Polycyclic Aromatic Hydrocarbons In Soils Research Articles

First data on concentrations and composition of polycyclic aromatic hydrocarbons in soil, bottom sediments and suspended matter of water throughout the whole Fatala River Basin (Republic of Guinea)

First data on concentrations and composition of polycyclic aromatic hydrocarbons in soil, bottom sediments and suspended matter of water throughout the whole Fatala River Basin (Republic of Guinea)

Enhanced Remediation of Polycyclic Aromatic Hydrocarbons in Soil Through Fungal Delignification Strategy and Organic Waste Amendment: A Review

AbstractNutrient-limited soils from growing global contamination with polycyclic aromatic hydrocarbons (PAHs) and the massive organic waste generation from agro-based and food industries have raised more demand for exploring and recycling the latter as sustainable, cost-effective, and green nutrient-rich sources for soil amendment. To further enhanced the potentials of these substrates in soil, immobilisation or biological pre-treatment techniques using fungi are employed. The white-rot fungi- basidiomycetes, are the most widely researched and efficient organisms to perform these functions because of their high lignin-degrading ability for organic materials, such as corn cob, straws, spent brewery grains, sugarcane bagasse, etc. This review addresses the importance of organic amendment to enhance the biodegradation efficiency of PAH from contaminated soils and it also highlights various biological techniques for improving PAH biodegradation using organic waste materials and white-rot basidiomycetes. This review will also show a better understanding of the concepts of fungal immobilisation and pre-treatment for PAH degradation in soil and show their insights as feasible and optimise techniques for developing remedial strategies for contaminated soils.

Distribution, sources, and risk assessment of polycyclic aromatic hydrocarbons in surface soils and plants from industrial and agricultural areas, Junggar Basin, Xinjiang

The contamination characteristics of Polycyclic Aromatic Hydrocarbons (PAHs) in different environmental functional areas are different. In this study, the contamination of PAHs in soils and common plants in typical mining and farmland areas in Xinjiang, China, was analyzed. The results showed that the contamination levels of PAHs in mining soils were significantly higher than those in farmland soils, and the mining soils were dominated by 4-5-ring PAHs and farmland soils by 3-4-ring PAHs. Analysis of their sources using a positive definite factor matrix model showed that PAHs in mining soils mainly originated from coal and natural gas combustion, and transportation processes; while farmland soils mainly came from biomass and coal combustion, and fossil fuel volatile spills. The cancer risk of PAHs in soils was evaluated using a combination of the Monte Carlo and the lifetime carcinogenic risk models, and the results showed that the overall level of cancer risk for mining soils was higher than that for farmland soils, and can put some people in high risk of cancer. For plant samples, except for individual crop samples, the contamination levels of mining plants and crops were similar, with 4-5-ring PAHs dominating in desert plants in mining areas and the highest proportion of 3-ring PAHs in crops in agricultural fields, and PAHs in both plants were mainly from biomass and coal combustion. The results of correlation analysis showed that 2-ring PAHs in crop roots were significantly positively correlated with it in corresponding soils, and some high-ring PAHs in crop leaves were significantly negatively correlated with it in corresponding soils. Therefore, there were significant differences in the pollution characteristics of PAHs in soils and common plants in mining and agricultural areas. Human health risks and ecological risks are mainly concentrated in mining areas, and appropriate intervention measures should be taken for pollution remediation.

Temporal trends of polycyclic aromatic hydrocarbons in soils amended with sludge, compost, and manure in a Scotland pasture: An 8-year field experiment

To optimize the effective utilization of organic waste in agricultural practices, a comprehensive assessment of associated risks and benefits is crucial. This study investigated the impact of three types of organic wastes (sludge, compost, and manure) on polycyclic aromatic hydrocarbons (PAHs) in contaminated soil in a Scottish pasture. The experimental setup comprised 16 plots with four treatments (compost, manure, sludge, and inorganic fertilizer) and four replicates. After eight years of this study, notable disparities in ΣPAH16 concentrations were observed among the different treatments, with compost-amended soil at 378 μg kg−1, sludge-amended soil at 331 μg kg−1, and manure-amended soil at 223 μg kg−1. The concentrations of ΣPAH16 in soil amended with compost and sludge exhibited a linear increase with extended sampling time. Significant changes in ΣPAH16 concentration were evident in the compost treatment plot, with an increase of 20% in the first year and 82% in the eighth year. Risk assessment suggested a low level of health risk from exposure to PAHs at the measured concentrations in the three organic wastes. In conclusion, this study highlights the importance of considering the effects of organic waste amendments on soil PAH levels to make informed decisions in sustainable agricultural practices. It also underscores the need for ongoing research to fully understand the implications of different organic waste applications on soil health and environmental quality.

Ecological and human health impact assessments based on long-term monitoring of soil PAHs near a coal-fired power plant.

The combustion of coal in power plants releases significant amounts of polycyclic aromatic hydrocarbons (PAHs), which are highly toxic and carcinogenic. This study assesses the ecological and human health impacts of PAHs contamination from a coal-fired power plant over 8years. The monitoring site selection considered the distance from the power plant and the prevailing wind direction in the investigated area. The results reveal that, during the monitoring period, PAH levels increased on average by 43%, 61%, and 37% in the zone of the prevailing wind direction, in the area proximate to the power plant, and the zone distant from it, respectively. The site, which has a radius of 4.5km in the prevailing wind direction, exhibited the highest ecological and human health impacts. Additionally, a strong correlation was observed between environmental and human health impacts, depending on the distance from the power plant, particularly in areas with the prevailing wind direction. These insights contribute to a comprehensive understanding of the intricate dynamics linking power plant emissions, PAHs contamination, and their far-reaching consequences on the environment and human health.

Evaluation and modelling of polycyclic aromatic hydrocarbon (PAH) bioavailability in soils affected by coal tar asphalt

There are large masses of coal tar asphalt present in old roads, containing high concentrations of polycyclic aromatic hydrocarbons (PAHs). Uncertainty surrounding the risk they pose causes problems during road reconstruction and for the reuse of the asphalt present. To help elucidate potential risks, a parsimonious linear equilibrium partitioning model for the bioavailability of PAHs in soils contaminated by tar asphalt particles was developed. Furthermore, a set of partitioning coefficients for PAHs between sampled coal tar binders and water were determined experimentally, as well as measurements of freely dissolved concentrations using polyoxymethylene samplers in batch tests and column recirculation experiments with various mixtures of different soils (peat and sandy loam) and tar asphalts. The model predictions of freely dissolved concentrations were conservative and within an order of magnitude of measurements in both batch and column tests. The model presented here only relies on soil organic carbon content and the fraction coal tar binder in the soil to model PAH partitioning. This model could be used for more realistic. Low tier risk assessments towards rational prioritization of sensitive areas for risk reduction efforts.

Insight into interaction among soil microbial community, soil metabolomics and enzyme activity after long-term PAH stress

The problem of soil polycyclic aromatic hydrocarbon (PAH) pollution in coking plant sites has been widely studied in recent years, but there is a lack of research on the correlation between soil microorganisms, soil metabolomics, and soil properties. Thus, in this study, the long-term impact of coke combustion on soil microbial community structure, enzyme activities, and metabolic pathways within a former coking plant site was investigated. Soil samples were collected from both the coking production area (CA group) and office area (OLA group), approximately 0 to 20 cm in depth. Compared with OLA group, elevated levels of 16 PAHs in the list of USA EPA were detected by gas chromatography-mass spectrometry in the CA group. Several dominant microorganisms, such as Altererythrobacter, Lysobacter, and Sulfurifustis, were identified by 16 s ribosomal DNA sequencing in the CA group. The fatty acid biosynthesis pathway exhibited specific inhibition, while the phenylalanine metabolic pathway was promoted in response to PAH stress. Long-term PAH exposure led to the inhibition of soil urease activity. The co-occurrence network of microorganisms revealed intricate patterns of co-metabolism and co-adaptation within complex bacterial communities, facilitating their adaptation to and decomposition of soil-borne PAHs. This research could provide valuable insights into the community characteristics and metabolic mechanisms of microorganisms inhabiting PAH-polluted soil within coking plant sites. The findings enhance our understanding of the indigenous soil microbiome and its intricate network dynamics under the persistent stress of PAHs, contributing to a more comprehensive knowledge of soil ecosystems in such environments.

Strategies and mechanisms for improving the detection accuracy of nonextractable residues of polycyclic aromatic hydrocarbons in soils

The methods that can accurately measure the concentrations of nonextractable residues (NERs) of hydrophobic organic contaminants (HOCs) in soil are still lacked in current studies. In this study, three methods, namely methanolic saponification treatment (MST), silylation treatment (ST), and acid deashing treatment (ADT), were investigated and then combined to extract the NERs of six types of polycyclic aromatic hydrocarbons (PAHs) from nine soil samples. The NER concentrations of PAHs obtained by ST (2.43–521.73 ng g−1) were comparable to or significantly higher than those obtained by MST (1.94–291.54 ng g−1), owing to the properties of soil and target compounds. Additionally, ADT could further release a considerable amount of PAH NERs (0.39–276.99 ng g−1) from the soils that had been treated with ST. The mechanism was that acid solution dissolved mineral components, significantly increasing the pore size of the soil matrices from 9.37–15.57 nm to 17.11–27.51 nm. The average percentage of each PAH obtained by ADT (the ratio of the amount obtained by ADT to the total NER content) exhibited a negative correlation with their ring numbers (R2 = 0.62, p < 0.05), whereas the percentage of targets recovered through ST increased linearly with their log KOW values (R2 = 0.75, p < 0.05). Moreover, there is a positive correlation (R2 = 0.73, p < 0.05) between the NER percentages of phenanthrene (obtained by ST–ADT) and the specific surface areas of soils, and the NER percentages of benzo(g,h,i)perylene is positively correlated to the content of total organic carbon (R2 = 0.62, p < 0.05). These results suggested that the amounts and locations of NERs were influenced by both the physicochemical characteristics of PAHs and soils. These findings provide some basic understandings of the entrapped mechanisms of PAH NERs, helping to establish strategies for improving their detection accuracy.

Effect of Low-density Polyethylene Microplastics on Natural Attenuation of Oxygenated Polycyclic Aromatic Hydrocarbons in Soil

The continuous accumulation of microplastics in agricultural soils may affect the natural attenuation of oxygen-containing polycyclic aromatic hydrocarbons (OPAHs). The effects of low-density polyethylene (LDPE) microplastics with the spiking proportion of 1 % and 0.01 % in soils on the natural attenuation of OPAHs were investigated via soil microcosm experiments. The relation between the response of bacterial communities and OPAHs dissipation was also explored. The initial content of OPAHs in the soil was 34.6 mg·kg-1. The dissipation of OPAHs in the soil on day 14 was inhibited by LDPE. The contents of OPAHs in LDPE groups were higher than that in the control by 0.9-1.6 mg·kg-1, and the inhibition degree increased with the proportion of LDPE. The contents of OPAHs were not significantly different among groups on day 28, indicating that the inhibitory effect of LDPE disappeared. LDPE did not change the composition of the dominant taxa in the OPAHs-contaminated soil community but influenced the relative abundances of some dominant taxa. LDPE increased the relative abundance of Proteobacteria and Actinobacteria at the phylum level and decreased that of Bacillus and increased those of Micromonospora, Sphingomonas, and Nitrospira (potential degrading bacteria of LDPE and endogenous substances) at the genus level, all four of which were the main genera dominating intergroup community differences. LDPE changed the α and β diversity of bacterial communities, but the extents were not significant. LDPE affected the function of the bacterial community, reducing the total abundance of PAHs-degrading genes and some degrading enzymes, inhibiting the growth of PAHs-degrading bacteria and thus interfering with the natural decay of OPAHs.

Influence of Thermal Desorption Technology on Removal Effects and Properties of PAH-Contaminated Soil Based on Engineering Experiments

Polycyclic aromatic hydrocarbon (PAH) contamination in soil poses a serious threat to ecological safety, human life, and health. Thermal desorption is commonly used to remediate PAH-contaminated soil. Current thermal desorption research primarily focuses on parameters for engineering designs through in-house simulations. In this study, based on a PAH-contaminated site thermal desorption remediation project, the removal efficiency of PAHs in soil (S1, S2) after disposal at different heating temperatures (400, 450, 500, 550 °C) and different residence times (20, 25 min) was investigated, and changes in soil properties before and after disposal were analyzed. The removal rate of 16 PAHs from soil at two concentrations reached 100% after 20 min at 500 °C and 550 °C, respectively. The three-phase structural distances of S1 and S2 soils, respectively, increased by 1.65 and 2.99 times after disposal, sand content increased by 3.20% and 8.27%, water-stable macroaggregates decreased by 8.14% and 2.06%, organic carbon content decreased by 7.27% and 27.05%, heavy fraction organic carbon increased by 33.68% and 5.12%, pH decreased from 10.00 and 10.35 to 8.81 and 8.69, and cation exchange decreased by 13.79% and 26.65%. Soil nutrient content such as TP, AP, TK, and AK increased after thermal desorption, and TN content decreased; approximately 1.0 mg/kg of NO3−-N remained. Our results are expected to support the design of programs for soil reuse after disposal.

Source identification of polycyclic aromatic hydrocarbons (PAHs) in soils around crude oil contaminated area in Ohaji/Egbema, Imo State

ABSTRACT This study aims to determine the source of polycyclic aromatic hydrocarbons (PAHs) in the soils surrounding an area in Ohaji/Egbema, Imo State, that has been contaminated by crude oil. Soil samples were collected in the study area using a soil auger at a depth of 0–20 cm at three sampling locations (sample A, sample B, and sample C) in the Mmahu community in Ohaji/Egbema. In each of the sampling locations, twenty sub-samples were collected from twenty sampling points and pooled together to form representative samples for each of the sampling locations. Prior to GC-MS analysis, the composite samples were air-dried, sieved through a 2-mm mesh, and then kept in pet bottles that had been previously cleaned. The GC-MS investigations were carried out using a Shimadzu Model 2010 GC-MS (Shimadzu, Japan) fitted with an HP-5 MS fused silica column. This was used to quantify the 16 USEPA priority PAHs in the studied soils. The sum of the 16 USEPA priority PAHs in the sample locations ranged from 0.0192 mg/kg in the control sample to 10.73 mg/kg in sample A. Compared to high molecular weight PAHs (4–6 rings), the total concentration of low molecular weight PAHs (2–3 rings) was found to be substantially greater. According to the PAH molecular diagnostic ratio, all sampling points had low to high molecular mass ratios >1, which suggests that the origin of the PAH contamination was petrogenic. The petrogenic source of contamination was attributed to oil spillage around the study area. The knowledge of source identification of PAHs in soils helps in the determination of the most appropriate remediation strategy in order to prevent further contamination and minimise the risks to human health and the environment.

Importance of soil ecoenzyme stoichiometry for efficient polycyclic aromatic hydrocarbon biodegradation

Efficient remediation of soil contaminated by polycyclic aromatic hydrocarbons (PAHs) is challenging. To determine whether soil ecoenzyme stoichiometry influences PAH degradation under biostimulation and bioaugmentation, this study initially characterized soil ecoenzyme stoichiometry via a PAH degradation experiment and subsequently designed a validation experiment to answer this question. The results showed that inoculation of PAH degradation consortia ZY-PHE plus vanillate efficiently degraded phenanthrene with a K value of 0.471 (depending on first-order kinetics), followed by treatment with ZY-PHE and control. Ecoenzyme stoichiometry data revealed that the EEAC:N, vector length and angle increased before day five and decreased during the degradation process. In contrast, EEAN:P decreased and then increased. These results indicated that the rapid PAH degradation period induced more C limitation and organic P mineralization. Correlation analysis indicated that the degradation rate K was negatively correlated with vector length, EEAC:P, and EEAN:P, suggesting that C limitation and relatively less efficient P mineralization could inhibit biodegradation. Therefore, incorporating liable carbon and acid phosphatase or soluble P promoted PAH degradation in soils with ZY-PHE. This study provides novel insights into the relationship between soil ecoenzyme stoichiometry and PAH degradation. It is suggested that soil ecoenzyme stoichiometry be evaluated before designing bioremeiation stragtegies for PAH contanminated soils.

Transformation and Degradation of PAH Mixture in Contaminated Sites: Clarifying Their Interactions with Native Soil Organisms.

Soil contamination of polycyclic aromatic hydrocarbons (PAHs), especially caused by the mixture of two or more PAHs, raised great environmental concerns. However, research on the migration and transformation processes of PAHs in soils and their interactions with native communities is limited. In this work, soil samples from uncontaminated sites around the industrial parks in Handan, Hengshui, and Shanghai were artificially supplemented with three concentrations of anthracene (Ant), 9-chloroanthracene (9-ClAnt), benzopyrene (BaP), and chrysene (Chr). Ryegrass was planted to investigate the degradation of PAHs and its interaction with native soil organisms in the constructed ryegrass-microbe-soil microcosmic system. The bacterial and fungal communities in soil were affected by PAHs; their species diversity and relative abundance changed after exposure to different concentrations of PAHs, among which Lysobacter, Bacillus, Pseudomonas, and Massilia bacteria were correlated to the degradation of PAHs. On the 56th day, the contents of BaP, Chr, and Ant decreased with the degradation process, while the degradation of 9-ClAnt was limited. Nineteen intermediates, including hydroxylation and carboxylated compounds, were identified. The present research would help clarify the potential interactions between PAHs and native organisms in contaminated sites, providing fundamental information for evaluating the transformation risks of PAHs in the natural environment.

Effects of Chinese “double carbon strategy” on soil polycyclic aromatic hydrocarbons pollution

Polycyclic aromatic hydrocarbons (PAHs) and carbon dioxide primarily originate from the combustion of fossil fuels and biomass. The implementation of the Chinese “double carbon strategy” is expected to impact the distribution of PAH emissions, consequently influencing the spatial distribution trend of PAHs in surface soil. Therefore, it is crucial to quantitatively evaluate the effectiveness of the Chinese “double carbon strategy” on soil PAH pollution for the purpose of “the reduction of pollution and carbon emissions”. This study utilized 15,088 individual PAH concentration data from 943 soil samples collected between 2003 and 2020 in China, in conjunction with PAH emissions at a 10 km resolution, for meta-analysis. The calculated PAH emissions in this study are in line with the global PAH emission inventory (PKU-PAH-2007), with a relative standard deviation at the provincial level of less than 25 %. Subsequently, a novel method was developed using emission density and Kow of PAHs to predict PAH concentrations in surface soil based on a least-squares regression model. Compared to other environmental models, the method established in this study significantly reduced the percent sample deviation to less than 70 %. Furthermore, energy consumption data for China were simulated based on the implementation plan of the “double carbon strategy” to project PAH emissions and soil PAH levels for the years 2030 and 2060. The predicted PAH emissions in China were estimated to decrease to 41,300 t in 2030 and 10,406.5 t in 2060 from 78,815 t in 2020. Moreover, the heavily contaminated areas of soil PAHs (i.e., total PAH concentrations in soil exceeding 1000 μg kg−1) were projected to decrease by 45 % and 82 % in 2030 and 2060, respectively, compared to levels in 2020. These findings suggest that the implementation of the “double carbon strategy” can fundamentally reduce the pollution of PAHs in surface soil of China.

The Combination of Buchloe dactyloides Engelm and Biochar Promotes the Remediation of Soil Contaminated with Polycyclic Aromatic Hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) cause serious stress to biological health and the soil environment as persistent pollutants. Despite the wide use of biochar in promoting soil improvement, the mechanism of biochar removing soil PAHs through rhizosphere effect in the process of phytoremediation remain uncertain. In this study, the regulation of soil niche and microbial degradation strategies under plants and biochar were explored by analyzing the effects of plants and biochar on microbial community composition, soil metabolism and enzyme activity in the process of PAH degradation. The combination of plants and biochar significantly increased the removal of phenanthrene (6.10%), pyrene (11.50%), benzo[a]pyrene (106.02%) and PAHs (27.10%) when compared with natural attenuation, and significantly increased the removal of benzo[a]pyrene (34.51%) and PAHs (5.96%) when compared with phytoremediation. Compared with phytoremediation, the combination of plants and biochar significantly increased soil nutrient availability, enhanced soil enzyme activity (urease and catalase), improved soil microbial carbon metabolism and amino acid metabolism, thereby benefiting microbial resistance to PAH stress. In addition, the activity of soil enzymes (dehydrogenase, polyphenol oxidase and laccase) and the expression of genes involved in the degradation and microorganisms (streptomyces, curvularia, mortierella and acremonium) were up-regulated through the combined action of plants and biochar. In view of the aforementioned results, the combined application of plants and biochar can enhance the degradation of PAHs and alleviate the stress of PAH on soil microorganisms.

Dynamics of microbial community and functional genes during bioremediation of PAHs-contaminated soil by two biostimulants

Biostimulation is a favored approach in bioremediation strategies for polycyclic aromatic hydrocarbons (PAHs). However, the addition of some biostimulants can instead be counterproductive to the soil. In this study, rhamnolipid and leaf litter were added as aids to PAHs biodegradation in soil. Quantitative Real-time PCR (qPCR) and 16 S ribosomal RNA (16 S rRNA) techniques were used to investigate the structural-functional response of soil microbial communities and changes in PAHs functional genes during 82 days of the degradation process. The study reveals that rhamnolipid and leaf litter increase the degradation rate of Benzo(a)pyrene by 20.49% and 11.64%, respectively, while having little effect on the degradation rate of phenanthrene. During the degradation process, each biostimulant increases the number of different bacterial genera capable of degrading PAHs, which influences both the structure and function of the microbial community and alters microbial diversity. Additionally, functional gene abundance was enhanced during degradation and showed an inverse relationship with residual PAHs concentration in the soil. These results indicate that different biostimulants have varying effects on microorganisms. This study enhances the understanding of useing of two biostimulants to degrade soil PAHs.

Distribution of 35 Polycyclic Aromatic Hydrocarbons in Pine Needle Samples from Selected Locations in the Republic of Korea.

Polycyclic aromatic hydrocarbons (PAHs), dust, and wax were measured in pine needles, and PAHs were also measured in surface soil. Pearson correlation analysis was performed between the analytical values. The main compounds responsible for the increase in total PAHs were non-carcinogenic phenanthrene and fluoranthene. Therefore, the % content of carcinogenic PAHs decreased with a slope = -0.037 (r = 0.47, p < 0.01), as the total PAH concentration in pine needles increased. Correlations between individual PAHs in pine needles and surface soil were very high when only low-number ring PAHs (2R- and 3R-PAHs) were statistically analyzed and significant when only high-number ring PAHs were statistically analyzed. Low-number ring PAH mainly moves in the gas phase and diffuses into the wax layer, so it was found to be statistically significant with the wax content of pine needles. High-number ring PAHs showed a high correlation with the amount of dust in pine needles because they mainly attached to dust particles and accumulated on the surface of pine needles. The ratios of fluoranthene/pyrene and methylphenanthrene/phenanthrene for predicting the origin of atmospheric PAHs have also been proven valid for pine needles.

Green mechanochemical activation of solid persulfate to remove PAHs in soil: Performance and mechanism

Due to the high biotoxicity and persistence of polycyclic aromatic hydrocarbons (PAHs), the remediation of PAHs-contaminated soil becomes an intractable problem. Persulfate-based advanced oxidation processes are widely used to degrade PAHs in aquatic environment. However, they are not convenient for used in soil due to the heterogeneity and complexity of soil matrix. In this study, a green and convenient ball milling process is introduced to activate persulfate for the remediation of PAHs-contaminated soil. About 82.5% PAHs were removed with 10% wt. Na2S2O8 (PS) addition and ball-milling for 2 h under 500 r/min. The degradation of PAHs is attributed to the attack of radicals (SO4·- and·OH) generated from the activation of PS by mechanochemistry. Moreover, stable Si-O bonds were disrupted during ball-milling process, and formed free electron on the surface of soil particles. This facilitates the electron transfer from oxidants to contaminants. The particle size, surface element composition, functional group, and thermogravimetric analysis confirmed the slight disturbance of ball-milling-assisted PS process on the physical and chemical properties of soil. Therefore, ball-milling assisted PS approach would be a promising technology for the remediation of PAHs-contaminated soil.

Predicting the bioavailability of polycyclic aromatic hydrocarbons in rhizosphere soil using a new novel in situ solid-phase microextraction technique

In situ measurement of the bioavailability of organic pollutants in soil is crucial for understanding their environmental behavior and assessing health risks. Due to the high heterogeneity of soil, microscale determination is crucial for achieving high accuracy, but few methods are available. In this study, microsized probes coated with polydimethylsiloxane (PDMS) were used to measure the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in soil in situ. The concentrations of PAHs enriched by the PDMS-coated probes correlated well with the results of bioassays using earthworms (R2 = 0.92–0.99) and ryegrass roots (R2 = 0.92–0.99). Compared with other chemical extraction methods, such as n-butanol extraction, the proposed method has advantages such as in situ operation, microvolume analysis, and negligible interference to the soil environment. In the soil rhizosphere zone, PAHs bioavailability decreased in the following order: rhizosphere > near-rhizosphere > far-rhizosphere. The bioavailability of PAHs in soil amended with biochar was also successfully characterized by the proposed method. Thus, this study developed an in situ and microscale method to predict the bioavailability of organic pollutants in contaminated soils and provides new insight into migration and transformation processes in rhizosphere soil.

Redox potential model for guiding moderate oxidation of polycyclic aromatic hydrocarbons in soils

In-situ chemical oxidation is an important approach to remediate soils contaminated with persistent organic pollutants, e.g., polycyclic aromatic hydrocarbons (PAHs). However, massive oxidants are added into soils without an explicit model for predicting the redox potential (Eh) during soil remediation, and overdosed oxidants would pose secondary damage by disturbing soil organic matter and acidity. Here, a soil redox potential (Eh) model was first established to quantify the relationship among oxidation parameters, crucial soil properties, and pollutant elimination. The impacts of oxidant types and doses, soil pH, and soil organic carbon contents on soil Eh were systematically clarified in four commonly used oxidation systems (i.e., KMnO4, H2O2, fenton, and persulfate). The relative error of preliminary Eh model was increased from 48–62% to 4–16% after being modified with the soil texture and dissolved organic carbon, and this high accuracy was verified by 12 actual PAHs contaminated soils. Combining the discovered critical oxidation potential (COP) of PAHs, the moderate oxidation process could be regulated by the guidance of the soil Eh model in different soil conditions. Moreover, the product analysis revealed that the hydroxylation of PAHs occurred most frequently when the soil Eh reached their COP, providing a foundation for further microorganism remediation. These results provide a feasible strategy for selecting oxidants and controlling their doses toward moderate oxidation of contaminated soils, which will reduce the consumption of soil organic matter and protect the main structure and function of soil for future utilization. Environmental implicationsThis study provides a novel insight into the moderate chemical oxidation by the Eh model and largely reduces the secondary risks of excessive oxidation and oxidant residual in ISCO. The moderate oxidation of PAHs could be a first step to decrease their toxicity and increase their bioaccessibility, favoring the microbial degradation of PAHs. Controlling the soil Eh with the established model here could be a promising approach to couple moderate oxidation of organic contaminants with microbial degradation. Such an effective and green soil remediation will largely preserve the soil’s functional structure and favor the subsequent utilization of remediated soil.