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Review

Contamination of Phthalic Acid Esters in China’s Agricultural Soils: Sources, Risk, and Control Strategies

by
Jin Han
1,
Zhenying Jiang
2,
Pengfei Li
3,
Jian Wang
3 and
Xian Zhou
3,*
1
Jiangsu Environmental Engineering Technology Co., Ltd., Nanjing 210019, China
2
Weihai Agricultural and Rural Affairs Service Center, Weihai 264200, China
3
Institute of Organic Contaminant Control and Soil Remediation, College of Resources and Environmental Sciences, Nanjing Agricultural University, Nanjing 211800, China
*
Author to whom correspondence should be addressed.
Agronomy 2025, 15(2), 433; https://doi.org/10.3390/agronomy15020433
Submission received: 26 December 2024 / Revised: 27 January 2025 / Accepted: 6 February 2025 / Published: 10 February 2025
(This article belongs to the Special Issue Risk and Management of Organic Contaminants in the Agricultural Environment)
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Abstract

:
Phthalic acid esters (PAEs), as an emergent pollutant in China’s agricultural environment, have raised significant environmental and health concerns due to their persistence, bioaccumulation, and potential risks. This review explores the sources, distribution, ecological impacts, and human health risks associated with PAEs in agricultural soils and crop systems across China. PAEs primarily originate from agricultural plastic materials, wastewater irrigation, and agrochemical additives, leading to widespread contamination. Concentrations of PAEs vary significantly by region, with hotspots identified in areas with intensive agriculture and industrial activities. The transfer of PAEs from soil to crops is a critical pathway for human exposure, particularly through vegetables and grains, posing carcinogenic and non-carcinogenic risks. The review highlights the fate and transformation processes of PAEs, including adsorption, migration, volatilization, and microbial degradation, which influence their environmental behavior and risks. Effective risk control measures, such as microbial remediation and advancements in biodegradation technologies, offer sustainable solutions to mitigate PAE contamination. This study emphasizes the critical need for comprehensive monitoring systems, stringent regulatory frameworks, and the implementation of sustainable agricultural practices to effectively reduce PAE concentrations in soils, thereby safeguarding soil health, ensuring food safety, and protecting human health.

1. Introduction

Phthalate plasticizers, commonly referred to as phthalates, are a group of synthetic organic chemicals widely used to enhance the flexibility, durability, and workability of plastics, particularly polyvinyl chloride (PVC) [1]. These compounds are integral to a variety of consumer products, including toys, medical devices, and food packaging. Major sources for phythalates in agricultural soils include plastic mulching films and other plastic materials, livestock manure and sewage sludge application, irrigation water, and crop protection products, making their presence in agricultural soils a significant environmental concern [2]. In China, the intensive use of plastic materials in agriculture has been driven by the need to increase crop yields and enhance productivity. Plastic mulching has become a common practice, particularly in vegetable cultivation and horticulture, and helps retain soil moisture, suppress weeds, and regulate soil temperature [3,4]. However, the degradation of these plastic materials in the agricultural environment can lead to the leaching of phthalates into the soil, raising concerns about their long-term effects on soil health and food safety [5,6].
Recent studies have documented the occurrence of phthalates in agricultural soils across various regions in China, revealing significant geographical variability influenced by local agricultural practices and industrial activities [7,8]. The accumulation of phthalates in soils poses potential risks to human health and the ecosystem, as these compounds are known to disrupt endocrine function and may have adverse effects on reproductive and developmental health [9,10]. Furthermore, their persistence in the environment raises questions about their bioaccumulation in crops, potentially leading to human exposure through the food chain [11,12]. Given the growing awareness of the environmental and health risks associated with phthalates, there has been an increasing focus on monitoring their presence in agricultural soils. Regulatory frameworks are also evolving in response to these concerns, with some phthalates being restricted or banned in various products [13]. However, the legacy of past practices and the ongoing use of plastic materials in agriculture continue to contribute to PAE contamination. Numerous studies have examined the extent of PAE pollution in agricultural soils across various regions of China. However, current studies on PAE contamination in agriculture have not been completely catalogued and reviewed, although a recent article reviewed the pollution status, ecological effects, and bioremediation strategies of phthalic acid esters in agricultural ecosystems, the article does not focus on detection methods and other repair techniques other than bioremediation [14,15].
This review aims to provide a comprehensive overview of the sources, distribution patterns, trends over time, and associated risks of phthalate plasticizers in agricultural soils in China. By synthesizing the current literature, we hope to highlight the need for effective monitoring and regulation, as well as the importance of adopting sustainable agricultural practices to mitigate the impacts of these contaminants on soil health and food safety.

2. Sources of Phthalic Acid Esters

Phthalic acid esters (PAEs) in agricultural soils have become a growing concern due to their persistence and potential health risks. They can enter agricultural soils through various sources, and their concentrations vary widely depending on factors such as proximity to industrial areas, soil management practices, and types of fertilizers and plastic films used (Figure 1). The primary sources and typical concentrations of PAEs in agricultural soils can be categorized as follows: (1) Plastic Mulching Films. Plastic mulching is widely used in agriculture to retain soil moisture, control weeds, and regulate soil temperature. These films are commonly made of polyvinyl chloride (PVC) or polyethylene (PE), which often contain PAEs like di(2-ethylhexyl) phthalate (DEHP) and dibutyl phthalate (DBP) as plasticizers [2]. Over time, PAEs can leach from these films due to UV radiation, temperature fluctuations, and microbial activity in the soil. With repeated use, PAE concentrations can build up in soils, especially where plastic mulch is not adequately disposed of or recycled [16,17]. (2) Wastewater and Sewage Sludge Application. Treated wastewater and sewage sludge are applied to agricultural fields in some areas as nutrient-rich fertilizers, especially in countries with limited freshwater resources. However, wastewater and sludge often contain PAEs from industrial effluents, household products, and personal care items. PAEs enter the sewage system when these items are used and disposed of, making their way into sewage sludge and wastewater. Commonly detected PAEs in sludge-amended soils include DEHP, DBP, and di-n-octyl phthalate (DnOP) [18,19]. Concentrations vary based on the amount and frequency of sludge application. (3) Pesticides, Fertilizers, and Agrochemical Additives. PAEs can be present in pesticides and fertilizers either as manufacturing impurities or from the plastic packaging materials that leach PAEs over time. Diethyl phthalate (DEP) and dimethyl phthalate (DMP) are sometimes found in pesticide formulations, as they may act as solubilizers or emulsifiers. Although PAE concentrations from this source alone may be relatively low, repeated use can contribute to cumulative contamination [20]. This is especially significant in intensively farmed areas. (4) Atmospheric Deposition. PAEs can be released into the atmosphere from industrial processes, vehicle emissions, and the burning of plastic waste. They can then be transported by air currents and deposited onto soil surfaces. Atmospheric PAEs may settle onto soil surfaces far from their original sources, especially in areas downwind of urban or industrial zones. Studies in rural areas near urban centers or industrial zones have detected PAE residues in soils, suggesting atmospheric deposition as a primary source in these cases [21,22]. (5) Agricultural Plastic Products. In addition to mulching films, other plastic materials used in agriculture, such as irrigation pipes, seedling trays, greenhouse coverings, and storage containers, contain PAEs. These materials may release PAEs directly into soil or water, particularly under high temperatures or prolonged UV exposure, leading to gradual accumulation. DEHP and DBP are again the predominant PAEs leached from these products, with reported concentrations varying based on the amount of plastic used in farming practices.

3. Concentration and Risk of PAEs in Agricultural Soil–Crop Systems

These sources collectively contribute to PAE levels in agricultural soils, leading to concerns over their persistence, bioaccumulation, and potential risks to human health through crop uptake and food chain transfer. Numerous studies have confirmed that PAE contamination is pervasive across China’s agricultural soils [23,24]. Thus, it is crucial to monitor the levels of PAEs in agricultural soils. Several analytical methods have been developed for this purpose, including ASE, SPE, UE, and Soxhlet extraction. These methods are typically coupled with analytical techniques such as GC/MS, LC/MS, or HPLC. Table 1 summarizes the extraction and analysis methods used for PAEs in soil.
Concentrations of PAEs vary significantly, influenced by regional agricultural practices, industrial activities, and the use of plastic materials [29]. National monitoring data suggest widespread pollution, often exceeding safety thresholds recommended by environmental standards (Table 2). In Northern China, including Beijing, Hebei, and Henan Provinces, the extensive use of plastic mulch films has contributed to moderate to high levels of PAE contamination. The total main PAEs (ΣPAEs) levels in some intensive farming areas were found to range between 1.29 and 12.2 mg/kg. In East China, the Yangtze River Delta, Zhejiang, Shandong, and Jiangsu Provinces are hotspots for PAE pollution due to the dense concentration of plastic manufacturing industries and urban activities. Agricultural soils in these regions have ΣPAE concentrations often exceeding 35 mg/kg. For example, studies in Shandong Province reported ΣPAEs in vegetable soils as high as 35.2 mg/kg. Western regions like Xinjiang and Gansu, where plastic mulch use is prevalent for arid land farming, also exhibit notable PAE pollution. In Xinjiang, ΣPAE concentrations in soils were reported between 3.23 and 2132.08 mg/kg. Agricultural soils in Gansu Province and Ningxia Hui Autonomous Region have ΣPAE concentrations with a range of 0.39~17.27 mg/kg and 0.031~2.96 mg/kg. In some places in the south, such as Guizhou and Guangzhou, the concentration of PAEs in agricultural soil is high, up to 25.6 mg/kg and 35.6 mg/kg, while the concentration in other provinces and cities is relatively low. The agricultural soil in Northwest China exhibits the highest concentrations of phthalic acid esters (PAEs), with the levels in the soil of a cotton field in Xinjiang reaching up to 1,232,076 μg/kg. This elevated concentration is likely attributed to the prolonged use of agricultural plastic films and their low recovery rates. The degradation and release of PAEs from these films significantly contribute to the accumulation of PAEs in the soil [30]. The concentration of PAEs in agricultural soils across most regions of China is significantly higher than in countries such as Serbia, France, the United Kingdom, and Denmark [31,32,33,34]. This disparity may be attributed to the widespread development of protected agriculture, including the extensive use of greenhouses, mulch films, fertilizers, pesticides, and sewage irrigation.
The transfer of PAEs from soils to crops represents a critical pathway for human exposure to these pollutants (Figure 2) [65]. Studies across China have documented the uptake of PAEs by various crops, raising food safety concerns. Vegetables, particularly leafy greens and root crops, show a high propensity for PAE accumulation [66]. In Zhejiang and Jiangsu Provinces, ΣPAE concentrations in lettuce and carrots ranged from 0.1 to 10 mg/kg, with DEHP being the predominant compound [67]. The study revealed that the concentration of PAEs in the edible portions of vegetables from Northeast China ranged from 32.4 to 602 ng·g−1. Leafy vegetables exhibited the highest levels of contamination, approximately one to three times greater than those found in root and fruit vegetables. The bioaccumulation factors (BAFs) of chemicals showed a significant negative correlation with their physicochemical properties, such as the octanol-water partition coefficient and the organic carbon partition coefficient [68]. Similarly, a survey conducted in the Yangtze River Delta found that the total concentrations of six PAEs (dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DnBP), benzyl butyl phthalate (BBP), di-(2-ethylhexyl) phthalate (DEHP), and di-n-octyl phthalate (DnOP)) in vegetables ranged from 10.9 to 16,400 ng·g⁻1 on a dry weight basis [39]. While rice exhibits lower PAE concentrations than vegetables, their widespread consumption makes even low-level contamination significant. Rice grains from regions using wastewater irrigation contained ΣPAEs of 1.77 to 4.13 mg/kg [69]. But high concentrations of PAEs were detected in wheat grains from mulching plots and ranged from 4.1 to 12.6 mg kg−1 in Changwu County, Shaanxi Province, China [70]. Meanwhile, fruit crops, such as apples and citrus, generally have lower PAE levels due to reduced soil–plant transfer. However, studies in greenhouse-grown fruits detected ΣPAE levels below one mg/kg [71].
Organic contaminants in agricultural soil can enter the human body through various pathways and pose a potential carcinogenic risk to human health. The non-carcinogenic and carcinogenic risks of PAEs to farmers and children in greenhouses were evaluated using methods recommended by the USEPA (2013). Among the PAE congeners studied, DMP, DEP, DnBP, and DnOP were identified as non-carcinogenic to human health, whereas BBP and DEHP posed carcinogenic risks. The risk assessments considered both dietary exposure (limited to the consumption of vegetables grown in plastic film greenhouse soils) and non-dietary exposure routes, including soil ingestion, dermal contact, and inhalation. For instance, PAEs present in soil can enter the human body through inhalation of soil particles, skin contact, or ingestion of soil [72]. Additionally, PAEs in soil can be absorbed by plant roots, accumulate in crops, and ultimately enter the human body via the food chain. A risk assessment of PAEs in the soil–crop system indicates that DnBP, DEHP, and DnOP exhibited elevated non-cancer risks, with values of 0.039, 0.338, and 0.038, respectively. The carcinogenic risk of DEHP for farmers working in plastic film greenhouses was approximately 3.94 × 10−5. Health risks were primarily associated with exposure through vegetable consumption and soil ingestion [61]. A study conducted by Wang et al. found that di-n-butyl phthalate (DBP) and di-(2-ethylhexyl) phthalate (DEHP) were detected in all soil and grain samples, with DEHP identified as the dominant PAE compound in grains. Based on the concentrations of DEHP in wheat grains, the calculated carcinogenic risk values for adults exceeded the recommended threshold of 10−4 [61].
In addition to its harmful effects on human health, PAEs are toxic to soil organisms. The presence of PAEs in soil can reduce microbial diversity, disrupt microbial community structures, and interfere with the normal physiological functions of microorganisms. For example, the addition of DEP or DEHP at concentrations comparable to those found in non-industrial environments (0.1 mg/g) showed no significant impact on the structural diversity (e.g., bacterial abundance and fatty acid methyl ester analyses) or functional diversity (e.g., BIOLOG analysis) of microbial communities. However, at higher concentrations, such as those representing a phthalate spill (DEP > 1 mg/g), there was a significant reduction in total culturable bacteria (47%) and pseudomonads (62%) within one day [73]. Research on the ecotoxicity of PAEs to soil animals remains in its early stages, with most current studies focusing on aquatic organisms. However, some studies have examined the effects of PAEs on soil invertebrates, such as earthworms. For instance, phthalates have been shown to enhance ROS generation, increase lipid peroxidation, and activate GST, resulting in oxidative stress and DNA damage in earthworms (Eisenia fetida) [74]. Furthermore, PAEs in farmland soils, particularly those with a low molecular weight and high lgKow values, are easily absorbed by crops, potentially harming crop growth. The extent of this damage is positively correlated with the degree of PAE contamination in the soil. In a study by Gao et al. (2018), wheat plants exposed to DEHP at concentrations of 10, 20, and 40 mg/kg showed reduced photosynthetic parameters, fluorescence parameters, and chlorophyll contents at the seedling, jointing, and booting stages, along with an increase in intercellular carbon dioxide concentration [75]. These findings highlight the negative effects of PAEs on both soil organisms and agricultural productivity.

4. Fate and Transformation of PAEs in Agricultural Soils

Soil plays a vital role as a medium for the accumulation, migration, and transformation of PAEs [76]. After entering the soil, PAEs follow multiple pathways of migration and transformation (Figure 3). A considerable portion may be absorbed by soil, volatilize into the atmosphere, or leach into groundwater or surface water, leading to cross-media pollution. These pollutants can eventually travel through the food chain and reach the human body. Meanwhile, another portion of PAEs may undergo degradation or transformation through the combined effects of physical, chemical, and biological factors. These processes can either partially or eliminate PAEs from the soil environment, depending on the environmental conditions and the characteristics of the compounds involved.

4.1. Adsorption

PAEs adsorb onto soil particles primarily through van der Waals forces, hydrogen bonding, and ionic interactions. The adsorption capacity of PAEs is different in different soil types. Research indicates that the adsorption process of dibutyl phthalate (DBP) in soils is primarily governed by physical sorption mechanisms [77]. Clay and organic-rich soils show strong adsorption, limiting downward migration. Studies have shown that the adsorption of PAEs in red soil is strengthened by the presence of dissolved organic matter [78,79]. Sandy soils with a lower organic content exhibit reduced adsorption, leading to higher mobility. Hydrogen bonding and hydrophobic partitioning are recognized as the primary mechanisms driving the adsorption of PAEs onto soil organic matter [80]. In addition, soil acidity and temperature also affect the adsorption capacity of PAEs. An increased pH decreases PAE adsorption as organic matter dissociates and forms negatively charged ions, repelling PAEs. The pH significantly affects the adsorption of hydrophobic organic matter, including changes in adsorbent structure, diffusion effects, and compound hydrophobicity. As the esterified hydroxyl chain length in PAEs increases, their polarity decreases, and hydrophobicity rises. A higher pH causes the dissociation of hydroxyl and carboxyl groups in soil organic matter, leading to stronger hydrophilicity, extended configurations, and a reduced adsorption capacity for PAEs. Additionally, elevated pH can hydrolyze some PAEs, forming negatively charged groups that repel soil organic matter, further reducing adsorption. The increased pH also loosens soil organic matter structures through electrostatic repulsion, weakens functional group interactions, and forms cross-linked structures that aggregate hydrophobic regions and block adsorption sites, ultimately decreasing adsorption capacity [81]. Elevated temperatures reduce adsorption as the soil–PHA interaction weakens [82,83].

4.2. Biodegradation

Microbial degradation is the primary pathway for organic contaminants’ removal in soils [84]. Soil bacteria, such as Pseudomonas and Rhodococcus, play a significant role, with degradation rates influenced by PAE structure (e.g., chain length) and soil conditions. PAEs are initially hydrolyzed into phthalic acid, which can undergo complete mineralization to CO2 and H2O under aerobic conditions (Figure 4) [85]. Anaerobic conditions slow down degradation. Tao et al (2019) isolated a Pseudomonas strain, DNE-S1, from soil that exhibits a high efficiency in degrading PAEs, particularly DEP, under alkaline conditions. The presence of Fe3+ was found to enhance DEP degradation by DNE-S1 through the upregulation of the dihydrodiol phthalate dehydrogenase (ophB) and dioxygenase-ferredoxin reductase (ophA4) genes, resulting in a 14.5% increase in the degradation rate for 500 mg/L DEP within 12 h [86]. A recent study identified and characterized a novel marine bacterium, Gordonia sihwaniensis RL-BY03, for its ability to degrade phthalic acid esters (PAEs) [87]. The strain RL-BY03 demonstrated the capability to utilize several types of PAEs as its sole carbon source. The optimal conditions for the degradation of di(2-ethylhexyl) phthalate (DEHP) were determined to be an initial pH of 8.0 and a temperature of 30 °C. Biochemical and molecular analyses revealed a correlated metabolic pathway in which RL-BY03 converted DEHP into di-n-butyl phthalate (DBP) and diethyl phthalate (DEP) through β-oxidation. These intermediates were subsequently hydrolyzed into phthalic acid, completing the degradation process [88].

4.3. Migration

The horizontal and vertical migration of phthalic acid esters (PAEs) in soil are key processes influencing their environmental distribution and potential ecological impacts. Horizontal migration primarily occurs via surface runoff and lateral subsurface flow. During rainfall or irrigation, PAEs dissolved in water or adsorbed onto soil particles can be transported across the soil surface, with the extent of movement depending on slope, soil type, and vegetation cover. Subsurface lateral flow often occurs when water moves along permeable soil layers or interfaces, particularly in soils with high permeability, such as sandy soils. In contrast, vertical migration refers to the downward or upward movement of PAEs within the soil profile, driven by water infiltration and vapor diffusion [89,90]. Downward migration, or leaching, is influenced by factors such as soil porosity, texture, and organic matter content. The research confirms that significant differences in the vertical distribution of DBP and DEHP in soil were observed between the two cultivars and between sterilization and non-sterilization treatments. Both DBP and DEHP were capable of leaching to the bottom soil layers, although their concentrations in both soil and pore water decreased with increasing soil depth. At the ripening stage, the concentrations of DBP and DEHP in pore water were strongly correlated with those in the corresponding soil layers [91]. Sandy soils promote rapid percolation and the deeper migration of PAEs, while clay or organic-rich soils adsorb PAEs, limiting their mobility [92]. Understanding the interplay between horizontal and vertical migration is essential for assessing the risks PAEs pose to soil, water, and air quality and for developing effective management strategies.

4.4. Volatilization

The volatilization of phthalic acid esters (PAEs) in soil is the process in which these compounds transfer from the liquid or adsorbed phases into the gaseous phase, contributing to their release into the atmosphere [93]. This phenomenon is influenced by the chemical properties of PAEs, particularly their vapor pressure and molecular weight. Lighter PAEs, such as dimethyl phthalate (DMP) and diethyl phthalate (DEP), with higher vapor pressures, are more prone to volatilization compared to heavier ones like di(2-ethylhexyl) phthalate (DEHP) [94]. Environmental factors such as soil temperature, moisture content, and organic matter levels also play critical roles. Warmer temperatures increase the kinetic energy of PAE molecules, enhancing their volatilization rate. Otton et al. found that the half-life of PAEs increased strongly (ca. eight-fold) with temperatures in the range of 5–22 °C and did not depend on alkyl chain length [95]. Conversely, a high level of soil moisture can reduce volatilization by trapping PAEs in the liquid phase, whereas dry conditions facilitate their transfer to the gas phase. While volatilization reduces the concentration of PAEs in soil, it poses environmental risks by transferring these compounds to the atmosphere, potentially contributing to air pollution and long-range atmospheric transport [96]. Understanding the mechanisms of volatilization is essential for evaluating the fate of PAEs in the environment and mitigating their impact on air quality.

5. The Control of PAE Contamination Risks in Soil–Crop Systems

Historically, the management of phthalate ester (PAE) contamination in soil–crop systems has focused on remediating polluted soils. Conventional remediation strategies, such as physicochemical methods and phytoremediation, have been extensively employed for soil contamination management (Table 3) [97]. However, these approaches exhibit considerable limitations when implemented in agricultural soils. Physicochemical methods, including physical absorption, thermal desorption, and chemical oxidation, are inherently invasive and can significantly disrupt soil structure and fertility [98]. The reliance on external chemical agents and high temperature in these methods pose risks of secondary pollution, lead to potential shifts in soil pH, and have adverse effects on native microbial communities. Additionally, the high operational costs and energy-intensive nature of these techniques render them impractical for large-scale agricultural applications, particularly those in which maintaining soil health and productivity is critical.
Microbial remediation is a promising technology for organic contaminant pollution risk control in soil–crop systems due to its environmentally friendly and cost-effective characteristics [99,100]. Microbial remediation has emerged as a highly effective and sustainable approach for mitigating the risks associated with phthalate ester (PAE) contamination in agricultural soils. Microbial remediation leverages the natural ability of microorganisms to degrade or transform PAEs into less harmful substances. Microbial species, including bacteria, fungi, and actinomycetes, play a critical role in the biodegradation of PAEs [101]. The primary mechanisms include the following: Enzymatic degradation: Microorganisms produce specific enzymes, such as esterases and hydrolases, that cleave the ester bonds in PAEs, breaking them down into monoesters and eventually into simpler, non-toxic compounds like carbon dioxide and water. Co-metabolism: Microorganisms degrade PAEs as part of their metabolic processes, often utilizing PAEs as a carbon source under nutrient-limited conditions. Synergistic interactions: Microbial communities work synergistically, where different species complement each other’s metabolic pathways, enhancing the overall degradation efficiency [102].
Recent advancements in microbial remediation technologies have further enhanced their applicability in soil–crop systems. Consortium approaches: Developing microbial consortia with complementary degradation pathways can improve the overall efficiency and robustness of the remediation process [103]. Recently, Li et al. (2024) identified and assembled a consortium of functional endophytic bacteria with a high efficiency and broad-spectrum capability for degrading polycyclic aromatic hydrocarbons (PAHs). This consortium demonstrated the ability to degrade 16 different PAHs. Following a 20-day colonization period in plants, the PAH content in vegetables was reduced by 40.63% [104]. Immobilized microorganisms: The encapsulation of microorganisms in carriers such as alginate beads or biochar can enhance their stability and activity in soil environments, providing a sustained remediation effect. A study by Zhou et al. (2024) investigated the effect of an inoculated microbial (IM) consortium applied to corn straw on the biodegradation of polycyclic aromatic hydrocarbon (PAH) in soil. The results indicated that the total PAH removal rate in the soil was 88.25% following 20 days of IM treatment, a 39.25% increase compared to the control, suggesting that IM enhances the degradation of PAHs in contaminated soils [105]. Genetic engineering: The genetic modification of microorganisms has enabled the production of more efficient PAE-degrading strains. For instance, recombinant Escherichia coli expressing esterase genes has shown enhanced PAE degradation capabilities [106]. Omics approaches: Metagenomics, proteomics, and transcriptomics provide insights into microbial communities and their functional genes, enabling the identification of key degraders and the optimization of remediation strategies [107].
Microbial remediation represents a promising solution for controlling the risk of PAE contamination in soil–crop systems. By leveraging the natural biodegradation capabilities of microorganisms, this approach offers a sustainable, cost-effective, and environmentally friendly alternative to conventional remediation methods. Continued research and innovation in microbial remediation technologies will be crucial for addressing the growing challenge of PAE pollution and ensuring the safety and productivity of farmland ecosystems.
Table 3. The Control of PAE Contamination Risks in Soil–Crop Systems.
Table 3. The Control of PAE Contamination Risks in Soil–Crop Systems.
MethodsAdvantageDisadvantageReference
Physical remediationThe bioavailability of pollutants can be reduced in a short timeAdsorbed PAEs are easily desorbed and cannot be removed directly from the soil[108]
Chemical remediationStrong oxidation capacity, wide application range, no secondary pollution, and strong operability for organic pollutantsNegative effects on soil physicochemical properties and microbial community composition[109]
BioremediationHigh efficiency, complete PAE degradation, low cost, and environmental friendlinessLong processing time, strict
requirements for external conditions		[110]

6. Conclusions and Outlook

This review highlights the pervasive contamination of phthalic acid esters (PAEs) in China’s agricultural soils, identifying their sources, environmental fate, and associated risks to human health and ecological systems. The findings underscore the critical role of agricultural practices, industrial activities, and improper waste management in exacerbating PAE pollution. Despite significant advancements in monitoring and regulatory measures, the persistence and bioaccumulation of PAEs in soil–crop systems continue to pose serious challenges to soil health, food safety, and sustainable agriculture.
Future research should prioritize the development of more effective, scalable, and eco-friendly remediation technologies, particularly microbial and bioengineering approaches. Advancements in omics technologies and genetic engineering offer promising avenues for identifying and enhancing microbial strains capable of degrading PAEs efficiently under varied environmental conditions. Additionally, exploring the synergistic potential of microbial consortia and immobilization techniques can further optimize biodegradation processes.
To mitigate the risks of PAE pollution, a multi-pronged approach is essential. Policymakers should strengthen the enforcement of existing regulations and incentivize the adoption of sustainable agricultural practices, such as the reduced reliance on plastic materials and improved waste management. Public awareness campaigns can also play a pivotal role in fostering responsible consumer behavior and community engagement.
Overall, addressing PAE pollution in agricultural systems requires coordinated efforts across scientific, regulatory, and societal domains. By embracing innovative technologies and sustainable practices, it is possible to safeguard agricultural productivity, protect environmental health, and ensure food safety for future generations.

Author Contributions

J.H., Z.J.: Methodology, Investigation, Data collection, Writing—original draft. P.L.: Writing—review and editing. J.W., X.Z.: Funding acquisition, Writing—review and editing. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financially supported by the National Key R&D Plan Key Projects (2023YFE0110800), the National Natural Science Foundation of China (42377011), and the Fundamental Research Funds for the Central Universities (KJYQ2025038).

Conflicts of Interest

Author Jin Han was employed by the company Jiangsu Environmental Engineering Technology Co., Ltd. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

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Agronomy 15 00433 g001
Figure 1. Source of PAEs in soil.
Figure 1. Source of PAEs in soil.
Agronomy 15 00433 g001
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Figure 2. Schematic diagram of PAEs in soil entering human body.
Figure 2. Schematic diagram of PAEs in soil entering human body.
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Figure 3. Schematic diagram of PAEs’ migration and transformation in soil.
Figure 3. Schematic diagram of PAEs’ migration and transformation in soil.
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Figure 4. Microbial aerobic degradation (a) and hydrolysis (b) pathways of PAEs.
Figure 4. Microbial aerobic degradation (a) and hydrolysis (b) pathways of PAEs.
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Table 1. The extraction and detection of PAEs in soil.
Table 1. The extraction and detection of PAEs in soil.
ExtractionDetectionLOD (μg L−1)Time (min)Recovery (%)Reference
ASEGC–MS system20–7017.275–120[25]
ASE-SPEGC–MS system0.03–27015.186–111Proposed method
ASEHPLC/FLD0.99–19.803073.03–91.89[26]
ASEMEEKC/UV0.2–0.4 (mg kg−1)1688.5–119.7[27]
QuEChERSGC–MS/MS0.09–0.43 ng g−13097.2–99.1[28]
ASE: accelerated solvent extraction, SPE: solid-phase extraction, QuEChERS: quick, easy, cheap, effective, rugged, and safe; GC–MS: gas chromatography–mass spectrometry; HPLC/UV: high-performance liquid chromatography/fluorescence detector; MEEKC/UV: microemulsion electrokinetic chromatography/ultraviolet detector.
Table 2. PAE concentration in agricultural soils in China (µg/kg).
Table 2. PAE concentration in agricultural soils in China (µg/kg).
LocationLocation SpecificationMinMaxReferences
North China
Shanxi (Lvliang)Crop soils/512 (Σ6PAEs)[35]
BeijingVegetable soil46.251287.96 (Σ15PAEs)[36]
Agricultural soil180012200 (Σ6PAEs)[37]
HeibeiVegetable soil/910 (Σ12PAEs)[38]
Crop soil/842 (Σ12PAEs)
TianjinAgricultural soil5010400 (Σ6PAEs)[39]
HuhehaoteAgricultural soil/3280 (Σ4PAEs)[40]
Shanxi (Changzhi)Agricultural soil/2380 (Σ4PAEs)
HenanVegetable soil/965 (Σ12PAEs)[38]
Crop soil/760 (Σ12PAEs)
Northwestern China
GansuAgricultural soil31.11141.7 (Σ6PAEs)[41]
Greenhouse soil394.72961.8 (Σ6PAEs)
XinjiangMelon patch soil57.33272.7 (Σ6PAEs)[42]
Cotton field soil123,9251232076 (Σ6PAEs)[43]
NingxiaCotton field soil13604490 (Σ16PAEs)[44,45,46,47,48]
Vegetable soil212317271(Σ11PAEs)
Agricultural soil7278728 (Σ16PAEs)
Greenhouse soil112111924 (Σ16PAEs)
Agricultural soil31715355 (Σ16PAEs)
Agricultural soil21065124 (Σ16PAEs)
Agricultural soil39111924 (Σ16PAEs)
Qinghai (Weinan)Agricultural soil/522 (Σ4PAEs)[40]
Qinghai (Yulin)Agricultural soil/279 (Σ4PAEs)
East China
Yangtze River DeltaAgricultural soils1679370 (Σ15PAEs)[49]
Agricultural soils5.41580 (Σ6PAEs)[50]
JiangsuGreenhouse soil42.5276.8 (Σ6PAEs)[51]
ZhejiangAgricultural soil30725219 (Σ12PAEs)[38]
ShandongVegetable soil7561590 (Σ16PAEs)[52]
Vegetable soil137418810 (Σ16PAEs)[53]
Greenhouse soil4531615 (Σ6PAEs)[54]
Agricultural soil218.41168.9 (Σ6PAEs)[55]
Greenhouse soil193935442 (Σ16PAEs)[56]
HenanVegetable soil/965 (Σ12PAEs)[38]
Crop soil/760 (Σ12PAEs)
TaiwanAgricultural soil/700 (Σ6PAEs)[57]
AnhuiAgricultural soil234.5304.8 (Σ16PAEs)[58]
FujianAgricultural soil/1018 (Σ15PAEs)[59]
JiangxiAgricultural soil274.8737.7 (Σ16PAEs)[58]
ShanghaiAgricultural soil284.5589.2 (Σ16PAEs)[58]
South China
GuangzhouAgricultural soil19533600 (Σ16PAEs)[60]
GuangdongAgricultural soil1832037.6 (Σ6PAEs)[61,62]
Vegetable soil1401140 (Σ16PAEs)
Leizhou PeninsulaAgricultural soilND1770 (Σ6PAEs)[63]
HainanAgricultural soils46614 (Σ16PAEs)[64]
GuangxiAgricultural soils78.8902.5 (Σ16PAEs)[48]
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Han, J.; Jiang, Z.; Li, P.; Wang, J.; Zhou, X. Contamination of Phthalic Acid Esters in China’s Agricultural Soils: Sources, Risk, and Control Strategies. Agronomy 2025, 15, 433. https://doi.org/10.3390/agronomy15020433

AMA Style

Han J, Jiang Z, Li P, Wang J, Zhou X. Contamination of Phthalic Acid Esters in China’s Agricultural Soils: Sources, Risk, and Control Strategies. Agronomy. 2025; 15(2):433. https://doi.org/10.3390/agronomy15020433

Chicago/Turabian Style

Han, Jin, Zhenying Jiang, Pengfei Li, Jian Wang, and Xian Zhou. 2025. "Contamination of Phthalic Acid Esters in China’s Agricultural Soils: Sources, Risk, and Control Strategies" Agronomy 15, no. 2: 433. https://doi.org/10.3390/agronomy15020433

APA Style

Han, J., Jiang, Z., Li, P., Wang, J., & Zhou, X. (2025). Contamination of Phthalic Acid Esters in China’s Agricultural Soils: Sources, Risk, and Control Strategies. Agronomy, 15(2), 433. https://doi.org/10.3390/agronomy15020433

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