Pesticide Residues In Apples Research Articles

Monitoring and Risk Assessment of Multi-Pesticide Residues in Apples: A Focus on Consumer Safety

Pesticide residues in human diets pose significant health hazards, particularly for vulnerable populations such as infants and children. This study aimed to determine pesticide residues in apples and to assess the cumulatively chronic risk posed to adult and child consumers from simultaneous exposure to multiple residues. During the 2022–2023 harvest seasons, 100 apple samples from Turkey were analyzed for the presence of 225 different pesticide residues. Pesticide extraction was performed using the QuEChERS method, followed by detection through liquid chromatography coupled with tandem mass spectrometry. Fifteen distinct pesticides (ten insecticides and five fungicides) were detected in 64 out of the 100 apple samples analyzed. Eleven samples contained pesticide residues that exceeded the maximum residue limit (MRL) set by the Turkish Food Codex and the European Union. Thiophanate-methyl was the most frequently detected pesticide (34%) in apples, with concentrations ranging from 0.012 to 0.108 mg kg−1, all of which were well below the MRL of 0.5 mg kg−1. Other commonly detected residues included chlorantraniliprole (28%), acetamiprid (24%), sulfoxaflor (22%), bifenazate (18%), indoxacarb (13%), diflubenzuron (12%), and carbendazim (10%). Under a worst-case scenario, the hazard index (HI) values for adults and children were 0.85% and 2.60%, respectively, indicating that these values remain significantly below the risk threshold of 100%, suggesting no associated health risks from apple consumption. However, regular monitoring of pesticide residues in fresh fruits and vegetables remains critically important.

Dissipation behavior and risk assessment of imidacloprid and its metabolites in apple from field to products

Pesticides play vital roles in controlling pests and boosting crop yields. Imidacloprid is widely used all over the world and may form in agricultural products. The presence of pesticide residues in apples raises serious health concerns. Understanding the residual fate of imidacloprid is critical for food safety and human health. In this study, the dissipation behavior, metabolism, household processing and risk assessment of imidacloprid and its metabolites in apple were investigated from filed to products. Field experiment results suggested that the half-lives of imidacloprid at 5 times the recommended dosage was 1.5 times that of the standard dosage. And the final residues of imidacloprid were less than the established maximum residue limits (MRLs). Clarification and simmering had little effect on the reduction the residues of imidacloprid and its metabolites. The calculated processing factors were lower than 1 for imidacloprid and its metabolites, implying that the residual ratios of imidacloprid and its metabolites in each steps of the food processing were reduced. The risk quotients were <1 for all Chinese people, indicating that acceptable risks associated with dietary exposure to imidacloprid in apple. However, the higher risks were observed in young people than adults, and females faced higher risks than males. Given high residue levels in pomace, imidacloprid and its metabolites should be further studied in commercial byproducts.

Farm to fork strategy for evaluating the qualitative and quantitative health risks to the Nepalese population associated with pesticide residues in apple and banana

Studies of pesticide use on commercial fruits are limited in Nepal. We surveyed the experiences and opinions of banana farmers in Nepal and monitored pesticide residues in apples and bananas. We monitored the residual status and associated health risks of 51 multi-group pesticides using Liquid Chromatography Triple Quadrupole Mass Spectrometry. Apple and banana samples were collected from different districts, farms, markets, and seller categories (our farm to fork survey). We found a significant bivariate positive correlation between farmers’ knowledge of pesticide negative effects and safety-promoting behavior among farmers. Residues of tebuconazole, difenoconazole, propargite and imidacloprid were most frequently detected. Of all the detected pesticides, propargite showed the highest concentration in apples, exceeding regulatory maximum residue limits (MRLs) in 24% of the samples. Epoxiconazole, tebuconazole, imidacloprid, quinalphos, fenpropathrin and bifenthrin in apples, and metalaxyl and imidacloprid in bananas also crossed their MRLs. Dietary exposure to pesticides among children and adults was estimated based on a hazard quotient and hazard index by using lower-bound and upper-bound approaches. Our results indicated that children consuming apples with residues of propargite are exposed to the greatest pesticide hazard.

A three-dimensional gold nanoparticles spherical liquid array for SERS sensitive detection of pesticide residues in apple

High-performance plasmonic substrates have recently attracted much research attention. Herein, a three-dimensional gold nanoparticles (AuNPs) spherical liquid array (SLA) with high “hot spots” and tunable nanometer gap by optimizing the proportion of AuNPs colloids over chloroform was synthesized based on a water–oil interfacial self-assembly strategy. The substrate demonstrated excellent surface-enhanced Raman scattering (SERS) performance using tetrathiafulvalene and rhodamine 6G (R6G) as probe molecules. With a simple extraction and soaking pretreatment process, the SLA exhibited high sensitivity for analysing triazophos on apple peels, with a limit of detection (LOD) of 0.005 µg/mL and recovery ranging from 96 to 110 %. Particularly, the chloroform produced an inherent characteristic peak at 665 cm−1, which was used as the internal standard to correct SERS signal fluctuation, leading to an improvement of the corresponding coefficient R2 from 0.97 to 0.99, thus improving the reproducibility. Therefore the SLA substrate possesses the potential for quantitative analysis of food contaminants.

Determination and risk assessment of 31 pesticide residues in apples from China's major production regions

The presence of pesticide residues in apple fruit raises serious health concerns. In multi-residue pesticide analysis, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction method has gradually replaced less efficient traditional extraction methods. This study developed a modified QuEChERS method coupled with ultra-high-pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) to simultaneously detect the residue of multiple pesticides in apple fruit. The method exhibited high linearity (R2 ≥ 0.99), and excellent recoveries (74.4–118.1 %) for 31 pesticides with relative standard deviations below 20 %. The limit of detection and limit of quantification were 0.1–4.0 μg/kg and 2.0–10.0 μg/kg, respectively. By using the established method, 20 pesticides were detected in 152 'Fuji' apple samples collected from the orchards of 17 cities in two major apple production regions of China, with an overall detection rate of 58.6 %. The residue levels were below the maximum levels set by GB 2763–2019. Moreover, both the chronic dietary intake risk (%ADI) and the acute dietary intake risk (%ARfD) for all the detected pesticides were lower than 100 %, indicating that the dietary intake risks are acceptable and would not pose potential health risks.

Development of a Simple Integrative Carbon Nanomaterial Microextraction Method with GC-MS for Assessing Pesticide Residues in Apples

The present study describes an efficient analytical method for analyzing apple pesticide residues. This novel approach employs ultrasound-assisted cleaning (UAC), solid-phase microextraction (SPME), and gas chromatography/mass spectrometry (GC-MS). A fiber coating with carbon nanomaterials (CNMs) was used for the extraction process. The methodology underwent extraction process optimization and analytical method validation. Moreover, its applicability for detecting pesticides in apples was evaluated. The validation showed satisfactory results with linearity coefficients greater than 0.99 (R2 &gt; 0.99) and linear working ranges from 0.5 ng·g−1 to 300.0 ng·g−1. The limits of detection and quantification (LODs and LOQs) ranged from 0.1 ng·g−1 to 0.3 ng·g−1 and from 0.5 ng·g−1 to 0.7 ng·g−1, respectively. The calculated recovery values ranged from 79% to 98%. The precision presented a relative standard deviation (RSD) lower than 14%. The validated method was applied to apple samples acquired from different markets and fruit stands in Belo Horizonte, Minas Gerais, Brazil. Organophosphate pesticides typically used in Brazilian apple production areas were detected in some samples. This study demonstrates the utility of UAC and CNM microextraction as an effective and highly efficient approach for analyzing pesticides in apples.

Frequently used pesticides and their metabolites residues in apple and apple juice from markets across China: Occurrence and health risk assessment

A large number of apples produced in China are consumed by people around the world every year. The pesticide residues in apples and apple juice are receiving more attention. Herein, 14 frequently used pesticides and 3 metabolites were selected as targets to investigate their residues in apples (120 samples) and apple juice (40 samples) in the markets across China, and the dietary intake risk for consumers was estimated. The monitoring results showed 91.7% of apple samples contained detectable pesticide residues, and six pesticides including thiamethoxam, carbendazim, pyraclostrobin, tebuconazole, chlorpyrifos and fenpyroximate exceeded limits of quantification with a detection rate of 63.3%, 61.7%, 22.5%, 21.7%, 8.3% and 2.5%, respectively. All pesticide residues were below their maximum residue limits (MRLs) in China. However, the banned pesticide chlorpyrifos in the Europe Union and the United States exceeded the local MRL (0.01 mg kg−1) in 7.5% of apples. No target chemicals occurred in juice samples. Risk assessment showed in deterministic assessment, the chronic and acute risk quotients of pesticides were ≤1.66 × 10−1% and 6.84%, respectively. The risk quotients of probability assessment were no more than 1.56%. The results indicated a negligible risk for consumers from consuming apples and apple juice from markets across China.

Comparison of pesticide residue and specific nutrient levels in peeled and unpeeled apples.

Studies have shown that the consumption of apples has a beneficial effect on cardiovascular diseases and some cancers, largely as a result of their micronutrient and phytoconstituent contents. Apple peel not only contains more polyphenols than the flesh, but also is likely to contain pesticide residues. The present study aimed to compare the contents of certain micronutrients and residual pesticide levels in peeled and unpeeled apples. Peeled apples contained fewer pesticide residues at lower concentrations than unpeeled apples. However, whether samples were peeled or not, the exposure values for pesticide residues in apples never exceeded the acceptable daily intake (ADI), but ranged between 0.04% and 2.10% of the ADI in adults for food intake estimated at the 95th percentile (277 g per person per day). Determination of polyphenol, fibre, magnesium and vitamin C levels showed that the nutritional differences observed between peeled and unpeeled apples were marginal. The consumption of apples, such as the apples tested in the present study, results in an exposure to pesticides that is low for unpeeled apples, and lower for peeled apples. Moreover, there was no significant loss of nutritional value from eating peeled apples based on the nutrients investigated. © 2022 Society of Chemical Industry.

Assessment of Pesticide Content in Apples and Selected Citrus Fruits Subjected to Simple Culinary Processing

Over the span of the last decade, certain pesticides have been banned in apple tree and citrus tree cultivations. Hence, it is important to conduct research focused on estimating the occurrence of residues of pesticides from the perspective of compliance with the relevant legislative regulations. Equally important is to estimate the reduction in pesticide residues through simple procedures such as washing and peeling. This research was conducted in the years 2012 and 2020. An assessment was made of the effect of in-house processing, such as conventional washing with tap water and peeling, on the level of pesticide residues in apples and citrus fruits (oranges, grapefruits and lemons). The level of pesticide residue was determined with the use of the QuEChERS method of extraction in conjunction with LC-MS/MS analysis. One can clearly observe a smaller number of pesticides identified in the edible parts of fruits in 2020 (seven pesticides in apples and three in citrus fruits) compared to 2012 (26 pesticides in apples and 4 in citrus fruits). In apples from 2012, only in the case of disulfoton was the maximum residue limit (MRL) exceeded, while in samples of apples from 2020 no instance of exceeded MRL was noted. This study did not reveal exceeded MRL values in the edible parts of citrus fruits in the analysed years. The absence of detected instances of pesticides not approved for use in the analysed years indicates that the producers complied with the relevant legislative regulations. The results obtained indicate that conventional washing with water (about 1.5 L/one fruit) did not have any effect on the level of pesticide residues in the analysed fruits. Apple peeling allowed for a reduction in pesticide levels in the range of 24% (carbendazim) to 100% (triflumuron, thiodicarb, tebuconazole).

Development of a Microwave-Assisted Extraction Protocol for the Simultaneous Determination of Mycotoxins and Pesticide Residues in Apples by LC-MS/MS

The possible presence of contaminants, pesticide residues and mycotoxins, in agricultural commodities is a critical issue for food safety, causing great concern. In this work, a simple and rapid analytical method employing liquid chromatography–tandem mass spectrometry (LC-MS/MS) was developed for the simultaneous determination of pesticide residues and mycotoxins in apples. Microwave-assisted extraction (MAE) was used for sample preparation. The MAE protocol was optimized after evaluating the effects of the following extraction parameters: (a) extraction solvent, (b) acidic environment, (c) temperature, and (d) extraction time. The multiresidue MAE-LC-MS/MS method was validated for linearity, accuracy (bias and precision), limits of detection (LODs), limits of quantification (LOQs), and matrix effect. The validation of the method was carried out according to the SANTE/12682/2019 document. The method demonstrated good linearity with R2 ≥ 0.99, acceptable accuracy in the recovery rate range 70–116%, acceptable interassay precision with RSD% ≤ 20, and low LODs and LOQs in the ranges 0.005–0.015 μg/g and 0.01–0.03 μg/g, respectively. Matrix effects were observed only for the 25% of the analytes. The performance of the MAE-LC-MS/MS method was compared to that of the QuEChERS sample preparation method, and the MAE-LC-MS/MS method proved to be rapid and effective.

The impact of apple preparation on the content of chlorpyrifos pesticide residues in the final products

Abstract The apples of Red Delicious are round fruits that have red colour when ripe according to which they are named. They can be eaten fresh, but also can be processed into a variety of processed products including apple juice. In order to grow or obtain better yield of a good quality apples, pesticides are usually used to protect apple trees, but they can adversely affect human health, therefore, some precautions should be taken when these chemicals are used as food contact materials. This study summarizes the presence of chlorpyrifos pesticide residues in apples that are prepared by different methods including mechanical treatments, fresh, washed, peeled as well as heat treatment of apples when prepared into an apple juice. For this purpose, the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method was used for residue extraction in apple samples after different methods of preparation, and their analyses were performed by liquid chromatography-mass spectrometry (LC-MS/MS). The concentration of the pesticide chlorpyrifos in different samples of apples was in the range of less than 0.0005 mg.kg−1 to 0.00348 mg.kg−1. This study provides a conclusion that all samples of apples are safe for consumption while the peeling method and heat treatment are the most efficient in reduction of chlorpyrifos content in the final products.

Evaluation of pesticide residues and risk assessment in apple and grape from western Azerbaijan Province of Iran

West Azerbaijan, especially the city of Urmia, is the center of Iranian apple and grape production hence the importance of this, residues of 85 pesticides in these products were investigated using modified QuEChERS extraction followed by UHPLC-MS/MS technique. Residues of 17 different pesticides detected in some apple samples. In grape sample only 7 pesticides detected. The levels of the residues found in all apple and grape samples were below the maximum residue levels (MRLs) of Iran, except for iprodione. Health risk assessment associated with pesticide residues in apples and grapes were estimated by hazard quotient (HQ) and hazard index (HI), which indicated that the HI value was lower than 1 in adults and children due to apple and consumption. HI in adults and children were 0.012 and 0.054 in apple; 0.001 and 0.003 in grape samples, respectively. Although the health risk assessment showed that the consumers are not at considerable risk but due to pesticide residue, implement control plans to manage the proper application of this pesticide, or replace it with safer alternatives in apple and grape is required.

Determination of Pesticides in Apples by High-Performance Liquid Chromatography–Mass Spectrometry (HPLC–MS) with High-Resolution Multiple Reaction Monitoring

High-performance liquid chromatography/quadrupole time-of-flight mass spectrometry (HPLC/QTOF–MS) is reported for quantitative determination of pesticide residues in apples. After a simple, rapid extraction, 300 mg MgSO4, 50 mg primary secondary amine (PSA), and 250 mg octadecyl (C18) were used for sample clean-up to ensure efficient recovery. The pesticides were quantified by HPLC/QTOF–MS using high-resolution multiple reaction monitoring (HR-MRM). Matrix-matched external standard calibration was used for quantitative analysis. The developed method was validated by spiking blank samples with the analytes and provided satisfactory accuracy verified by recoveries from 78.9% to 109.4% and good precision (relative standard deviation ≤12.4%). The limits of quantification for all analytes were between 0.85 and 3.0 µg/kg. The method was successfully applied to the analysis of forty batches of real samples, demonstrating its effectiveness for routine application.

Determination and dietary intake risk assessment of 14 pesticide residues in apples of China

The presence of pesticide residues in apples raises serious health concerns. In this study, a novel, sensitive, high-performance method was developed to simultaneously analyze the residues of 14 pesticides in apples using modified QuEChERS sample pretreatment coupled with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The optimized purification procedure demonstrated satisfactory recovery and precision for all the tested pesticides. The limits of detection (LOD) and quantification (LOQ) values of 14 pesticides in the apple matrix ranged from 0.03 μg/kg to 0.3 μg/kg and 0.1 μg/kg to 1.0 μg/kg, respectively. The proposed method detected six pesticides in the apple samples collected from 20 counties in China's major apple-producing regions. Furthermore, the risk quotient (RQ, %) of the detected pesticides was evaluated by the national estimated acceptable daily intake. The RQs of six pesticides in Chinese people of different age groups were less than 100%.

Tetragonal Superlattice of Elongated Rhombic Dodecahedra for Sensitive SERS Determination of Pesticide Residues in Fruit.

The self-assembly of plasmonic nanoparticles into highly ordered superlattices could pave the way toward novel nanomaterials for surface-enhanced Raman scattering (SERS). Here, we propose the formation of large-area superlattices of elongated rhombic dodecahedra in a vertical orientation via a controlled droplet evaporation process. Expectedly, the constant humidity of the experimental condition could control the evaporation speed of droplets and this procedure promotes the balance between driven depletion attraction and electrostatic repulsion in the system, leading to the generation of well-organized three-dimensional (3D) superlattices. The unique geometry of elongated rhombic dodecahedra could establish the tetragonal superlattices, which breaks the conventional hexagonal symmetry of gold nanorods. Specifically, the influence of the type and concentration of surfactants, the concentration of nanoparticles, and the amount of droplets on the preparation results were systematically investigated to find the optimal assembly parameters. Remarkably, such close-packed tetragonal arrays of vertically aligned elongated rhombic dodecahedra exhibit more excellent SERS performance compared with the traditional hexagonal superstructure of gold nanorods. Benefiting from the high sensitivity and reproducibility of elongated rhombic dodecahedron superlattices, their applications in the determination of pesticide residues in apple and grape peels were successfully demonstrated. As a result, this study may advance the production of innovative plasmonic nanomaterials for a broad range of fields.

Balls-in-tube matrix solid phase dispersion (BiT-MSPD): An innovative and simplified technique for multiresidue determination of pesticides in fruit samples

Sample preparation of complex matrices, like food samples, continues to be a challenge demanding great effort for improvements. In this study, a new technique named balls-in-tube matrix solid-phase dispersion (BiT-MSPD) is proposed based on a simplification of the conventional MSPD technique being all sample preparation performed directly in a closed extraction tube with the assistance of steel balls. An innovative method using BiT-MSPD was successfully established for the determination of 133 pesticide residues in apple, peach, pear and plum by ultra-high performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS). Several sorbents were evaluated as solid support in different proportions with the sample. The homogenization step using mortar, glass rod or steel balls, with methanol and acetonitrile as extraction solvent, was evaluated. Vortex and ultrasound assisted extractions were also tested. Best results were obtained with C18, homogenization with steel balls, acetonitrile as solvent and ultrasound assisted extraction. Validation presented adequate trueness and precision results for the evaluated pesticides with recovery results ranging from 72 to 113% and RSD ≤ 17%. Practical limit of detection (LOD) and quantification (LOQ) for the compounds were 3 and 10 µg kg−1, respectively. The developed method proved to be easier and faster to perform than the MSPD, considering that extraction and clean-up are performed in the same tube without the need to transfer to cartridges, recipients or to use a separate clean-up step. The proposed BiT-MSPD technique was successfully applied to fruit samples and has great potential to be applied in other matrices, like cereals and meat, since the steel balls promote an efficient sample dispersion and extraction of pesticides. The BiT-MSPD permit a fully automation of the entire sample preparation step.

Fusion of machine vision technology and AlexNet-CNNs deep learning network for the detection of postharvest apple pesticide residues

Pesticide residue is an important factor that affects food safety. In order to achieve effective detection of pesticide residues in apples, a machine-vision-based segmentation algorithm and hyperspectral techniques were used to segment the foreground and background regions of the apple image. By calculating the roundness value and extracting the region with the highest roundness value in the connected region, a region of interest (ROI) mask was created for the apple. Four pesticides (chlorpyrifos, carbendazim and two mixed pesticides) and an inactive control were used at the same concentration of 100 ppm (except for the control group), and the hyperspectral region of the corresponding sample image was extracted by obtaining the different types of pesticide residues in the ROI masks. To increase the diversity of the samples and to expand the dataset, Gaussian white noise with a varying signal-to-noise ratio was added to each of the hyperspectral images of the apple. The number of samples was increased from four types of 12 samples to four types of 72 samples, giving 4608 hyperspectral data images in each category. The structure and parameters of a convolutional neural network (CNN) were determined using theoretical analysis and experimental verification. All the extracted hyperspectral images of apples were normalized to 227 × 227 × 3 pixels as the input of the CNN network for pesticide residue detection. There were 18,432 sample data of four types for 72 samples. Of these, 12,288 images were selected using a bootstrap sampling method as the training set, and 6144 as the test set, with no overlap. The test results show that when the number of training epochs was 10, the accuracy of the test set detection was 99.09%, and the detection accuracy of the single-band average image was 95.35%. A comparison with traditional k-nearest neighbor (KNN) and support vector machine classification algorithms showed that the detection accuracy for KNN was 43.75% and the average time was 0.7645 s. These results demonstrate that our method is a small-sample, non-contact, fast, effective and low-cost technique that can provide effective pesticide residue detection in postharvest apples.

Pesticide residues in Lebanese apples and health risk assessment

ABSTRACTIn Lebanon, apples are among the most consumed commodities; however, pesticide residues in apples have not been evaluated so far. Therefore, this study presents the occurrence of pesticide residues in apples produced in Lebanon during 2012–2016. A total of 212 samples were analysed for the presence of pesticides using the QuEChERS multi-residue extraction method, followed by GC-MS. Pesticide residues were not observed in 23% of the samples. Whereas pesticide residues were found in 77% of the samples, among them 61% exceeded the maximum residue limits (MRL) and 16% contained residues below the MRL. The most frequently detected pesticide residues were chlorpyrifos (n = 142), methidathion (n = 34), cypermethrin (n = 21), lambda-cyhalothrin (n = 16), myclobutanil (n = 13) and diazinon (n = 9). A preliminary long-term exposure assessment for the detected pesticides in apples showed that Hazard Quotient (HQ) was in the range of 0.1–8% of the ADI’s, indicating no risk to human health.

A novel acrylamide modified primary-secondary amine analogue as impurities remover for determination of carbendazim and dimethyl phthalate in apples

A novel acrylamide modified Primary-Secondary Amine (PSA) analogue (acrylamide/3-aminopropyltriethoxysilane/ silica) was prepared and used as impurities remover for pesticide residues (carbendazim and dimethyl phthalate) in apples by QuEChERS combined with pipette-tip micro solid-phase extraction method. The properties of acrylamide/3-aminopropyltriethoxysilane/silica were characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. Under the optimized conditions, factors such as amount and type of adsorbents were investigated. The limit of detection and limit of quantity of the method were 0.012 μg/mL and 0.04 μg/mL for carbendazim, 0.023 μg/mL and 0.08 μg/mL for dimethyl phthalate, respectively. The recoveries of proposed method at three spiked levels analysis were 84.9–90.0% for carbendazim and 84.1–88.2% for dimethyl phthalate, respectively, with the relative standard deviation less than 2.9%. The acrylamide/3-aminopropyltriethoxysilane/silica as potential adsorbent showed strong ability for removing the matrix, and it achieved great ability to retain the targets. It will provide a new material choice for detecting pesticide residues in apple samples.

Monitoring of pesticide residues in apples from the Greek market

In this study, a novel hollow mesoporous carbon spheres-based fiber (HMCSs-F) was fabricated to immobilize HMCSs onto a stainless steel wire for solid-phase microextraction (SPME). Characterization results showed that the HMCSs-F possessed a large specific surface area, high porosity and uniform pore size. To demonstrate the extraction performance, a series of polycyclic aromatic hydrocarbons (PAHs) was chosen as target analytes. The experimental parameters including extraction and desorption conditions were optimized. Compared to commercial fibers, the HMCSs-F exhibited better extraction efficiency for PAHs. More interestingly, a good extraction selectivity for PAHs from the complex matrix was observed in these HMCSs-F. The enhanced SPME performance was attributed to the unique pore structure and special surface properties of the HMCSs. Furthermore, under the optimum conditions, the limits of detection (LODs) for the HMCSs-F were in the range of 0.20–1.15 ng L−1 with a corresponding relative standard deviation that was below 8.6%. The method was successfully applied for the analysis of PAHs in actual environmental water samples with recoveries ranging from 85.9% to 112.2%. These results imply that the novel HMCSs-F have potential application in environmental water analysis.