the effects of bioaugmentation of soil indigenous microorganisms by the addition of anaerobic activated sludge and biostimulation of biochar on the removal of PHE from the soil were analyzed against each other. Lastly, the changes in the structure of the microbial community under the effect of bioaugmentation and biostimulation were illustrated by sequencing analyses. The results of this study showed that the removal efficiency of PHE reached 72.0% after the addition of anaerobic activated sludge. The incorporation of anaerobic activated sludge and biochar resulted in a 25.3% increase in PHE removal compared to a single soil, suggesting that the combination of bioaugmentation and biostimulation can have a synergistic effect on the anaerobic biodegradation of PHE in contaminated soils. The results of sequencing analysis further indicated that the introduction of an exogenous microbial community changed the dominant genera associated with PHE degradation and introduced methanogenic archaea, which enriched the metabolic pathways of the carbon cycle in the system. On this basis, the addition of biochar resulted in higher anaerobic microbial community diversity, functional dominant species were enriched, and the direct interspecies electron transfer (DIET) process between electroactive bacteria (Bacteroides, f_Geobacteraceae) and Methanosaeta was facilitated, which accelerated the degradation of PHE by anaerobic microbial communities. The results of this study provide regulatory tools and basic data support for enhanced bioremediation of PAHs in flooded soils.

Determining the sources and distribution of polycyclic aromatic hydrocarbons in the soil of different oil fields at Basrah governorate, Iraq

The object of the research is polycyclic aromatic hydrocarbons (PAHs). For the purpose of determining the source and distribution of PAHs, soil samples from the 11 oil fields in the Basrah governorate (Seba, Safwan, Majnoon, Ratawi, Bergezia, Qurna1, Qurna2, Shuaaba, South and North Rumaila, and al Zubair) were taken at a depth of 0 to 20 cm. According to their molecular weight, they were separated into two main groupings. The first group of compounds consisted of six compounds: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, and anthracene. These light (low molecular weight) compounds have two to three fused aromatic rings. The first group includes nine chemicals: floranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b), benzo(k), benzo(a), benzo(a), indeno(1,2,3,c,d), and benzo(g,h,i)perylene. These heavy (high molecular weight) compounds included four or more fused aromatic rings. The PAHs compounds ranged in value from the lowest (0.16 ng/g dry weight of benzo(a)anthracene at station West Quarna1) to the highest (680 ng/g dry weight of benzo(g,h,i)perylene that emerged at station North Rumail). The total concentration of PAHs ranged from 77.67 ng/g in South Rumaila Field while highest concentration is 2284.27 ng/g in North Rumail. The PAHs compound has low and high molecular weight, their ratio of LMW/HMW (low molecular weight/high molecular weight) and phenanthrene/anthracene, fluoranthene/pyrene indicated that the source of PAHs was pyrogenic only. The PAH diagnostic ratios and principal component analysis (PCA) indicated that PAHs in soils essentially originated from emissions and combustion. This study gave a baseline on the source and distribution of these compounds in oil fields at Basrah governorate and can be used as a baseline for coming study in the future.

Laccase as a useful assistant for maize to accelerate the phenanthrene degradation in soil.

Polycyclic aromatic hydrocarbon (PAH) pollution has attracted much attention due to their wide distribution in soil environment and serious harm to human health. In order to establish an efficient and eco-friendly technology for remediation of PAH-contaminated soil, phytoremediation utilizing maize assisted with enzyme remediation was explored in this study. The results showed that the participation of laccase could promote the degradation of phenanthrene (PHE) from soil and significantly reduce the accumulation of PHE in maize. The degradation efficiency of PHE in soil could reach 77.19% under laccase-assisted maize remediation treatment, while the accumulation of PHE in maize roots and leaves decreased by 41.23% and 74.63%, respectively, compared to that without laccase treatment, after 24days of maize cultivation. Moreover, it was found that laccase addition shifted the soil microbial community structure and promoted the relative abundance of some PAH degrading bacteria, such as Pseudomonas and Sphingomonas. In addition, the activities of some enzymes that were involved in PAH degradation process and soil nutrient cycle increased with the treatment of laccase enzyme. Above all, the addition of laccase could not only improve the removal efficiency of PHE in soil, but also alter the soil environment and reduce the accumulation of PHE in maize. This study provided new perspective for exploring the efficiency of the laccase-assisted maize in the remediation of contaminated soil, evaluating the way for reducing the risk of secondary pollution of plants in the phytoremediation process.

Monitoring the Content of Polycyclic Aromatic Hydrocarbons in Soils and Natural Herbal Vegetation of Technogeneously Polluted Territory

Currently, one of the most important problems is the pollution of natural systems by polycyclic aromatic hydrocarbons (PAHs) as a result of human industrial activity. In this connection, it is necessary to carry out monitoring of territories subjected to the anthropogenic impact. As a result of the monitoring study of the impact zone of the fuel and energy complex enterprises, it was found that polycyclic aromatic hydrocarbons (PAHs) in the soil of the impact zone accumulate mainly up to 2 km along the line of the prevailing wind rose from the enterprise. The group composition of PAHs is dominated by 4-ring compounds, exceeding the background values by 23 times. At the same time, plants growing on the territory of the impact zone mainly accumulate such compounds as fluoranthene, pyrene, benzo[a]anthracene and phenanthrene, which is 70–82% of the total content of polyarenes in various parts of plants.

Distribution, Sources, and Health Risk of Polycyclic Aromatic Hydrocarbons in Farmland Soil of Helan, China

With the development of industry and agriculture, polycyclic aromatic hydrocarbons (PAHs) in the agricultural sector have gradually increased to different degrees, leading to an escalation in environmental pollution. In turn, this escalation has presented a significant possibility of endangering agricultural practices on farmland and has had a serious impact on regional sustainable development. Therefore, a total of 117 samples of soil were gathered to research the pollution level, distribution, sources, and health risk of PAHs in Helan farmland soils. A reference was used for the identification and quantification of PAH content using high-performance liquid chromatography (HPLC) with an ultraviolet detector, and their spatial distribution was analyzed utilizing the Arc Geographic Information System (ArcGIS). The source of PAHs was analyzed by absolute principal component scores/multiple linear regression (APCS-MLR). The lifetime cancer risk increment model and Monte Carlo sensitivity analysis were used to assess the potential health hazards to humans associated with PAHs in soil. Within the current study area, PAHs were higher in the northwest. The results showed that the total content of PAHs in Helan farmland soil ranged from 17.82 to 1544.73 ng·g−1 with a mean of 408.18 ng·g−1, which indicated the middle degree of pollution in farmland soil. The verification results of the APCS-MLR model showed that the correlation coefficient between the measured values and the predicted values ranged from 0.661 to 0.984, which suggested that the APCS-MLR model demonstrated favorable suitability for conducting source analysis of PAHs in the soil within the study region. Based on the contribution of PAHs from each source, the main sources of PAHs in Helan farmland soil were the combustion source (biomass, diesel, and natural gas combustion) and the transportation source (gasoline for vehicles and traffic exhaust emissions). The health risks’ estimation showed that PAHs in farmland soil did not have potential health risks for adults but represented a carcinogenic risk for children via the main exposure pathway of ingestion with the mean intake of 1.28 × 10−5. Meanwhile, the carcinogenic risks (CRs) of dermal contact for the mean value of adults (9.32 × 10−7) was found to be higher than that for children (3.18 × 10−8). From the Monte Carlo simulation, the soil particle uptake rate was the most sensitive to the health risks of children and adults with risk probabilities of 26% and 52%, and the risk probabilities from body weight were −11% and −1%, whose negative value indicated that the increase in body weight could reduce the health risks to human. These findings could provide reference for the study of soil organic pollution in Helan farmland soil and contribute significantly to the preservation of the ecological environment, maintaining human health and safety, and promoting the sustainable development of regional farmland.

Comparative study on anthropogenic impacts on soil PAHs: Accumulation and source apportionment in tourist and industrial cities in Hebei Province, China

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous organic contaminants in urban soils. The accumulation and source identifications of PAHs within a city have been frequently studied. However, impacts of urbanization development modes on PAHs accumulation patterns by taking a city as a whole have been seldom reported. Four cities with two development modes in Hebei province, Chengde and Zhangjiakou (tourist cities) and Handan and Tangshan (industrial cities), were selected. The concentrations of 16 priority PAHs in soils in the study areas were investigated. The results showed that the average concentrations of Σ16PAHs in Handan (2517 μg/kg) and Tangshan (2256 μg/kg) were more than twice of those in Chengde (696 μg/kg) and Zhangjiakou (926 μg/kg) approximately. Lines of evidence, provided by a combination of diagnostic ratios, pairwise correlation, and PMF methods, revealed that the dominant sources of PAHs in either city were industrial emission, vehicle emission, and petrogenic/biogenic process but with different proportions. Linear fittings based on Bayesian kernel machine regression analysis (BKMR) were constructed to illustrate the impact of industrialization on PAHs accumulation. The probability of excessing the 10 % (376 μg/kg) and 50 % (1138 μg/kg) of current ∑16PAHs would be higher than 90 % given the gross industrial production per unit area >5.00 × 106 and 20.5 × 106 CNY/km2, respectively. The proposed threshold values of industrialization are of significance for determining industrial structure and proportion in urban management.

Remediation of heavily PAHs-contaminated soil with high mineral content from a coking plant using surfactant-enhanced soil washing

This study investigated the effectiveness of various surfactants at different concentrations in removing high concentrations of polycyclic aromatic hydrocarbons (PAHs) from soil with high mineral content, focusing on the impact of surfactant treatment on the mobility of the residual PAHs in soil. The results revealed that the cationic surfactant (CTMAB) inhibited removal of PAHs in the whole tested concentration range of 0.1–8 g/L. In contrast, the non-ionic and anionic surfactants (Triton X-100 and SDBS) significantly enhanced removal of PAHs as their amendment concentrations reached 2 g/L and above. Triton X-100 exhibited steadily increased efficacy with increasing amendment concentrations and maintained favorable solubilization capability when continuously amended, making it the preferable choice for remediating PAHs-contaminated soil. Surfactant and water washing processes altered soil physicochemical properties by removing some clay minerals (e.g., faujasite) and organic matter that can bind or sequester PAHs, potentially increasing their extractability and bioavailability in the washed soil, thereby posing higher ecological risks compared to the original one. Although soil washing decreased retention of the remaining PAHs in soil, it did not significantly impact PAHs release from soil by flowing water. These findings provide insights into the long-term effectiveness and ecological impacts of surfactant-enhanced washing as a potential remediation technique for PAHs-contaminated soil.

Distribution and transfer rules of polycyclic aromatic hydrocarbons in soil-wheat ecosystems in China.

The translocation and accumulation patterns of polycyclic aromatic hydrocarbons (PAHs) in the soil-crop system have important implications for the fate of PAHs and human health. This study summarized the concentrations of 16 priority PAHs in the soils and various parts of mature winter wheat in China, sourced from a screening of previous literature in English and Chinese databases. The study analyzes the distribution characteristics, transfer patterns, and human health risks of PAHs in sites studied in Shaanxi, Henan, and Shandong provinces. The results showed that the concentrations of Σ16 PAHs in the rhizosphere soil of wheat ranged from 10.30 to 893.68 ng/g, in descending order of Shaanxi > Henan > average > Shandong. In sites with mild to moderate contamination (200 < Σ16 PAHs < 600 ng/g; i.e., Henan and Shaanxi), the concentration of Σ16 PAHs in the roots was higher than that in the stems or the grains, while in contamination-free sites (Σ16 PAHs < 200 ng/g; i.e., Shandong), the highest concentration of Σ16 PAHs was found in the stems. Generally, the concentrations of PAHs increased in the order of roots-stems-grains. The predominant PAHs in each part of wheat were 2- or 3-ring compounds, with five- or six-ring PAHs being more prevalent in wheat from Shanghe, Shandong. The bioaccumulation factors of different wheat parts from Shaanxi and Henan were consistently smaller than 1, and low- and medium-ring (2-4 rings) PAHs had bigger bioconcentration factors than high-ring (5-6 rings) PAHs. However, the accumulation of PAHs in the aboveground parts of wheat was larger than that in the underground parts of the Shandong sites. The linear regression relationship between the octanol-water partition coefficient and root concentration factor (RCF) of PAHs reflected that low and medium-ring PAHs were more easily absorbed by wheat roots than high-ring PAHs in Shaanxi and Henan. Our assessment of the health risks of oral wheat intake in adults and children by the incremental lifetime cancer risk (ILCR) model found a potential carcinogenic risk for both age groups in each province, with higher risks in adults than in children.

Rate of Horizontal Spread of Fluorene in a Sandy Loam under Natural Environment

Rate of horizontal movement of a pollutant such as polycyclic aromatic hydrocarbons in soil plays a major role in spread of pollutants in the segments of the environment. However, the study regarding this aspect is not widely reported. In the present work, the rate of horizontal spread of Fluorene in soil is determined in an experiment spread over a year under natural environment. Known amount of the hydrocarbon was added to a soil at a particular point, extraction of the same was done later on at definite time interval at definite distances from the point of application and quantitative determination was done by HPLC analysis of the extract. Eleven number of important physico-chemical parameters of the soil sample were determined/calculated in order to know the quality of the soil. The values of parameters are in agreement to the characteristics of a good soil. The experimental soil is a mild acidic sandy loam. It has been found that one-year time is sufficient for the applied quantity of the hydrocarbon to spread itself uniformly to attain a concentration, which is at par with natural concentration of the hydrocarbon in the experimental soil. Studies on kinetics of the reaction imply that the reaction occurs in different phases, rate constants being gradually increased with time. The positive influence of increase in ambient temperature and rainfall on disappearance of the hydrocarbon is seen in the experiment. It has been found that the most probable speed of the hydrocarbon for horizontal movement is 3.75 cm per month in the experimental soil.

Contamination and source-specific health risk assessment of polycyclic aromatic hydrocarbons in soil from a mega iron and steel site in China

The iron and steel industry has always been a key and difficult point of environmental pollution control. In the present study, 493, 175, 153, 72, and 42 soil samples were collected from the soil depths of 0–0.5, 0.5–2, 2–3, 3–4, and 4–5 m (herein called the layers) of the Shougang Steel site, respectively. Compared with the evaluation criteria, the Shougang Steel surface soil was severely polluted by polycyclic aromatic hydrocarbons (PAHs). Inverse distance-weighted interpolation and the Kruskal-Wallis H test revealed that the soil PAH pollution in the iron-making area, especially the coking area, was severer than those in other areas. The PAH concentrations first decreased, and then, increased with the increase of depth. With the increase in depth, the contributions of 2- and 3-ring PAHs increased, while those of 4-, 5-, and 6-ring PAHs decreased. The bivariate local indicators of spatial association (LISA) analysis was used to identify the areas prone to soil PAH pollution due to atmospheric deposition of industrial waste gas and traffic emissions. The method could be used to analyze the impact of anthropogenic activities on soil's PAH pollution for other contaminated sites. Three main pollution sources of soil PAHs, the backfill source, the combustion of coal, and the traffic emissions, were identified based upon three diagnostic ratios, positive matrix factorization and the bivariate LISA analysis, and accounted for 53.8%, 23.5%, and 22.7%, respectively. The combination of bivariate LISA analysis and other source analysis methods could improve the accuracy of source analysis. Benzo[a]pyrene contributed the most to the total health risk among sixteen PAHs. The health risks related to the three pollution sources decreased in the order of backfill sources > coal combustion > traffic emissions. The incremental life-time carcinogenic risks were all below 10−4, indicating negligible or acceptable risks.

Remediation of PAHs contaminated soil enhanced by nano-zero-valent iron combined with white rot fungi Peniophora incarnata

Polycyclic aromatic hydrocarbons (PAHs) are hazardous organic contaminants commonly found in soils. This study investigated an integrated remediation approach combining white rot fungal augmentation and nano-zero-valent iron (nZVI) activated persulfate oxidation to enhance the degradation of PAHs in soil. The white rot fungus Peniophora incarnata demonstrated efficient degradation of lower molecular weight PAHs including phenanthrene (91% removal) and anthracene (71% removal) in liquid culture, but had limited degradation of high molecular weight benzo[a]pyrene (35% removal). Inoculation of P. incarnata in non-sterilized soil led to 54% phenanthrene and 46% anthracene removal after 42 days. Co-inoculation with Pseudomonas aeruginosa slightly improved the degradation by 15% and 13%, respectively. However, benzo[a]pyrene removal was negligible through bioremediation alone. Direct nZVI/persulfate oxidation removed 55–75% of lower molecular weight PAHs and 68% of benzo[a]pyrene in soil. Integrated treatment combining nZVI/persulfate oxidation followed by P. incarnata inoculation resulted in 92–96% degradation of phenanthrene, anthracene and benzo[a]pyrene after 42 days, which was significantly higher than either approach alone. The enhanced PAH removal was attributed to the coupled effects of chemical oxidation and microbial degradation. P. aeruginosa is capable of directly metabolizing and mineralizing lower molecular weight PAHs such as phenanthrene and anthracene. The presence of this additional PAH-degrading bacterium likely contributed to the increased degradation observed. Overall, the sequential nZVI/persulfate and fungal treatment provides an effective and sustainable option for remediating soils co-contaminated with PAHs and other persistent organics. Further research should optimize treatment parameters and evaluate long-term impacts on soil quality.

Polycyclic aromatic hydrocarbons dissolution in supercritical carbon dioxide by molecular dynamics simulation

With the rapid development of industry, the problem of soil contamination has grown increasingly serious, posing a serious threat to the wellness of people. Polycyclic aromatic hydrocarbons (PAHs) are among the most common soil contaminants. Supercritical CO2 extraction has been widely used to treat PAHs in soils. Solute solubility in supercritical fluids is a fundamental thermophysical parameter that must be investigated and modeled. In this work, we employed molecular dynamics simulation to investigate the microscopic dissolution process in supercritical CO2 of four PAHs: naphthalene, anthracene, pyrene, and benzo(α)pyrene. We also looked into the implications of changing the ring number of PAHs on the ability of supercritical CO2 to dissolve PAHs by calculating the interaction energy, radial distribution function, and the coordination number between PAHs and supercritical CO2. The results indicated that the PAHs’ capacity to dissolve in supercritical CO2 decreased gradually with the increase of ring number. The interaction energy between PAHs and supercritical CO2 decreases as the number of PAHs rings increases. Among them, the van der Waals interaction energy plays a decisive role in the dissolution of PAHs in supercritical CO2. As the number of PAHs rings increased, the positions of the first peak and valley of the radial distribution function remained the same, which appeared at about 4.3 Å and 6.1 Å, respectively. However, the magnitudes of the peaks and valleys decreased. As the number of PAHs rings increased, the coordination number of the C atoms of supercritical CO2 around the C atoms of PAHs decreased.

Biochar alters the persistence of PAHs in soils by affecting soil physicochemical properties and microbial diversity: A meta-analysis

Polycyclic aromatic hydrocarbons (PAHs) pollution in soil is a pervasive environmental issue worldwide. Although biochar has the potential to immobilize PAHs in soils, there remains a study gap in the use of systematic analyses to assess the effectiveness of biochar for PAH removal and the factors that affect biochar. Hence, a meta-analysis utilizing 56 published studies was aimed to assess the impact of biochar on the PAH content, soil physicochemical properties, and microbial diversity in PAH-contaminated soils and to elucidate what factors impact the capability of biochar to alter PAH persistence. With biochar application, soil Ctot PAH concentrations were significantly reduced (15.4%), while the levels of Cfree PAHs and Cbioacc PAHs were reduced by 55.6% and 46.5%, respectively. Additionally, biochar improved the physicochemical properties of PAH-contaminated soil and increased the diversity of microorganisms. Particularly, the relative abundance of PAH degraders increased significantly (43.7%), which indicated that PAH biodegradation was significantly enhanced. Soil physicochemical properties and biochar production conditions are indispensable for the study of the PAH persistence. The overall findings revealed that the pyrolysis of woody biochar at 300–500 °C was beneficial for reducing the PAH persistence in acidic, coarse, or fine and high soil organic matter content (>20 g/kg) soils.

Spatial distribution and risk assessment of polycyclic aromatic hydrocarbons in soils from contaminated sites in Eastern China.

A total of 16 polycyclic aromatic hydrocarbons (PAHs) were measured in 28 soil column samples from two contaminated industrial sites in Eastern China. The total concentration of 16 PAHs (∑PAHs) in the surface soil (0-20cm) was measured up to 52,600ng/g (dry weight basis) with a remarkable spatial difference in the studied contaminated sites. The concentrations of the ∑PAHs in soils decreased with the increase in soil depth (0-10m). The surface and subsurface soil presented a tenfold higher concentration than the soil with depth greater than 4m. Additionally, the vertical migration tendency of the PAHs was found to be correlated significantly with their hydrophobicity (R2 = 0.79, P < 0.01). Naphthalene (with lowest octanol-water partition coefficient among the studied PAHs) showed the greatest average soil depth at which its peak concentration occurred. Furthermore, risk quotient analysis by using benzo[a]pyrene as reference compound showed that 71.4% of the samples exhibited high ecological risk for soil. Moreover, the total carcinogenic risk of the PAHs in the surface soil samples was assessed at 5.61 × 10-5-1.28 × 10-4 and 4.41 × 10-6-9.43 × 10-5 for male and female workers, respectively, in which 67.9%-71.4% of the samples showed potential risk. Generally, these results suggest a further consideration of ecological and health risks associated with PAHs in contaminated sites in Eastern China.

The effect of shrubs admixture in pine forest stands on soil bacterial and fungal communities and accumulation of polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) are a group of persistent toxic pollutants. The species composition of the stand is important in shaping the quality of soil organic matter and, consequently, the PAH content. The main purpose of the research was to determine the role of shrubs in shaping PAH accumulation in forest soils. The study covered the soils of the pine stands of the Rybnik Forest District, which experiences some of the highest deposition of industrial emissions in Europe. Pine stands with admixture of shrubs (alder buckthorn Frangula alnus and European hazelnut Coryllus avellana) growing in the same soil conditions were selected for the study. Samples for analyses were collected from the organic horizon (O) (from a depth of 0–7 cm) and humus mineral horizon (A) (from a depth of 7–15 cm). The organic C and total N concentrations, pH, alkaline cation content, soil enzyme activity and PAH content were determined. Additionally, the taxonomic composition of soil bacterial and fungal communities was determined. The highest activity of enzymes was noted in soils under influence of shrubs. The enzymatic activity was positively correlated with the content of total N, organic C, pH H2O and KCl and negatively with the C/N ratio. The highest PAH content was recorded in the soils of pine stands without the admixture of shrubs. Our research indicates the importance of shrubs in shaping the properties of surface horizons of forest soil and, consequently on the accumulation of PAHs. Shrubs stimulate biochemical activity of soils which results in lower PAHs accumulation by providing more easily decomposable organic matter.

Evaluation of the content and degradation rates of PAHs in biochars, in terms of assessing the environmental risks of their application for soil remediation

The growing worldwide practice of biochar application as soil ameliorants, as well as adsorbents for remediation of soil contaminated with oil products and heavy metals, can lead to an increase the risk of environmental pollution by pyrolysis by-products. One of the most dangerous components of biochars is polycyclic aromatic hydrocarbons (PAHs), which are inevitably formed during the production of pyrogenic material. In this work, biochars obtained from various plant materials (millet, corn, willow, linden) under different pyrolysis temperatures were tested for the content of polycyclic aromatic hydrocarbons. The total content of PAHs in the studied samples ranged from 8.49 to 221.21 µg/kg, which does not exceed the limit concentrations established by the International Biochar Initiative. At the same time, polynuclear hydrocarbons with high carcinogenic and immunotoxic properties are found in the composition of biochars. A natural question arises about the effect of the final pyrolysis temperature on the total content and composition of PAHs in pyrolysis by-products. To study the degradation of polycyclic aromatic hydrocarbons in soil, linden biochar obtained by pyrolysis at 250 °C was used, from which the contaminants were extracted and applied to the soil so that the concentration of the marker was 20 and 40 µg/kg. The determination of the residual amount of polycyclic aromatic hydrocarbons was carried out after 1, 2, 6, and 11 months of incubation. Complete degradation of some 3–5-membered polycyclic aromatic hydrocarbons was found after 1–2 months of incubation. The most persistent pollutants were benzo(a)pyrene, benzo(b)fluoranthene, and pyrene, the concentration of which decreased to 31–71% on after 11 months of incubation. The slower degradation was found in the variant of the experiment with the high concentration level of polycyclic aromatic hydrocarbons. It was concluded that in soils selective accumulation of polynuclear PAHs, that most resistant to biodegradation, can occur.

Characterisation of former manufactured gas plant soils using parent and alkylated polycyclic aromatic hydrocarbons and Rock-Eval(6) pyrolysis

Soils sampled from 10 former manufactured gas plants (MGP) in the UK were investigated using gas chromatography mass spectrometry (GC-MS/MS) and Rock-Eval (6) Pyrolysis (RE). RE is a screening tool used to characterise bulk organic matter in soils via the release of carbon compounds during pyrolysis and oxidation. Both the distributions and concentrations of 30 parent and 21 alkylated polycyclic aromatic hydrocarbons (PAHs) and the parameters of RE were analysed to establish relationships between soils and the MGP processes history. Principal component analysis (PCA) using the PAHs distributions and RE parameters can assist with differentiating between MGP processes. MGP processes utilizing oil provided the clearest results, attributed to petrogenic signatures with high proportions of low molecular weight PAHs. Processes using lower temperature processes were distinguished by higher proportions of high molecular weight PAHs. RE parameters alone were unable to distinguish MGP processes but showed potential in estimating the lability and thus the amount of PAH that could be released from soils. This research provides new insights that may be useful in understanding and characterising the risks posed to human health from PAHs in soils.

Source apportionment and source specific health risk assessment of HMs and PAHs in soils with an integrated framework in a typical cold agricultural region in China

A new innovative methodology system framework for source apportionment and source-specific risk assessment has been proposed and actively applied to identify the contamination characteristics, oriented sources and health risks associated with contamination levels of Heavy metals (HMs) and Polycyclic Aromatic Hydrocarbons (PAHs) in soils, a typical cold agricultural region in Northeastern China. To achieve this meaningful goal, a large-scale dataset including 1780 top soil samples, 10 HMs and 16 priority PAHs has been organized and collected from a typical study area in China. The total concentrations of the 10 selected HMs in study area range from 0.05 to 2147.40 mg/kg, with an average of 549.25 ± 541.37 mg/kg. The average concentrations of PAHs for (3–6)-rings are 16.60 ± 18.90, 26.40 ± 28.20, 9.51 ± 13.00 and 1.99 ± 5.30 ng/g, respectively. On the base of optimized literature source fingerprints for HM and PAH, a widely used receptor model, positive matrix factorization (PMF) has been applied to apportion the contamination sources HMs and PAHs in soils. Then source-specific health risk of soil HMs and PAHs have been assessed using the probabilistic incremental lifetime cancer risk model incorporated with source apportionment results data. Fertilizer residues/coke oven comprise the primary contamination source contributors of HMs and PAHs with corresponding contributions of 32.23 % and 27.93 % for HMs and 37.94 % for PAHs. Fertilizer/pesticide residues contributes most to the risks of soil HMs (28.8 %), followed by fossil fuel combustion (24.6 %), mining activities (20.2 %), traffic and vehicle emission (16.3 %) and electroplating/dyeing (14.1 %). Meanwhile, the ranking of health risks from the five identified contamination sources of soil PAHs are resident discharge, coal-fired boilers, coke oven emission, gasoline combustion and power plant, with the contribution of 27.1 %, 25.3 %, 17.3 %, 15.5 % and 14.8 %.And relatively, source-specific risk assessment demonstrates fossil fuel and coal combustion contribute the greatest impact to the total risk of HMs and PAHs (61.7 % and 56.1 %), respectively. This study provides a good example of how the source specific health risk assessment can be utilized to reduce the contamination in soils.

A highly porous fiber coating based on a Zn-MOF/COF hybrid material for solid-phase microextraction of PAHs in soil

This study involved the development of a novel adsorbent by combining a Zn-based MOF with a melamine-based COF, resulting in the formation of a hybrid material known as Zn-MOF/COF. The adsorbent was characterized using FT-IR, SEM, XRD, EDX, and BET analysis techniques. The resulting Zn-MOF/COF sorbent was employed to prepare solid-phase microextraction (SPME) fibers for the extraction and enrichment of polycyclic aromatic hydrocarbons (PAHs) in contaminated soil samples, after coupling with GC-FID. A Box-Behnken design (BBD) was used to optimize key variables of SPME conditions.Under optimal conditions of 85 °C for 30 min extraction with 23 μL g−1 sample's moisture level, linear responses of six PAHs were ranging from 1 to 20000 ng g⁻1 with determination coefficients greater than 0.99. Limits of detection (LODs) were over the ranges of 0.1–1 ng g-1. The RSDs for intra-fiber and inter-fiber analyses were obtained 2.2–6.6% and 5.2–11.6%, respectively. Relative recoveries values for real soil samples were found to be 91.1–110.2%. The results showed lower cost and higher extraction efficiency for the Zn-MOF/COF fiber, compared with commercial and homemade adsorbents.