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Article

Occurrences, Possible Sources, and Risk Impacts of Organochlorine Pesticides in Soil of Changchun Central Urban Area, Northeast China

by
Wei Zhao
,
Jilong Lu
*,
Yawen Lai
,
Yaru Hou
,
Xinyun Zhao
,
Qiaoqiao Wei
,
Xiaoxiao Zou
and
Zhiyi Gou
College of Geo-Exploration Science and Technology, Jilin University, Changchun 130026, China
*
Author to whom correspondence should be addressed.
Sustainability 2023, 15(24), 16801; https://doi.org/10.3390/su152416801
Submission received: 8 November 2023 / Revised: 30 November 2023 / Accepted: 7 December 2023 / Published: 13 December 2023
(This article belongs to the Section Environmental Sustainability and Applications)
Browse Figures
Versions Notes

Abstract

:
Eighteen organochlorine pesticides (OCPs) in soil samples from the Changchun central urban area, Northeast China were analyzed using accelerated solvent extraction combined with gas chromatography/mass spectrometry (ASE-GC/MS) for the purpose of elucidating their contamination status, distribution characteristics, influencing factors, and feasible dangers in this city region. The complete concentrations of OCPs ranged from 15.63 to 92.79 ng/g, with a geomean of 36.46 ng/g. Hexachlorocyclohexane(HCHs), dichlorodiphenyltrichoroethane (DDTs), and chlordanes were the most dominant OCPs, with γ-HCH and p,p′-DDT being the predominant isomers. Higher concentrations of OCPs often centered to the northeast and southwest of the Changchun metropolis, and these artificial influences contributed to the destiny of OCPs in the soils. The residues of OCPs were derived from the historic utility of the technological DDT, dicofol, and lindane. A Pearson’s correlation evaluation indicated that TOC was once a key factor controlling OCP accumulation. The ecological risk evaluation based on the soil quality guidelines (SQGs) advises that the presence of DDTs, lindane, and heptachlor may additionally pose a poisonous ecological danger to soil organisms. The contrast outcomes of the incremental lifetime cancer risk (ILCR) confirmed that the highest cancer risk of OCPs to the posed populace was once low, whilst some unique areas with excessive OCP residues ought to be given attention. The research results provide basic information for evaluating the extent of OCP pollution in the soil of major cities in Northeast China and can help authorities establish environmental protection regulations and soil remediation techniques.

1. Introduction

Organochlorine pesticides (OCPs) are synthetic chlorinated organic compounds with benzene or cyclopentadiene as the main component [1]. They are categorized as persistent organic pollutants (POPs) because of their ubiquity, persistence, and bioaccumulation in the environment [2]. Their immoderate toxicity poses significant threats to human health and biodiversity [3]. Some OCPs have been recognized as endocrine disruptors (EDS) owing to their functionality of altering and affecting hormonal behavior in human beings or other organisms [4]. OCPs are hydrophobic and lipophilic, and soil media are important reservoirs for the surrounding OCPs due to their excellent retention competencies [5]. Consequently, even after the phasing out of OCPs many years ago, the giant quantity of pesticides collected in the soil remains a significant supply of re-emission into the surroundings [6].
China used to be the greatest producer and purchaser of OCPs, specifically the typical OCPs represented via hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT). HCHs and DDTs have the traits of high efficiency, broad-spectrum insecticidal capabilities, and low cost. They have been broadly produced and used in crop production, public health, and pest management in China [7]. Between the 1950s and the 1980s, China is estimated to have produced 4.9 million tons of HCHs and 0.46 million tons of DDT, accounting for 33% and 20%, respectively, of the world’s total production [8]. Although the manufacture and use of OCPs were formally outlawed in 1983, a small amount of HCH and DDT are still produced in China as raw materials for other chemicals such as lindane and dicofol [9,10]. The global distillation effect has broadly dispersed OCPs, and these pesticide metabolites and residues are still regularly found in environmental media in various parts of China, endangering the ecological environment’s safety [11]. OCP pollution in urban soil is even worse than in agricultural soil. The residual levels of soil OCPs at the regional scale in China show significant spatial variability, indicating a regional distribution pattern of south > central > north [12]. Urban soil is an important component of urban ecology and has a significant impact on the quality of urban ecological environments. Organochlorine pesticides were widely produced and applied in fields to treat agricultural plant diseases and pests, as well as for urban disease prevention and control in the 1950s and 1960s. These pollutants have high toxicity, bioaccumulation capabilities, and persistence, and they persist in soil, affecting urban soil quality and having significant adverse effects on human health and the sustainable development of cities. Therefore, understanding the residual characteristics of OCPs in urban soil environments and assessing their potential risks are of great significance to ensuring the quality of urban ecological environments and the health of urban residents, and it has important value for ensuring the sustainable and healthy development of cities.
As an important industrial and agricultural production base in northeast China, Changchun is an important economic, political, cultural, and transportation center in Jilin Province. The total area of the city is 20,593 km2, of which the central urban area is 543 km2 [13]. Changchun is located in the hinterland of the northeast Songliao Plain. The predominant soil varieties are black soil, dark brown calcium soil, and meadow soil [14]. Numerous studies have been conducted on residual OCP amounts in soil from other parts of China [12,15,16,17,18,19,20,21]; however, the literature regarding the level of OCP contamination in the Changchun central urban area is surprisingly scant. The central urban area of Changchun is the core carrying area of urban functions and also the most densely populated area of the city. Therefore, it is crucial to conduct routine soil investigations to determine the level of OCP pollution in the central urban areas of Changchun, northeast China. Thus, the main goals of this study were to (1) investigate the presence of OCPs and their geographic distribution in Changchun’s various types of soil, (2) identify their composition and potential sources, (3) determine how OCPs relate to soil properties, and (4) assess their potential for causing cancer and ecological risks. This study provides basic theoretical data for local environmental protection departments, to help develop reasonable soil pollution control plans and organic chlorine pollution risk management practices.

2. Materials and Methods

2.1. Soil Sample Collection

Forty-eight surface soil samples were collected from the central urban area of Changchun (as shown in Figure 1). According to their geographical location and land-use type, the sampling sites were classified into 8 park zone samples (PZ1–PZ8), 10 industrial zone samples (IZ1–IZ8), 10 residential zone samples (RZ1–RZ8), 11 commercial traffic zone samples (CT1–CT11), 5 cultural and educational zone samples (CE1–CE5), and 4 outskirt farmland samples (OF1–OF4). Five surface subsamples (0–20 cm) were taken from each sampling site and mixed together into a single composite sample using the diagonal method. Each sampling site was laid out in a 10 m by 10 m grid. After removing stones, leaves, and other impurities, all soil samples were sieved through an 80-mesh sieve and freeze-dried at −50 °C for 24 h. They were then sealed in polyethylene containers and kept at −4 °C until further analysis.

2.2. Reagents and Materials

The OCP standard solution contained α-, β-, γ- and δ-HCH, p,p′-DDE, p,p′-DDT, o,p′-DDT, p,p′-DDD, hexachlorobenzene (HCB), heptachlor (HEPT), hepoxide (HEPX), trans-chlordane (TC), cis-chlordane (CC), aldrin, dieldrin, and endrin; α-endosulfan (α-end) and β-endosulfan (β-end) mixed in methanol were purchased from Tan-Mo Technology Co., Ltd. (TM standard, Beijing, China). As a substitute for actual standards, 2,4,5,6-tetrachloro-mxylene in n-hexane solvent was employed to monitor the quality of the pre-treatment procedure. A deuterated mixture standard solution containing naphthalene-d8(NaP-d8), acenaphthene-d10(Ace-d10), phenanthrene-d10(Phe-d10), chrysene-d12 (Chr-d12), and perylene-d12(Pyr-d12) in dichloromethane solvent was used as the internal standard chemical for quality monitoring during instrument detection. Haodi Chemical Reagent Co., Ltd. (Changchun, China) supplied the analytic-quality anhydrous ethanol, dichloromethane (DCM), n-hexane, and solvents for acetone chromatography. By soaking the copper powder [Cu] in 2 N of HCl for 12 h, the powder was activated. The Cu powder was then cleaned with acetone after being washed 3 times with water. The major objective of adding [Cu] during extraction is to eliminate the sulfur element from the soil samples [22]. Granular diatomite (20–40 mesh) and quartz sand were used as desiccants and filters were refined in a muffle furnace for 4 h at 400 °C before being stored in a desiccator.

2.3. Extraction and Analysis of 18 OCPs

The 18 OCPs were extracted from the soil samples using the accelerated solvent extraction (ASE) method. The specific extraction method has been described in our previous study [23]. In brief, an accelerated solvent extractor (Shanghai Spectrum Instruments, Shanghai, China) was used to extract exactly 15.0 g of freeze-dried soil samples that had been spiked with a surrogate standard combination using a DCM-hexane (1:1, v/v) mixture. The finished extracts were concentrated to a volume of around 2 mL using a vacuum rotary evaporator (Shanghai Yarong Instruments, Shanghai, China) with a water bath temperature of 50 °C and a spin rate of 60 rpm; they were then cleared using a Florisil cartridge column (1000 mg, 6 mL) set up in a solid phase setup. The magnesium silicate column was activated with 5 mL DCM and 10 mL n-hexane prior to filtration, and the fraction was then discarded. The extracts were then passed over the column with 10 mL of DCM/n-hexane (2:8, v/v) to elute them. For further instrumentation analysis, all eluents were gathered, concentrated to 1.0 mL, and then transferred to a clean vial.
Using a Clarus 580/680 gas chromatograph-SQ8 mass spectrometer (ClarusSQ8 GC-MS, PerkinElmer, Waltham, MA, USA), a DB-5 elastic quartz capillary column (30 m × 0.25 mm × 0.25 m), and ultrapure helium (>99.999% pure) as the carrier gas, 18 OCPs were analyzed in the Changchun urban soil samples. The instrument parameter conditions (including gas chromatography reference conditions and mass spectrometry reference conditions) were set in accordance with the National Environmental Protection Standard of the People’s Republic of China (HJ 835-2017) [24] and adjusted appropriately to ensure that all compounds were well detected. The sample extracts (each 1.0 L) were injected in the splitless mode. The oven temperature program was set to hold at 80 °C for 2 min, increase to 180 °C at a rate of 20 °C/min, hold for 5 min, increase to 240 °C at a rate of 5 °C/min, hold for 5 min, and then increase from 240 °C to 290 °C at a rate of 10 °C/min before holding for 8 min. The MS was operated in electron impact ionization mode with an electron energy of 70 eV. The inlet and transfer line temperatures were both 280 °C and the iron source temperature was 230 °C. We analyzed the OCP standard solution using GC-MS in MS scanning mode, to record its retention time for qualitative analysis. We quantified each OCP compound using an internal standard calibration with a peak area based on the selective ion monitoring (SIM) mode. Before detecting the target OCPs using the instrument, we parallel-tested the mixed internal standard solution 6 times with a concentration of 10 ug/mL, to test the accuracy of the instrument testing. The results are shown in Figure 2, and the relative error of the internal standard compound ranged from −6.07% to 11.17%, indicating that the accuracy of instrument testing meets the testing requirements.

2.4. Quality Control and Data Analysis

Strict quality control methods including blank samples, parallel samples, blank-spiked samples, and matrix-spiked samples were used to check the accuracy of the data. A set of blank experiments and parallel experiments were carried out for each batch of samples. After 7 parallel determinations of the blank sample (quartz sand replacement) with a scalar amount of 0.01 ng/g, the detection limit of the method was found to be 3.143 times the standard deviation of the results. The concentrations of target compounds in blank samples were lower than the detection limits, and the detection limits of specific OCPs ranged from 0.05 to 0.62 ng/g. The target compounds’ relative standard deviations (RSDs) in parallel samples ranged from 3% to 14%, the recovery rate for spiked samples was 81–108%, and the recovery rate of substitutes in all samples was 79–105%, which is in line with the recovery standard. The final data results were not corrected by the recovery rate.

2.5. Cancer Risk Assessment Model

Endocrine diseases, immunological and nervous system issues, and even cancer may result from human exposure to OCPs in the soil [25]. The regional environmental screening values recommended by the US Environmental Protection Agency (EPA) were used to evaluate these OCPs’ health effects. Lifetime increased cancer risk (ILCR) measures a person’s likelihood of developing cancer over their lifetime due to exposure to potential chemical carcinogens. We determined the impact of soil residue OCPs on different population groups in Changchun through 3 exposure pathways: (1) inadvertent ingestion of soil OCPs, (2) dermal absorption of soil OCPs, and (3) inhalation of soil OCPs [26]. Equations (1)–(3) were adapted from the USEPA standard models to determine the ILCRs of the 3 pathways [27,28,29]:
I L C R ingestion = C soil × ( C S F i n g e s t i o n × ( B W / 70 ) 3 ) × I R soil × E F × E D B W × A T × C F
I L C R dermal = C soil × ( C S F dermal × ( B W / 70 ) 3 ) × S A × F E × A F × A B S × E F × E D B W × A T × C F
I L C R inhalation = C soil × ( C S F inhalation × ( B W / 70 ) 3 ) × I R air × E F × E D B W × A T × P E F
where ILCRingestion, ILCRdermal, and ILCRinhalation are the lifetime increased cancer risks caused by oral ingestion, dermal contact, and respiratory inhalation of OCPs in soil, respectively. Csoil represents the concentration of OCPs in soil, ng/g dw. CSFingestion, CSFdermal, and CSFinhalation are the carcinogenic slope factors of OCPs through oral ingestion, dermal contact, and respiratory inhalation of OCPs in soil, respectively, and the specific values are shown in Table S2 (Supplementary Materials). Table S1 (Supplementary Materials) contains further information about the other corresponding exposure characteristics. As numerous exposure characteristics, including body weight (BW), ingestion rate (IRsoil), and inhalation rate (IRair), increase with age, the ILCR was divided into three age groups: childhood (0–10 years old), adolescence (11–18 years old), and adult (19–70 years old). The integrated risk information system’s (IRIS) carcinogenic slope factors (CSF) for each particular OCP are shown in Table S2 of the Supplementary Materials. The sum of the individual risks from the 3 exposure pathways was used to estimate the overall cancer risks for various age groups.

2.6. Statistical Analysis

Microsoft Excel 2021 and IBM SPSS Statistics (version 21.0 for Windows) were used to implement the statistical analyses. Values below the detection limit were calculated as being half of the detection limit. As a result of the observed OCP data’s deviation from a normal distribution (Kolmogorov–Smirnov test, p < 0.05), the geometric mean (GM) rather than the arithmetic mean (AM) was employed for the duration of the data analysis. The Origin 8.0 software package (Origin Lab, Northampton, MA, USA) was used to create data graph plots. The obtained OCP data were used as inputs for the geographic information system’s (ArcGIS 10.4 software, ESRI Inc., Redlands, CA, USA) inverse distance weighted (IDW) interpolation approach, to map the expected distribution of OCP residue in the main urban area soils of Changchun.

3. Results

Table 1 provides the statistical analysis of 18 target OCP concentrations in the soil of the Changchun central urban area. The total concentrations of 18 OCPs (∑18OCPs) in the soils ranged from 15.63 to 92.79 ng/g, with GM = 36.46 ng/g and AM = 39.60 ng/g. Figure 3 displays the percentage composition of OCPs and their proportion among individual homologs. OCP levels were dominated by HCHs (including α-, β-, γ-, and δ-HCH) and DDTs (including p,p′-DDE, p,p′- DDD, o,p′-DDT, and p,p′-DDT), which contributed 41.3% and 30.0% of the ∑18OCPs, respectively. The concentration of ∑HCHs ranged from 2.62 to 60.14 ng/g, with a mean value of 14.08 ng/g, which was higher than that of the ∑DDTs ranging from 4.4 to 24.02 ng/g, with an average of 10.8 ng/g. The geomean concentrations of CHLs (including TC and CC), HCB, DRINs (aldrin, dieldrin, and endrin), ENDs (α-Endosulfan and β-Endosulfan), and HEPTs (HEPT and HEPX) were 2.55, 2.09, 1.92, and 1.51 ng/g, comprising 7.7%, 6.3%, 5.3%, 4.8%, and 4.6% of total OCPs, respectively. Although the respective concentrations of the remaining OCPs were kept at low levels, the detection frequencies were all much higher than 88% (except for HEPT).
Comparing the Changchun central urban area soil’s residual levels of HCHs, DDTs, and total OCPs with those of other cities or regions worldwide (Table S3, Supplementary Materials), we found that the residual levels of HCHs and DDTs were comparable to those found in soil samples collected from Anhui, Taiyuan, and Urumqi of China; Korba of India; and Nigeria. However, the HCH and DDT residues in Changchun urban soil were much greater than those in the polar region and isolated regions such as Guiyang, Tibet of China and the James Ross Island of Antarctica. Simultaneously, they both exceeded those of some developed countries/regions, including Italy, the UK, and Norway in Europe and Costa Rica and Mexico in America. The concentration of HCHs in the present study was lower than those reported in the mixed soil from Yantai, China and the urban soil from Nagaon, India. Whereas the concentration of DDTs in this study was inverse to that of HCHs, it was lower than those recorded in urban or mixed soils from Poland; Korba and Nagaon of India; and Wuhan, Ningbo, and Yantai of China. The comparison results showed that the residue level of HCHs and DDTs in the urban soil from Changchun were moderate.

4. Discussion

4.1. OCPs Residue Levels in the Urban Soil Collected from Changchun

Contrary to the OCP monitoring results for the soil of most research locations in China [30,31], the concentration of HCHs was higher than that of DDTs in Changchun’s central metropolitan area. However, this agrees with the findings of a previous study conducted in the school soil of Changchun [32]. According to Walker et al. (1999) [33], the HCHs showed moderately high vapor pressures and a lower octanol–water coefficient (Kow) than DDT pesticides, which made them easier to volatilize into the atmosphere and transport over a large area. However, the application amount is still the determining factor of OCP residues in soil. The geomean concentrations of CHLs (including TC and CC), HCB, DRINs (aldrin, dieldrin, and endrin), ENDs (α-endosulfan and β-endosulfan), and HEPTs (HEPT and HEPX) were 2.55, 2.09, 1.92, and 1.51 ng/g, comprising 7.7%, 6.3%, 5.3%, 4.8%, and 4.6% of total OCPs, respectively. Although the respective concentrations of the remaining OCPs were kept at modest levels, all detection frequencies (with the exception of HEPT) were substantially greater than 88%. This fact suggests that although HCHs and DDTs are presumably applied in higher proportions than the other OCPs, the remaining OCPs have also been widely employed in Changchun’s various regions.

4.2. Composition and Source Identification of Selected OCPs

HCHs make up the majority of pollutants in Changchun’s primary urban soils, accounting for 41.3% of all OCPs. HCHs were used as a commercial insecticide in two formulations: (I) industrial technical-grade HCHs, comprising α-HCH (60–70%), β-HCH (5–12%), γ-HCH (10–15%), and δ-HCH (6–10%), and (II) lindane, almost entirely composed of γ-HCH (>99%) [34]. The four HCH isomers’ environmental levels varied according to their configurations and physicochemical characteristics such as their relative stability, which ordered as β-HCH > δ-HCH > α-HCH > γ-HCH [35]. The proportion of α-HCH/γ-HCH varied from 4 to 7, suggesting the application of technical HCHs, whereas virtually none indicated the usage of lindane [36]. In the natural environment, microbial degradation and photosynthesis processes can convert γ-HCH and α-HCH into β-HCH [33]. Therefore, to ascertain whether the HCH levels were caused by previous pollution, the ratio of β-HCH/(α-HCH + γ-HCH) was utilized [37]. In the current analysis, γ-HCH was the most prevalent isomer (making up 46.2% of all HCHs), followed by β-HCH (31.5%), δ-HCH (13.5%), and α-HCH (8.8%) (Figure 2). The ratios of α-HCH/γ-HCH ranged from 0.04 to 1.62, with an average value of 0.22, suggesting that the central urban area soil of Changchun most likely included HCH left over from lindane use in the past. The range of β-HCH/(α-HCH + γ-HCH) was 0.06 to 3.25, with an average value of 0.69, Nearly 58% of the soil samples had a β-HCH/(α-HCH + γ-HCH) ratio between 0.1 and 0.5, and 21% of the soil samples had a ratio of >1. As a result, the main source of HCHs in the soil samples from Changchun was historical lindane use, although technological HCHs also made a contribution. Lindane is an efficient and broad-spectrum organic chlorine insecticide, which is not only widely used for pest control for crops in the field but also has good control effects on hygiene pests. After lindane–which was historically used for agricultural pests and diseases, entered the soil–it was affected by the expansion of the central urban area of Changchun, resulting in the presence of historical sources of lindane in the residual OCPs in the soil of the central urban area. This was similar to the residual form of HCHs in the soil of the Anhui industrial zone [38].
DDTs were the second dominant contaminant in the soil from Changchun, accounting for 30% of the total OCPs (Figure 2). The use of technological DDTs and dicofol in industry and agriculture was the main cause of DDT contamination in China. p,p′-DDT (80–85%) and o,p′-DDT (15–20%) make up technological DDTs. The biodegradation of p,p′-DDT into p,p′-DDE and p,p′-DDD in anaerobic and aerobic settings, respectively, is possible once it is present in the environment [39]. Thus, it is possible to determine whether the sources of DDT pollution were “new” or “old” by comparing the ratios of (p,p′-DDD + p,p′-DDE)/p,p′-DDT. If the ratio of (p,p′-DDE + p,p′-DDD)/p,p′-DDT is greater than 1, it indicates that DDTs have undergone long-term breakdown and transformation without the addition of new contaminants [40]. The DDT pollution source was estimated using the o,p′-DDT/p,p′-DDT ratio [41]. According to previous studies, the technical DDT had an o,p′-DDT/p,p′-DDT ratio of 1.3–9.3, whereas the dicofol-type DDT had one of 4.8–9.2 [10]. The most prevalent isomer in our samples, p,p′-DDE, made up 37.4% of all DDTs, followed by p,p′-DDT (35.5%), o,p′-DDT (19.3%), and p,p′-DDD (7.9%) (Figure 3). Only one sample had a ratio of p,p′-DDD/p,p′-DDE greater than 1, showing that p,p′-DDT was being aerobically broken down in the surface soil of Changchun’s central metropolitan region. A mean value of 0.61 was found for the ratio of o,p′-DDT/p,p′-DDT, which varied from 0.01 to 4.30. The ratios of (p,p′-DDD + p,p′-DDE)/p,p′-DDT ranged from 0.07 to 39.56, with a mean value of 3.76, indicating that the past use of dicofol or technological DDT was the primary cause of the high contamination of DDTs in Changchun’s central metropolitan soil. Pesticide production and sales enterprises are scattered throughout the central urban area of Changchun. In the past, there have been production and commercial transportation processes for technological DDT or other substitutes. As a result, there are still DDT residues in the soil of the central urban area of Changchun at present.
Chlordane was first developed in China in the 1950s [34] and was widely used as an agricultural insecticide, herbicide, and termiticide against termites in China from the 1960s to 2009 [35]. More than 140 different molecules make up technological chlordane, with cis- and trans-chlordane (CC, 11% and TC, 13%) making up the majority. The ratio of TC/CC1.0 typically denotes the ageing of chlordane, since TC decays more readily than CC in the environment [30]. Chlordane levels in soils ranged from 0.21 to 12.39 in this study, with GM at 2.55 ng/g and AM at 3.03 ng/g. This finding exceeded those found in soil samples from Beijing [42], the Himalayas [43], and Ningbo [30]. In 81% of the soil samples, the TC/CC ratio was greater than 1, indicating the use of chlordane in the past. Termite, ant, and soil insect control in seed grains were the main applications for HEPT. Due to the rapid conversion of HEPT into HEPX or other metabolites [44], the ratios of HEPX/HEPT >1 and <1 indicate that HEPT originates from historical and recent usage, respectively [45]. In our investigation, the HEPX/HEPT ratio varied from 0.03 to 6.29 and was higher than 1 in 67% of the soil samples, indicating the study area’s past usage of HEPT.
Technological endosulfan contains 70% and 30% α-endosulfan and β-endosulfan [46]. The ratios of α-/β-endosulfan < 2.33 and >2.33 denote the historical and contemporary employment of technical endosulfan, respectively, because α-endosulfan degrades more readily in soil than β-endosulfan [43]. The ratios of α-/β-endosulfan were all lower than 2.33 in our study, indicating the historical usage of endosulfan in Changchun.
HCB is an organochlorine fungicide; it is mainly used as a seed dressing to eliminate smut in agricultural production. Industrial HCB can be released into the environment during the use of sodium pentachlorophenol, which is utilized as an intermediary in the manufacturing of pentachlorophenol and sodium pentachlorophenol. The concentration of HCB in the soils used in this investigation ranged from n.d. to 8.67, with GM = 2.09 ng/g and AM = 2.50 ng/g. Due to its high volatility and low vapor pressure, HCB is typically adsorbed on air particles and can be transported over a long distance by the atmosphere. Although the detection rate of HCB in this study was 98%, the average detection concentration was relatively low, suggesting that regional air deposition may be the source of HCB in urban soil.
Aldrin, dieldrin, and endrin were never produced industrially, employed to control insects in agriculture in China, or brought in for sale from other countries [9,30]. While these never-used OCPs were also found in the urban soil from Changchun, with high detection frequencies (92% for aldrin, 88% for dieldrin, and 100% for endrin). Aldrin’s residue levels ranged from nd to 6.46 ng/g, with a GM equal to 0.23 ng/g, and dieldrin’s residue levels ranged from nd to 0.9 ng/g, with a GM equal to 0.42 ng/g. Endrin was present in concentrations between 0.5 and 2.52, with a GM of 1.24 ng/g. The residue levels were generally consistent with those from Ningbo [30], Shanghai [45], Zhejiang [47], and the peri-urban vegetable soils of Changchun [9]. Given that these chemicals were employed in certain developing nations near the tropical belt region, this may be ascribed to long-range air transport deposition [42].

4.3. Effect of Land Use and Geographical Distribution of OCPs in Changchun Urban Soil

Land-use type is thought to be a significant factor impacting the residues of certain OCPs in soil, since it directly impacts the usage history and dissipation of OCPs by altering soil conditions. Six different land-type soils from the Changchun central urban area were sampled in order to determine the impact of land-use types on the distribution of OCPs in soil. The average concentration distribution of each OCP in the soils from the various land-use categories of Changchun is shown as a bar chart in Figure 4. It highlights that the soils from the parking zone, residential zone, and the cultural and educational area sites were most polluted by γ-HCH, whereas the industrial zone and the outskirt farmland soils were predominately contaminated by p,p′-DDE, and the commercial traffic soils were only contaminated by p,p′-DDT. In general, the soils most polluted by the total OCPs were those from the cultural and educational areas and the park zone sites of Changchun.
IDW interpolation was applied to depict the geographical distribution of certain selected OCPs, in order to comprehend the regional variance of OCP residues in Changchun’s urban soil. As presented in Figure 5, individual OCP geographical patterns were largely comparable, with the highest concentrations being recorded in the southwest (PZ5) and northeast (PZ2, PZ4, CE1, RZ3) sites, as well as the sites (CE5) near Jilin Agricultural University in the southeast of the main urban areas of Changchun. This spatial distribution result matched the distribution traits of OCPs in Changchun’s peri-urban vegetable soils [7]. OCPs tend to transport with atmospheric particulates or gaseous phases as their semi-volatile properties [8]. Changchun experiences a consistent southwest wind throughout the year, which might be a reason why the northeast of the study area has a substantially greater OCP residue. Even if the general trend is identical, there are still some localized variances between the spatial distribution patterns of DDTs and HCHs. This may be due to the sources of DDTs and HCHs varying according to specific human activities in different regions. Affected by the sewage treatment plant, the soil in the upper reaches of the Yitong River exhibits a high concentration of DDTs. Meanwhile, the high concentrations of DDTs also appear in the cultivated land near the east interchange and outside the northern thermal power plant. A large number of processing and manufacturing industries are distributed in the eastern interchange area, which confirms the pollution of soil in Changchun being caused by DDTs in the process of industrial production. To control termites in structures and dams, chlordane was produced [9]. Hotspots in the north and southwest demonstrate how crucial a role chlordane plays in the spread of termites. The southwest, where there are plenty of automotive components and mold manufacturing facilities, also has high concentrations of DDTs, HCHs, and chlordane.

4.4. Relationship between OCP Concentration and Soil Properties

The total organic carbon (TOC), pH, and moisture content (MC) of each soil sample were measured. The results of these soil parameters are shown in Table 1, and the comprehensive analytical procedures are published in our prior study [23]. The main Changchun urban area soil pH ranged from 5.3 to 8.36, with an average value of 7.46, which indicates that the urban soil pH of Changchun is alkaline. Urban soil has a TOC concentration ranging from 0.56% to 4.79%, with an average content of 1.63%. OCPs are typically hydrophobic compounds, and the soil’s total organic carbon (TOC) is crucial in tying OCPs to the soil. After being put in the soil, the majority of OCPs will be absorbed by the soil’s organic matter, and this high absorption will prevent their breakdown and leaching [48]. As a result, it is believed that the soil TOC is a crucial element in the contamination of soil OCPs. An association between TOC and OCP concentrations in soil was discovered in earlier studies [49]. The Spearman correlation coefficients between the OCP concentrations and soil parameters are shown in Figure 6 to further highlight the effects of soil properties on OCP pollution in this study. The findings indicate that a relatively strong correlation exists between individual OCPs monomers, except for γ-HCH. The correlation between SOM and residual OCPs in soil is not strong, possibly due to the complex and diverse sources of urban soil, uneven soil texture, and unstable SOM content. The amounts of endosulfans were inversely linked with soil pH, and other research also shows that endosulfan in alkaline soil is more easily degraded [44]. The correlation coefficient between γ-HCH and pH value is 0.39 at a significance level of <0.05, showing a certain positive correlation. The relationship between γ-HCH and soil pH is worthy of further research and verification. The negative correlation between soil moisture content and residual OCPs in soil once again confirms the hydrophobic properties of OCPs.

4.5. Ecotoxicological and Health Risk Assessment of OCPs in the Soil from Changchun

To demonstrate the potential ecological harm of OCP residues in Changchun’s main urban area soil, the soil and sediment quality guidelines (SQGs) were adopted. The recommended threshold effects level (TEL) values and probable effects level (PEL) guidelines proposed by Macdonald et al. (1996) [50] and effects range-low value (ERL) and effects range-median value (ERM) guidelines proposed by Long et al. (1995) [51] are two groups of evaluation thresholds included in the guidelines [12]. ERM refers to a likelihood of less than 50%, and ERL is the threshold of effect concentration with an ecological risk probability of less than 10%. While the existence of residues over the PEL value signifies that unfavorable effects may occur frequently, the presence of residues below the TEL value indicates that negative biological consequences may occur infrequently [36].
According to the guidelines and statistical results in Table 2, the concentrations of p,p′-DDT, p,p′-DDD, p,p′-DDE, and ΣDDTs exceeded the TEL values in 90%, 29%, 96%, and 100% of the urban soil samples, respectively. The concentrations of these compounds were also higher than the ERL values in these samples. While the concentrations of the other isomers and the total DDTs were within the ERM and PEL values, the level of p,p′-DDT was significantly higher in 17% and 25% of all sampling sites, indicating a rare possibility of negative ecological impacts for DDT metabolite exposure to the soil organisms. A total of 100% of the sampling sites had residue levels of γ-HCH that were higher than the TEL and PEL values, which suggested that lindane input and accumulation associated with urban agricultural operations may have detrimental ecological consequences on Changchun’s urban soil. Furthermore, 98% of soil samples have chlordane concentrations exceeding ERL, with nearly 13% of these samples even exceeding ERM and TEL. In addition, 23% of these samples have chlordane levels exceeding PEL, indicating that chlordane residues in the surface soil of Changchun urban area pose serious ecological risks. The concentration of dieldrin in 10% of the samples exceeded the TEL value, without exceeding the PEL value, which suggests that dieldrin rarely has toxic biological effects on the urban soil organisms of Changchun. The concentrations of endrin all exceeded the ERL value, without exceeding the PEL value, suggesting that endrin in the urban soil from Changchun may cause certain adverse ecological effects, though the probability may be below 10%. For the heptachlor, the ERL value was surpassed at 44% of the sampling locations, while the TEL value was exceeded at 13% of those sites. Meanwhile, the concentration of heptachlor in three samples (including CE1, CE5, and PZ1) exceeded the PEL value, and that in the CE1 sample even exceeded the ERM value, which indicates that the heptachlor residue in some specific sampling sites may exhibit a high likelihood of adverse ecological effects.
The ILCRs for children, adolescents, and adults in Changchun’s central urban area were calculated, and the results are presented in Figure 7. In particular, ILCR values of 10−6 and 10−4 indicate extremely low risk, 10−3 and 10−1 indicate moderate risk, and 10−4 and 10−1 indicate very high risk of cancer [54]. The calculated results of the overall cancer risk under three routes of exposure for different age group exposure populations were between the threshold values of 10−6 and 10−4, which indicates that children, adolescents, and adults inhabiting Changchun may be at low risk of developing cancer due to OCP-polluted soils. However, the estimated ILCRs of OCP residues in individual sampling sites (including CE1 and CE5) exceed the threshold value of 10−4 but are lower than 10−3, which may indicate a moderate risk to the exposure receptor. Our evaluation results in Changchun urban soil are lower than the exposure cancer risk of OCPs in Ningde agricultural soil [2] but higher than that in Iran’s agricultural soil [47,55]. For the different age group exposure populations, the total ILCRs under the three exposure pathways and individual ILCRs under the ingestion route were children > adults > adolescence, while individual ILCRs via dermal contact and inhalation exhibited a trend of adults > adolescence > children. Most of these differences may be attributable to children being more likely to ingest contaminated soil via the mouth on account of their soil-playing [56], while their skin surface contact area is relatively small and their respiratory system is underdeveloped compared with adolescents and adults [57]. For different exposure pathways, the trend of rising cancer risk shows that ingestion > dermal > inhalation, as similarly documented for OCP-polluted soils of Xiangfen County, China [58]. Children are more susceptible to the urban soil from Changchun, since digestion was the main exposure pathway in our study.

5. Conclusions

This study presented the first comprehensive results regarding the level of OCP contamination in central urban area soils in Changchun, Northeast China. The total concentrations of OCPs ranged from 15.63 to 92.79 ng/g, with a geomean of 36.46 ng/g. Among the 18 OCPs, DDTs, HCHs, and chlordanes were the top three most prevalent compounds, accounting for 41.3%, 30.0%, and 7.7% of the total number of OCPs, respectively. The northeast and southwest of Changchun city had the highest OCP concentrations, which were influenced by industrial manufacturing processes, agricultural irrigation, urban diseases, and insect pests. HCHs, DDTs, chlordane, heptachlor, and endosulfan were found to be mainly formed from past applications, according to the diagnostic proportions of OCPs and their byproducts. Meanwhile, HCB, aldrin, dieldrin, and endrin were related to the process of long-distance air transport and sedimentation. According to the SQGs, the occurrence of DDTs, lindane, and heptachlor may cause adverse hazardous ecological harm to soil organisms. Calculation results of ILCRs ranged from 10−6 to 10−4, revealing that the residues of OCPs in the main urban area soil of Changchun had a low cancer risk for their exposed populations (especially for children); meanwhile, the moderate cancer risk at some specific sampling sites (such as CE1 and CE5) still require considerable attention.

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/su152416801/s1: Table S1: values of the parameters for estimation of the incremental lifetime cancer risk (ILCR); Table S2: the carcinogenic slope factor (1/(mg/kg/d)) of OCPs through ingestion, dermal contact, and inhalation; Table S3: comparison of OCP concentration with related studies in domestic and foreign cities around the world (ng/g). Refs. [59,60,61,62,63,64,65,66,67,68,69,70,71] are cited in Supplementary Materials.

Author Contributions

Data curation, Y.H.; Funding acquisition, J.L.; Investigation, X.Z. (Xiaoxiao Zou) and Z.G.; Project administration, Y.L.; Software, X.Z. (Xinyun Zhao); Validation, Q.W.; Writing—original draft and revision—final, W.Z. All authors have read and agreed to the published version of the manuscript.

Funding

The authors wish to express gratitude for funding support from the Special Study on Mineral Resources Planning in Changchun (JM-2020-11-13594) and the Jilin Provincial Department of Ecology and Environment Projects (SXGJXX2017-2).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available upon request from the corresponding author.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Cheng, C.; Hu, T.; Liu, W.; Mao, Y.; Shi, M.; Xu, A.; Su, Y.; Li, X.; Xing, X.; Qi, S. Modern lake sedimentary record of PAHs and OCPs in a typical karst wetland, south China: Response to human activities and environmental changes. Environ. Pollut. 2021, 291, 118173. [Google Scholar] [CrossRef] [PubMed]
  2. Qu, C.; Qi, S.; Yang, D.; Huang, H.; Zhang, J.; Chen, W.; Yohannes, H.K.; Sandy, E.H.; Yang, J.; Xing, X. Risk assessment and influence factors of organochlorine pesticides (OCPs) in agricultural soils of the hill region: A case study from Ningde, southeast China. J. Geochem. Explor. 2015, 149, 43–51. [Google Scholar] [CrossRef]
  3. Kim, J.T.; Choi, Y.J.; Barghi, M.; Kim, J.H.; Jung, J.W.; Kim, K.; Kang, J.H.; Lammel, G.; Chang, Y.S. Occurrence, distribution, and bioaccumulation of new and legacy persistent organic pollutants in an ecosystem on King George Island, maritime Antarctica. J. Hazard. Mater. 2021, 405, 124141. [Google Scholar] [CrossRef]
  4. Zhan, L.; Lin, T.; Wang, Z.; Cheng, Z.; Zhang, G.; Lyu, X.; Cheng, H. Occurrence and air-soil exchange of organochlorine pesticides and polychlorinated biphenyls at a CAWNET background site in central China: Implications for influencing factors and fate. Chemosphere 2017, 186, 475–487. [Google Scholar] [CrossRef] [PubMed]
  5. Tao, S.; Liu, W.; Li, Y.; Yang, Y.; Zuo, Q.; Li, B.; Cao, J. Organochlorine Pesticides Contaminated Surface Soil As Reemission Source in the Haihe Plain, China. Environ. Sci. Technol. 2008, 42, 8395–8400. [Google Scholar] [CrossRef]
  6. Cai, Q.Y.; Mo, C.H.; Wu, Q.T.; Katsoyiannis, A.; Zeng, Q.Y. The status of soil contamination by semivolatile organic chemicals (SVOCs) in China: A review. Sci. Total Environ. 2008, 389, 209–224. [Google Scholar] [CrossRef]
  7. Zhao, L.; Teng, Y.; Luo, Y. Status of Organochlorine Pesticide Contaminated Sites in China and Advances in Site Remediation. Soils 2018, 50, 435–445. (In Chinese) [Google Scholar]
  8. Ma, Y.; Yun, X.; Ruan, Z.; Lu, C.; Shi, Y.; Qin, Q.; Men, Z.; Zou, D.; Du, X.; Xing, B.; et al. Review of hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT) contamination in Chinese soils. Sci. Total Environ. 2020, 749, 141212. [Google Scholar] [CrossRef]
  9. Zhang, J.; Wang, Y.; Hua, D. Occurrence, distribution and possible sources of organochlorine pesticides in peri-urban vegetable soils of Changchun, Northeast China. Hum. Ecol. Risk Assess. Int. J. 2017, 23, 2033–2045. [Google Scholar] [CrossRef]
  10. Qiu, X.H.; Zhu, T.; Yao, B.; Hu, J.; Hu, S. Contribution of dicofol to the current DDT pollution in China. Environ. Sci. Technol. 2005, 39, 4385–4390. [Google Scholar] [CrossRef]
  11. Pokhrel, B.; Gong, P.; Wang, X.; Chen, M.; Wang, C.; Gao, S. Distribution, sources, and air-soil exchange of OCPs, PCBs and PAHs in urban soils of Nepal. Chemosphere 2018, 200, 532–541. [Google Scholar] [CrossRef] [PubMed]
  12. Yu, H.; Liu, Y.; Shu, X.; Ma, L.; Pan, Y. Assessment of the spatial distribution of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in urban soil of China. Chemosphere 2020, 243, 125392. [Google Scholar] [CrossRef]
  13. Changchun Statistical Bureau. Changchun Statistical Yearbook; Changchun Statistical Bureau: Changchun, China, 2020; pp. 37–39. [Google Scholar]
  14. Yang, Z.; Lu, W.; Long, Y.; Bao, X.; Yang, Q. Assessment of heavy metals contamination in urban topsoil from Changchun City, China. J. Geochem. Explor. 2011, 108, 27–38. [Google Scholar] [CrossRef]
  15. Zhang, J.W.; Zhang, H.; Gao, P.; Gao, L.B.; Liu, Y. The exposure pattern and health risk of HCHs and DDTs in soils of Taiyuan. Asian J. Ecotoxicol. 2017, 12, 354–366. (In Chinese) [Google Scholar]
  16. Tadesse, A.W. Occurrences, Potential Sources and Health Impacts of Organochlorine Pesticides in Soil from Wuhan, Central China. Bull. Environ. Contam. Toxicol. 2021, 107, 296–311. [Google Scholar] [CrossRef] [PubMed]
  17. Wang, X.P.; Sheng, J.J.; Gong, P.; Xue, Y.G.; Yao, T.D.; Jones, K.C. Persistent organic pollutants in the Tibetan surface soil: Spatial distribution, air-soil exchange and implications for global cycling. Environ. Pollut. 2012, 170, 145–151. [Google Scholar] [CrossRef] [PubMed]
  18. Pang, X.G.; Wang, H.J.; Gao, Z.J.; Dai, J.R.; Wang, C.L. The Distribution of Residual Organochlorine Pesticides in soils of Yantai City, Shandong Province. Geophys. Geochem. Explor. 2011, 35, 671–674. (In Chinese) [Google Scholar]
  19. Jiang, Y.F.; Wang, X.L.; Sun, Y.Z.; Wang, F. Residues of Organochlorine Pesticides in Urban Soil of Shanghai. Environ. Sci. 2010, 31, 409–414. (In Chinese) [Google Scholar]
  20. Zhang, H.B.; Luo, Y.M.; Zhao, Q.G.; Wong, M.H.; Zhang, G.L. Residues of organochlorine pesticides in Hong Kong soils. Chemosphere 2006, 63, 633–641. [Google Scholar] [CrossRef]
  21. Guo, Y.; Yu, H.Y.; Zeng, E.Y. Occurrence, source diagnosis, and biological effect assessment of DDT and its metabolites in various environmental compartments of the Pearl River Delta, South China: A review. Environ. Pollut. 2009, 157, 1753–1763. [Google Scholar] [CrossRef]
  22. Gereslassie, T.; Workineh, A.; Atieno, O.J.; Wang, J. Determination of Occurrences, Distribution, Health Impacts of Organochlorine Pesticides in Soils of Central China. Int. J. Environ. Res. Public Health 2019, 16, 146. [Google Scholar] [CrossRef]
  23. Zhao, W.; Li, J.; Lu, J.; Lan, T.; Zang, L.; Guo, J.; Li, T. Polycyclic Aromatic Hydrocarbons (PAHs) in Main urban area Soils of Changchun, Northeast China: Status, Sources, and Potential Toxic Risk Assessment. Pol. J. Environ. Stud. 2022, 31, 2943–2960. [Google Scholar] [CrossRef] [PubMed]
  24. HJ 835-2017; Soil and Sediment-Determination of Organochlorine Pesticides-Gas Chromatography/Mass Spectrometry. Ministry of Environmental Protection, The People’s Republic of China: Beijing, China, 2017.
  25. Sruthi, S.N.; Shyleshchandran, M.S.; Mathew, S.P.; Ramasamy, E.V. Contamination from organochlorine pesticides (OCPs) in agricultural soils of Kuttanad agroecosystem in India and related potential health risk. Environ. Sci. Pollut. Res. Int. 2017, 24, 969–978. [Google Scholar] [CrossRef] [PubMed]
  26. De Miguel, E.; Iribarren, I.; Chacón, E.; Ordnoñez, A.; Charlesworth, S. Risk-based evaluation of the exposure of children to trace elements in playgrounds in Madrid (Spain). Chemosphere 2007, 66, 505–513. [Google Scholar] [CrossRef] [PubMed]
  27. Hu, W.; Huang, B.; Zhao, Y.; Sun, W.; Gu, Z. Distribution, sources and potential risk of HCH and DDT in soils from a typical alluvial plain of the Yangtze River Delta region, China. Environ. Geochem. Health 2014, 36, 345–358. [Google Scholar] [CrossRef]
  28. Peng, C.; Chen, W.; Liao, X.; Wang, M.; Ouyang, Z.; Jiao, W.; Bai, Y. Polycyclic aromatic hydrocarbons in urban soils of Beijing: Status, sources, distribution and potential risk. Environ. Pollut. 2011, 159, 802–808. [Google Scholar] [CrossRef] [PubMed]
  29. EPA/540/R-92/003; Risk Assessment Guidance for Superfund: Volume I—Human Health Evaluation Manual (Part B, Development of Risk-Based Preliminary Remediation Goals). USEPA: Washington, DC, USA, 1991.
  30. Tang, J.F.; Feng, J.; Li, G.; Liang, M.; Wang, R.; Cai, C. Occurrence and possible sources of organochlorine pesticides in soils of Ningbo, East China. Earth Environ. Sci. Trans. R. Soc. 2018, 109, 495–500. [Google Scholar] [CrossRef]
  31. Zhang, G.; Lan, T.; Yang, G.; Li, J.; Zhang, K. Contamination, spatial distribution, and source contribution of persistent organic pollutants in the soil of Guiyang city, China: A case study. Environ. Geochem. Health 2021, 44, 3265–3278. [Google Scholar] [CrossRef]
  32. Lu, J.L.; Zhao, W.; Wei, Q.; Hou, Y.; Si, J.; Li, T.; Zang, L. Residue occurrence and potential risk assessment of HCHs and DDTs in campus surface soils: In case of Jilin University in Changchun, China. IOP Conf. Ser. Earth Environ. Sci. 2020, 585, 012199. [Google Scholar] [CrossRef]
  33. Walker, K.; Vallero, D.A.; Lewis, R.G. Factors Influencing the Distribution of Lindane and Other Hexachlorocyclohexanes in the Environment. Environ. Sci. Technol. 1999, 33, 4373–4378. [Google Scholar] [CrossRef]
  34. Bajwa, A.; Ali, U.; Mahmood, A.; Chaudhry, M.J.; Syed, J.H.; Li, J.; Zhang, G.; Jones, K.C.; Malik, R.N. Organochlorine pesticides (OCPs) in the Indus River catchment area, Pakistan: Status, soil-air exchange and black carbon mediated distribution. Chemosphere 2016, 152, 292–300. [Google Scholar] [CrossRef]
  35. Wei, H.; Hu, D.; Li, K.B. Sediments contamination levels of organochlorine pesticides in Weihe River, Northwestern China. Environ. Earth Sci. 2016, 75, 797. [Google Scholar] [CrossRef]
  36. Wang, W.; Bai, J.; Xi, M.; Zhao, Q.; Zhang, G.; Wen, X.; Xiao, R. Occurrence, sources, and risk assessment of OCPs in surface sediments from urban, rural, and reclamation-affected rivers of the Pearl River Delta, China. Environ. Sci. Pollut. Res. Int. 2017, 24, 2535–2548. [Google Scholar] [CrossRef] [PubMed]
  37. Wang, B.; Wu, C.; Liu, W.; Teng, Y.; Luo, Y.; Christie, P.; Guo, D. Levels and patterns of organochlorine pesticides in agricultural soils in an area of extensive historical cotton cultivation in Henan province, China. Environ. Sci. Pollut. Res. Int. 2016, 23, 6680–6689. [Google Scholar] [CrossRef] [PubMed]
  38. Yang, J.; Zhao, Y.; Zhen, Q.; Chen, X.; Zhang, Y. Concentrations and sources of persistent organochlorine residues in the sediments and soils from an industrially impacted area in Anhui, China. Soil Water Res. 2020, 15, 148–157. [Google Scholar] [CrossRef]
  39. Gopalan, N.K.; Chenicherry, S. Fate and distribution of organochlorine insecticides (OCIs) in Palakkad soil, India. Sustain. Environ. Res. 2018, 28, 179–185. [Google Scholar] [CrossRef]
  40. Barron, M.G.; Ashurova, Z.J.; Kukaniev, M.A.; Avloev, H.K.; Khaidarov, K.K.; Jamshedov, J.N.; Rahmatullova, O.S.; Atolikshoeva, S.S.; Mamadshova, S.S.; Manzenyuk, O. Residues of organochlorine pesticides in surface soil and raw foods from rural areas of the Republic of Tajikistan. Environ. Pollut. 2017, 224, 494–502. [Google Scholar] [CrossRef] [PubMed]
  41. Qiu, X.; Zhu, T. Using the o,p′-DDT/p,p′-DDT ratio to identify DDT sources in China. Chemosphere 2010, 81, 1033–1038. [Google Scholar] [CrossRef]
  42. Wang, X.F.; Wang, D.Z.; Qin, X.F.; Xu, X.B. Residues of organochlorine pesticides in surface soils from college school yards in Beijing, China. J. Environ. Sci. 2008, 20, 1090–1096. [Google Scholar] [CrossRef]
  43. Devi, N.L.; Yadav, I.C.; Raha, P.; Shihua, Q.; Dan, Y. Spatial distribution, source apportionment and ecological risk assessment of residual organochlorine pesticides (OCPs) in the Himalayas. Environ. Sci. Pollut. Res. Int. 2015, 22, 20154–20166. [Google Scholar] [CrossRef]
  44. Qu, C.; Albanese, S.; Li, J.; Cicchella, D.; Zuzolo, D.; Hope, D.; Cerino, P.; Pizzolante, A.; Doherty, A.L.; Lima, A.; et al. Organochlorine pesticides in the soils from Benevento provincial territory, southern Italy: Spatial distribution, air-soil exchange, and implications for environmental health. Sci. Total Environ. 2019, 674, 159–170. [Google Scholar] [CrossRef]
  45. Jiang, Y.F.; Wang, X.T.; Jia, Y.; Wang, F.; Wu, M.H.; Sheng, G.Y.; Fu, J.M. Occurrence, distribution and possible sources of organochlorine pesticides in agricultural soil of Shanghai, China. J. Hazard. Mater. 2009, 170, 989–997. [Google Scholar] [CrossRef] [PubMed]
  46. Tesi, J.N.; Tesi, G.O.; Ossai, J.C.; Agbozu, I.E. Organochlorine pesticides (OCPs) in agricultural soils of Southern Nigeria: Spatial distribution, source identification, ecotoxicological and human health risks assessment. Environ. Forensics 2020, 2, 1–13. [Google Scholar] [CrossRef]
  47. Jorfi, S.; Atashi, Z.; Akhbarizadeh, R.; Khorasgani, Z.; Ahmadi, M. Distribution and health risk assessment of organochlorine pesticides in agricultural soils of the Aghili plain, Southwest Iran. Environ. Earth Sci. 2019, 78, 603. [Google Scholar] [CrossRef]
  48. Dai, J.; Li, S.; Zhang, Y.; Wang, R.; Yu, Y. Distributions, sources and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in topsoil at Ji’nan city, China. Environ. Monit. Assess. 2008, 147, 317–326. [Google Scholar] [CrossRef] [PubMed]
  49. Chakraborty, P.; Zhang, G.; Li, J.; Sivakumar, A.; Jones, K.C. Occurrence and sources of selected organochlorine pesticides in the soil of seven major Indian cities: Assessment of air-soil exchange. Environ. Pollut. 2015, 204, 74–80. [Google Scholar] [CrossRef]
  50. Macdonald, D.D.; Carr, R.S.; Calder, F.D. Development and evaluation of sediment quality guidelines for Florida coastal water. Ecotoxicology 1996, 5, 253–278. [Google Scholar] [CrossRef] [PubMed]
  51. Long, E.R.; Macdonald, D.D.; Smith, S.L.; Calder, F.D. Incidence of Adverse Biological Effects Within Ranges of Chemical Concentrations in Marine and Estuarine Sediments. Environ. Manag. 1995, 19, 81–97. [Google Scholar] [CrossRef]
  52. Liu, Z.; Du, Y.; Da, C. Vertical Distribution Characteristics of Organochlorine Pesticides in a Sediment Core from Huaihe River, Anhui. J. Anqing Normal Univ. (Nat. Sci. Ed.) 2019, 25, 82–88. [Google Scholar]
  53. Tang, Z.; Huang, Q.; Yang, Y.; Zhu, X.; Fu, H. Organochlorine pesticides in the lower reaches of Yangtze River: Occurrence, ecological risk and temporal trends. Ecotoxicol. Environ. Saf. 2013, 87, 89–97. [Google Scholar] [CrossRef]
  54. Niu, L.; Xu, C.; Yao, Y.; Liu, K.; Yang, F.; Tang, M.; Liu, W. Status, influences and risk assessment of hexachlorocyclohexanes in agricultural soils across China. Environ. Sci. Technol. 2013, 47, 12140–12147. [Google Scholar] [CrossRef] [PubMed]
  55. Kafaei, R.; Arfaeinia, H.; Savari, A.; Mahmoodi, M.; Rezaei, M.; Rayani, M.; Sorial, G.A.; Fattahi, N.; Ramavandi, B. Organochlorine pesticides contamination in agricultural soils of southern Iran. Chemosphere 2020, 240, 124983. [Google Scholar] [CrossRef] [PubMed]
  56. Qu, C.; Albanese, S.; Lima, A.; Li, J.; Doherty, A.L.; Qi, S.; De Vivo, B. Residues of hexachlorobenzene and chlorinated cyclodiene pesticides in the soils of the Campanian Plain, southern Italy. Environ. Pollut. 2017, 231 Pt 2, 1497–1506. [Google Scholar] [CrossRef]
  57. Qu, C.; Albanese, S.; Chen, W.; Lima, A.; Doherty, A.L.; Piccolo, A.; Arienzo, M.; Qi, S.; De Vivo, B. The status of organochlorine pesticide contamination in the soils of the Campanian Plain, southern Italy, and correlations with soil properties and cancer risk. Environ. Pollut. 2016, 216, 500–511. [Google Scholar] [CrossRef] [PubMed]
  58. Ma, J.; Pan, L.B.; Yang, X.Y.; Liu, X.L.; Tao, S.Y.; Zhao, L.; Qin, X.P.; Sun, Z.J.; Hou, H.; Zhou, Y.Z. DDT, DDD, and DDE in soil of Xiangfen County, China: Residues, sources, spatial distribution, and health risks. Chemosphere 2016, 163, 578–583. [Google Scholar] [CrossRef]
  59. US Environmental Protection Agency. Supplemental Guidance for Developing Soil Screening Levels for Superfund Sites; US Environmental Protection Agency, Office of Solid Waste and Emergency: Washington, DC, USA, 2002. [Google Scholar]
  60. Sun, H.; Qi, Y.; Zhang, D.; Li, Q.X.; Wang, J. Concentrations, distribution, sources and risk assessment of organohalogenated contaminants in soils from Kenya, Eastern Africa. Environ. Pollut. 2016, 209, 177–185. [Google Scholar] [CrossRef]
  61. EPA-540-R-070-002 OSWER 9285.7-82; Risk Assessment Guidance for Superfund Volume I: Human Health Evaluation Manual (Part F, Supplemental Guidance for Inhalation Risk Assessment). Office of Superfund Remediation and Technology Innovation Environmental Protection Agency: Washington, DC, USA, 2009.
  62. Klanova, J.; Matykiewiczova, N.; Macka, Z.; Prosek, P.; Laska, K.; Klan, P. Persistent organic pollutants in soils and sediments from James Ross Island, Antarctica. Environ. Pollut. 2008, 152, 416–423. [Google Scholar] [CrossRef]
  63. Falandysz, J.; Brudnowska, B.; Kawano, M.; Wakimoto, T. Polychlorinated biphenyls and organochlorine pesticides in soils from the southern part of Poland. Arch. Environ. Contam. Toxicol. 2001, 40, 173–178. [Google Scholar] [CrossRef]
  64. Meijer, S.N.; Steinnes, E.; Ockenden, W.A.; Jones, K.C. Influence of Environmental Variables on the Spatial Distribution of PCBs in Norwegian and U.K. Soils: Implications for Global Cycling. Environ. Sci. Technol. 2002, 36, 2146–2153. [Google Scholar] [CrossRef]
  65. Bidleman, T.F.; Leone, A.D. Soil-air exchange of organochlorine pesticides in the Southern United States. Environ. Pollut. 2004, 128, 49–57. [Google Scholar] [CrossRef]
  66. Daly, G.L.; Ying, D.; Lei, Y.D.; Teixeira, C.; Muir, D.G. Organochlorine Pesticides in the Soils and Atmosphere of Costa Rica. Environ. Sci. Technol. 2007, 2007, 1124–1130. [Google Scholar] [CrossRef]
  67. Wong, F.; Alegria, H.A.; Bidleman, T.F. Organochlorine pesticides in soils of Mexico and the potential for soil-air exchange. Environ. Pollut. 2010, 158, 749–755. [Google Scholar] [CrossRef] [PubMed]
  68. Kumar, B.; Verma, V.K.; Mishra, M.; Gaur, R.; Kumar, S.; Sharma, C.S. DDT and HCH (Organochlorine Pesticides) in Residential Soils and Health Assessment for Human Populations in Korba, India. Hum. Ecol. Risk Assess. 2014, 20, 1538–1549. [Google Scholar] [CrossRef]
  69. Mishra, K.; Sharma, R.C.; Kumar, S. Contamination levels and spatial distribution of organochlorine pesticides in soils from India. Ecotoxicol. Environ. Saf. 2012, 76, 215–225. [Google Scholar] [CrossRef] [PubMed]
  70. Artikov, H.; Kočárek, M.; Fraňková, A.; Abdrakhmanov, T.; Borůvka, L.; Sharipov, U. Residues of organochlorine pesticides in irrigated sierozem-meadow soils around buried chemicals stock. Soil Water Res. 2018, 13, 108–114. [Google Scholar] [CrossRef]
  71. Chen, M.; Chen, L.; Huang, P. Residues and possible sources of organochlorine pesticides in surface soil of Urumqi. China Environ. Sci. 2014, 34, 1838–1846. (In Chinese) [Google Scholar]
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Figure 1. Locations of soil sampling sites in the central urban area of Changchun, northeast China.
Figure 1. Locations of soil sampling sites in the central urban area of Changchun, northeast China.
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Figure 2. Accuracy data of internal standard compound monitoring instruments. (ER: relative error, denoting the error between the test mean and accuracy value; red dotted line represents the standard concentration of 10 μg/mL for internal standard compounds).
Figure 2. Accuracy data of internal standard compound monitoring instruments. (ER: relative error, denoting the error between the test mean and accuracy value; red dotted line represents the standard concentration of 10 μg/mL for internal standard compounds).
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Figure 3. Percentage composition of OCPs and their proportion among individual homologs.
Figure 3. Percentage composition of OCPs and their proportion among individual homologs.
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Figure 4. OCP distribution in the soils of different land types in Changchun.
Figure 4. OCP distribution in the soils of different land types in Changchun.
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Figure 5. Distribution of components of OCPs (A), HCHs (B), DDTs (C), and chlordanes (D) in the central urban soils collected from Changchun.
Figure 5. Distribution of components of OCPs (A), HCHs (B), DDTs (C), and chlordanes (D) in the central urban soils collected from Changchun.
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Figure 6. Spearman correlation coefficients (p ≤ 0.05) across the various OCP concentrations and soil characteristics in the central urban area of Changchun.
Figure 6. Spearman correlation coefficients (p ≤ 0.05) across the various OCP concentrations and soil characteristics in the central urban area of Changchun.
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Figure 7. Estimated ILCRs via various pathways for children, adolescents, and adults dwelling in Changchun. (The two red dotted lines from bottom to top in the graph represent the upper limit values of very low risk (10−6) and low risk (10−4), respectively).
Figure 7. Estimated ILCRs via various pathways for children, adolescents, and adults dwelling in Changchun. (The two red dotted lines from bottom to top in the graph represent the upper limit values of very low risk (10−6) and low risk (10−4), respectively).
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Table 1. Concentrations (ng/g, dry weight) of organochlorine pesticides (OCPs) in the central urban area soil samples of Changchun City, NE China (n = 48).
Table 1. Concentrations (ng/g, dry weight) of organochlorine pesticides (OCPs) in the central urban area soil samples of Changchun City, NE China (n = 48).
CompoundsStatistical Parameters (ng/g)CVMDLs (ng/g)DFSR
MinMaxAMGM
α-HCH0.3311.171.381.00140%0.17100%84%
β-HCHN.D.18.904.943.2385%0.5498%101%
γ-HCH1.5430.877.246.4261%0.28100%82%
δ-HCH0.158.582.111.5881%0.15100%109%
p,p′-DDEN.D.22.584.443.8667%0.28100%101%
p,p′-DDDN.D.2.880.940.6185%0.2090%108%
o,p′-DDTN.D.6.122.291.5980%0.4594%84%
p,p′-DDTN.D.18.464.212.9981%0.3694%90%
HCBN.D.8.672.502.0962%0.2998%86%
HEPTN.D.7.121.110.59136%0.5246%83%
HEPXN.D.1.630.780.6747%0.6298%83%
TCN.D.10.291.320.82136%0.3690%84%
CCN.D.7.611.711.4961%0.05100%81%
AdrinN.D.6.460.440.23212%0.0692%89%
DiedrinN.D.0.900.420.3648%0.2088%87%
Endrin0.512.521.241.1540%0.39100%98%
α-EndN.D.5.860.620.38142%0.1490%84%
β-EndN.D.13.881.210.95156%0.8088%81%
ΣHCHs2.6260.1416.3614.0859%---
ΣDDTs4.4024.0211.8710.8046%---
ΣHEPTs0.557.951.901.5084%---
ΣCHLs0.2112.393.032.5571%---
ΣDRINs1.019.892.111.9262%---
ΣENDs0.6413.951.831.51108%---
Σ18OCPs15.6392.7939.6036.4643%---
TOC (%)0.56%4.79%1.67%0.0240%---
Soil pH a5.378.367.477.439%---
MC (%)1.08%4.43%2.64%0.0321%---
AM: arithmetic mean; GM: geometric mean; N.D.: below the detection limit; CV: coefficient of variation; MDLs: method detection limits; DF: detection frequency; SR: spiked recovery; TOC: total organic carbon; MC: soil moisture content. ΣHCHs = α-HCH + β-HCH + γ-HCH + δ-HCH; ΣDDTs = p,p′-DDE + p,p′-DDD + p,p′-DDT + p,p′-DDT; ΣHEPTs = heptachlor (HEPT) + hepoxide (HEPX); ΣCHLs = trans-chlordane (TC) + cis-chlordane (CC); ΣDRINs = aldrin + dieldrin + endrin; ΣENDs = α-endosulfan + β-endosulfan; Σ18OCPs = ΣHCHs + ∑DDTs + HCB + ΣHEPTs + ΣCHLs + ΣDRINs + ΣENDs; a: the unit of pH is 1.
Table 2. Assessments of potential ecotoxicological risks of selected OCPs in central urban soil from Changchun using two sediment quality guidelines (SQGs) (unit: ng/g).
Table 2. Assessments of potential ecotoxicological risks of selected OCPs in central urban soil from Changchun using two sediment quality guidelines (SQGs) (unit: ng/g).
Selected OCPsRange (Mean)ERL aAbove ERL eERM bAbove ERM eTEL cAbove TEL ePEL dAbove PEL e
p,p′-DDTN.D.–18.46 (4.21)190%717%1.1990%4.7725%
p,p′-DDDN.D.–2.88 (0.94)217%200%1.2229%7.810%
p,p′-DDEN.D.–22.58 (4.44)2.296%270%2.0796%3740%
∑DDTs4.40–24.02 (11.87)1.58100%46.10%3.89100%51.70%
γ-HCH1.54–30.87 (7.24)----0.32100%0.99100%
Chlordane0.21–12.39(3.03)0.598%613%4.512.5%2.923%
DieldrinN.D.–0.9 (0.42)----0.7110%4.30%
Endrin0.51–2.52 (1.24)0.02100%450%2.670%62.40%
HeptachlorN.D.–7.12 (1.11)0.544%62%2.2613%4.796%
-: not available; a: effects range-low value; b: effects range-median value; c: threshold effects level; d: probable effects level; e: percentage of samples above the corresponding levels. Guideline data are from references [36,52,53].
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Zhao, W.; Lu, J.; Lai, Y.; Hou, Y.; Zhao, X.; Wei, Q.; Zou, X.; Gou, Z. Occurrences, Possible Sources, and Risk Impacts of Organochlorine Pesticides in Soil of Changchun Central Urban Area, Northeast China. Sustainability 2023, 15, 16801. https://doi.org/10.3390/su152416801

AMA Style

Zhao W, Lu J, Lai Y, Hou Y, Zhao X, Wei Q, Zou X, Gou Z. Occurrences, Possible Sources, and Risk Impacts of Organochlorine Pesticides in Soil of Changchun Central Urban Area, Northeast China. Sustainability. 2023; 15(24):16801. https://doi.org/10.3390/su152416801

Chicago/Turabian Style

Zhao, Wei, Jilong Lu, Yawen Lai, Yaru Hou, Xinyun Zhao, Qiaoqiao Wei, Xiaoxiao Zou, and Zhiyi Gou. 2023. "Occurrences, Possible Sources, and Risk Impacts of Organochlorine Pesticides in Soil of Changchun Central Urban Area, Northeast China" Sustainability 15, no. 24: 16801. https://doi.org/10.3390/su152416801

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