Abstract
This study validated the analysis of organochlorine pesticides (OCPs) in shellfish and cephalopods using a gas chromatograph equipped with a mass spectrometry (GC–MS/MS), and monitored residual pesticide levels. The QuEChERS method was used to analyze OCPs and was validated by checking the linearity, limit of detection (LOD), limit of quantitation (LOQ), accuracy, and precision. Octopus minor and Venerupis philippinarum, were purchased from four cities in the South Korean peninsula. The LOD values were 0.10–0.80 ng/g in shellfish and 0.21–0.77 ng/g in cephalopods, while the LOQ values were 0.31–2.41 ng/g in shellfish and 0.63–2.33 ng/g in cephalopods. Accuracy ranged from 83.5 to 117.4% and 79.8 to 118.4%, and precision ranged from 0.3 to 27.5% and 1.2 to 27.9%, in shellfish and cephalopods, respectively, conforming to the Codex Alimentarius Commission guidelines. Although residual OCP levels were below detection limits, the QuEChERS method may be effective for analyzing the OCPs in shellfish and cephalopods.
Keywords: Fishery product, Monitoring, QuEChERS, Residual pesticides
Introduction
Organochlorine pesticides (OCPs) were widely used to control insects in agriculture between the 1950s and 1980s (Hu et al., 2010). For instance, DDT and BHC were the most widely used OCPs during this period and resulted in lasting contamination worldwide (Wu et al., 1999; Zhou et al., 2001). Both aldrin and dieldrin were also used as insecticides during this period. In animals and plants, aldrin is metabolized to dieldrin, which is more resistant to biodegradation (WHO, 1991). Most OCPs are subject to conversion processes, can persist in the environment for a long time and can thus be transported over long distances (Hu et al., 2010; Takeuchi et al., 2009). Due to these characteristics, OCPs do not remain at the delivery site, but instead enter aquatic environments through several ways such as surface run-off, atmospheric deposition and soil percolation (Dirbaba et al., 2018). In aquatic organisms, OCPs such as DDT, BHC, aldrin, and dieldrin are of great concern due to their high bioaccumulative ability and toxic effects (Guruge and Tanabe, 2001). Even at low concentrations, OCPs can impair reproductive fitness and cause hormone-dependent cancers (Zacharewski, 1998).
To avoid health hazards posed by pesticide residues, the Codex Alimentarius Commission and many governments published a list of pesticides and their maximum residue limits (MRLs). However, Korean MRLs have limited scientific support to aid in establishing appropriate regulation guidelines, and it is, therefore, necessary to assess the risk of pesticide residues by monitoring organisms to align with Codex regulations (Chun and Kang, 2003; Lee and Lee, 2001).
In 2016 the average annual intake of aquatic products in South Korea was the highest in the world at 58.4 kg (FAO, 2016). Although the Korean government has set MRLs for OCPs in agricultural products, it has not set MRLs in marine products. Analysis of trace pollutants in biotic matrices usually involves the following steps: (1) isolation of analytes from a sample matrix, (2) removal of co-extracted compounds that may interfere with later chromatographic analysis, and (3) identification, quantification and confirmation of target compounds (Hajšlová and Zrostlíková, 2003). However, the characterization of residual pesticides in matrices is a challenge because of large amounts of co-extracted compounds which can interfere with and adversely affect analyses, particularly when dealing with very low concentration of analytes (Wilkowska and Biziuk, 2011).
There are a variety of conventional extraction methods for pesticide analysis, such as supercritical fluid extraction, Soxhlet extraction, accelerated solvent extraction, microwave assisted extraction, and ultrasonic extraction (Buah-Kwofie and Humphries, 2019). However, these methods are predominantly high cost and laborious, including broadscale purification to remove fat and other matrix components (Chung and Chen, 2011). Recently, sample preparation methods using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure have been applied to different environmental matrices and foods (Santana-Mayor et al., 2019; Lehotay et al., 2010). The method is based on partitioning through the addition of salt and an extraction using acetonitrile (Anastassiades et al., 2003). A dispersive solid phase extraction (d-SPE) promotes cleaner extracts at the clean-up step. The major sorbent in d-SPE is a primary-secondary amine (PSA) which is able to remove sugars, fatty acids, organic acids, and polar pigments. C18 silica sorbent is used to get rid of non-polar interfering substances such as lipids. Magnesium sulfate can be added to separate water from the organic solvent (Wilkowska and Biziuk, 2011). Although the QuEChERS method was first developed primarily for the analysis of vegetable products (Anastassiades et al., 2003), it has previously been shown to be effective for the analysis of residual pesticides in fish (Norli et al., 2011). However, the use of QuEChERS for the analysis of OCPs in shellfish and cephalopods has not yet been reported. Therefore, this study aimed to validate an effective and rapid method of a modified QuEChERS extraction procedure for the determination of OCPs in shellfish and cephalopods by using gas chromatography–mass spectrometry (GC–MS/MS).
Materials and methods
Sample collection
One hundred seventy-three samples were purchased from local markets caught in Gangneung, Tongyeong, Boryeong and Gunsan in South Korea. For analytical purposes, the samples were divided into two groups, a shellfish group and a cephalopods group, according to their matrices. All samples were stored at − 20 °C until preparation. To validate the analysis of OCPs, Octopus minor was used as the representative matrix for the 45 cephalopod samples and Venerupis philippinarum was used to represent the 128 shellfish samples.
Chemical reagents
A pesticide standard mixture of α-BHC, β-BHC, γ-BHC, δ-BHC, aldrin, dieldrin, p,p′-DDE, p,p′-DDD, o,p′-DDT, and p,p′-DDT was purchased from Accu Standard Chemicals (New Haven, CT, USA). Stock solutions of pesticide standards were prepared at a concentration of 200 ng/ml with acetone and stored at − 4 °C before analysis. Magnesium sulfate (MgSO4, ≥ 99.5%) was obtained from Sigma-Aldrich Co (Saint Quentin Fallavier, France). Sodium chloride (NaCl, ≥ 99.5%) was obtained from Junsei Chemical (Tokyo, Japan). Prep C18, 55–105 μm, 125 Å, for purification, was purchased from Waters Corp (Milford, DL, USA). The PSA was purchased from Agilent Technologies (Santa Clara, CA, USA). Acetone, acetonitrile, chloroform and methanol were procured from J.T Baker (Phillipsburg, NJ, USA). Formic acid and hexane were obtained from Wako Co (Tokyo, Japan). All solvents were prepared to HPLC-grade.
Sample preparation for residual pesticides analysis
All samples were well-homogenized and approximately 5 g was added to 50 mL centrifuge tubes and shaken with 80% acetonitrile for 1 min. After standing for 15 min, 1 g NaCl and 3 g MgSO4 were added and vortexed for 1 min. Following this, 1 mL of chloroform was added to calm the impurities, and the mixture was shaken for 1 min. After centrifugation for 10 min at 2135 × g, 6 mL of the supernatant was separated and added to another centrifuge tube. Subsequently, 150 mg of PSA and 1 g of MgSO4 were added to the separated extract, shaken for 1 min, before 1 mL of chloroform was added, and the mixture shaken again for 1 min. A further centrifugation was carried out for 10 min under the same conditions as above. Using a new centrifuge tube, 4 mL of supernatant was retrieved and 100 mg of C18 powder added before shaking for 1 min. Finally, 1 mL of chloroform was added and shaken for 1 min, followed by centrifugation at 2135 × g for 10 min. After centrifugation, 4 mL of the supernatant was retrieved, 40 μL of 5% formic acid in methanol solution was added, and the mixture was concentrated in a nitrogen bath at 4 °C. It was then reconstituted in 1 mL 20% acetone in hexane, filtered through a 0.45 μm PTFE filter, transferred to 2 mL amber screw-cap vials and analyzed by GC–MS/MS.
GC–MS/MS analysis
An Agilent (Palo Alto, CA, USA) 7890A gas chromatograph, equipped with a HP-5MS column (30 m × 0.25 mm i.d × 0.25 μm film thickness; J&W Scientific, Folsom, CA, USA), and a 5975C mass spectrometer, were used for the analysis of OCPs. Helium gas was used at a constant flow rate of 1 mL/min. The injection was performed in split-less mode at 275 °C. The oven temperature program was held at 60 °C for 2 min, initially. Then, the temperature was elevated to 165 °C at a rate of 30 °C/min, then increased to 195 °C at a rate of 15 °C/min (held for 1 min), increased from 195 to 210 °C at a rate of 2 °C/min, then elevated to 220 °C at a rate of 5 °C/min and then programmed to 300 °C at 10 °C/min, held for 1.5 min. The ion source temperature was 270 °C (Table 1).
Table 1.
Analytical condition of GC–MS/MS
| Instrument | GC–MS/MS |
| Column | HP-5MS (30 m × 0.25 mm × 0.25 μm, Agilent, USA) |
| Carrier gas | He (1 mL/min) |
| Injector | 275 °C splitless (Purge Time 0.75 min) |
| Oven temp | 60 °C (2 min) → 30 °C/min → 165 °C → 15 °C/min → 195 °C (1 min) → 2 °C/min → 210 °C → 5 °C/min → 220 °C → 10 °C/min → 300 °C (1.5 min) |
| Source temp | 270 °C |
| Quadrupole temp | 7890A GC–MS triple quad (QQQ) (Agilent, USA) |
The quantitative ions, qualitative ions, collision energy and retention time of α-BHC, β-BHC, γ-BHC, δ-BHC, aldrin, dieldrin, p,p′-DDE, p,p′-DDD, o,p′-DDT, and p,p′-DDT were shown in Table 2.
Table 2.
Quantitative ions, qualitative ions, collision energy, and retention time for organochlorine pesticides
| Analyte | Rt (min) | Precursor ion (m/z) | Fragmentation (m/z) | CE (eV) |
|---|---|---|---|---|
| Aldrin | 16.51 | 263 | 192 | 40 |
| 293 | 221 | 20 | ||
| 263 | 228 | 30 | ||
| BHC (alpha, beta, delta) | 12.56 | 181 | 145 | 20 |
| 13.69 | 219 | 146 | 25 | |
| 14.27 | 181 | 109 | 25 | |
| Cypermethrin (4 isomers) | 24.93 | 181 | 127 | 30 |
| 24.99 | 181 | 152 | 25 | |
| 25.05 | 165 | 91 | 15 | |
| 25.12 | ||||
| Dieldrin | 18.74 | 263 | 193 | 30 |
| 263 | 228 | 20 | ||
| 279 | 242 | 10 | ||
| o,p-DDT | 19.68 | 235 | 165 | 20 |
| 235 | 199 | 20 | ||
| 199 | 164 | 20 | ||
| p,p-DDD | 18.74 | 235 | 165 | 30 |
| 235 | 199 | 30 | ||
| 199 | 163 | 30 | ||
| p,p-DDE | 18.55 | 246 | 176 | 25 |
| 246 | 211 | 25 | ||
| 318 | 247 | 10 | ||
| p,p-DDT | 20.77 | 235 | 165 | 20 |
| 235 | 199 | 20 | ||
| 199 | 163 | 30 | ||
| Permethrin (2 isomer) | 22.22 | 183 | 168 | 10 |
| 22.36 | 183 | 153 | 15 | |
| 163 | 91 | 15 |
Validation of the analytical method for OCPs
The analytical method for the determination of OCPs was validated by determining the linearity (R2), limit of detection (LOD), limit of quantitation (LOQ), and accuracy and precision. Linearity (R2) was calculated from the calibration curve ranges of the OCPs. The LOD and LOQ were estimated based on a standard deviation of the y-intercept to the mean of slope ratio of 3:1 and 10:1, respectively. All analytical experiments were conducted in triplicate. Accuracy and precision were gained from the measurement of spiking 10 ng/g, 50 ng/g, and 200 ng/g into matrices, with five repetitions for each concentration, and performed for intra- and inter-day analysis. Chromatograms of pesticide standard materials in sellfish and cephalopod were shown in Figs. 1 and 2.
Fig. 1.
Chromatogram of pesticide standard materials in shellfish
Fig. 2.
Chromatogram of pesticide standard materials in cephalopod
Results and discussion
Validation of the analytical method for OCPs
The LOD, LOQ and linearity (R2) values for validation of the 10 OCPs in shellfish and cephalopods are listed in Table 3. The R2 values ranged from 0.996 to 0.999 in both shellfish and cephalopods. The calibration curves of all OCPs were measured as seven-point ranges, which were 1.00 to 200.00 ng/g.
Table 3.
Limit of detection (LOD), limit of quantification (LOQ), calibration curve equations and linearity (R2) for validation of 10 organochlorine pesticides in shellfish and cephalopods matrix (n = 3)
| Matrix type | OCPs | LOD (ng/g) | LOQ (ng/g) | Calibration curve equations | R2 |
|---|---|---|---|---|---|
| Shellfish | α-BHC | 0.243 | 0.736 | Y = 180.4X + 163.2 | 0.9980 |
| β-BHC | 0.287 | 0.871 | Y = 896.0X + 28.0 | 0.9981 | |
| γ-BHC | 0.101 | 0.305 | Y = 224.5X + 118.9 | 0.9976 | |
| δ-BHC | 0.144 | 0.436 | Y = 65.0X − 4.4 | 0.9995 | |
| Aldrin | 0.198 | 0.600 | Y = 156.4X − 16.9 | 0.9986 | |
| Dieldrin | 0.289 | 0.874 | Y = 38.8X + 37.5 | 0.9966 | |
| p,p′-DDE | 0.104 | 0.314 | Y = 518.8X + 357.7 | 0.9968 | |
| p,p′-DDD | 0.796 | 2.414 | Y = 4108.9X − 4617.4 | 0.9991 | |
| o,p′-DDT | 0.329 | 0.997 | Y = 2200.1X − 5170.9 | 0.9996 | |
| p,p′-DDT | 0.179 | 0.542 | Y = 746.8X − 2196.7 | 0.9996 | |
| Cephalopods | α-BHC | 0.210 | 0.635 | Y = 96.7X + 35.2 | 0.9998 |
| β-BHC | 0.286 | 0.867 | Y = 368.4X − 192.8 | 0.9999 | |
| γ-BHC | 0.362 | 1.097 | Y = 95.7X + 135.9 | 0.9993 | |
| δ-BHC | 0.349 | 1.057 | Y = 15.9X + 17.0 | 0.9993 | |
| Aldrin | 0.541 | 1.640 | Y = 46.7X − 20.2 | 0.9997 | |
| Dieldrin | 0.385 | 1.168 | Y = 23.6X − 11.6 | 0.9996 | |
| p,p′-DDE | 0.658 | 1.993 | Y = 409.3X − 1168.4 | 0.9962 | |
| p,p′-DDD | 0.768 | 2.327 | Y = 1279.5X + 1559.4 | 0.9990 | |
| o,p′-DDT | 0.679 | 2.058 | Y = 432.4X − 942.8 | 0.9980 | |
| p,p′-DDT | 0.622 | 1.886 | Y = 461.7X − 1035.4 | 0.9999 |
The LOD values ranged from 0.10 to 0.80 ng/g in the shellfish and 0.21–0.77 ng/g in the cephalopods, and the LOQ values ranged from 0.31 to 2.41 ng/g in the shellfish matrices and 0.64–2.33 ng/g in the cephalopod matrices. The results of linearity, LOD, and LOQ, were suitable for analysis of the OCPs in shellfish and cephalopods.
The accuracy and precision measurement for the validation of the 10 OCPs in shellfish and cephalopods matrix are shown in Table 4. The accuracy and precision experiments were performed through inter- and intra-day analysis. The results of the recovery tests for the shellfish and cephalopods matrices ranged from 83.5 to 117.4% and from 79.8 to 118.4%, respectively. The precision results for the shellfish varied from 0.3 to 27.5% and those of cephalopods groups varied from 1.2 to 27.9%. As shown in Table 4, some recovery values higher than 100% were obtained, however, the average recovery values were close to 100%. Several recovery results greater than 100% could be explained by very low spiking level, 10 ng/mL, which may result in technical error and matrix effects. Nevertheless, the results of the accuracy tests satisfied the maximum requirements given for low spiking levels, which were up to 120% (Codex Alimentarius Commission, 2003). As seen in Table 4, intra-day, at low spiking level, 10 ng/g precision results higher than 20% were obtained. Generally, inter- and intra-day precision up to a maximum of 20% is allowed, however, at a spiking level of 10 ng/g up to 30% is allowed by Codex Alimentarius Commission. Therefore, the values for the precision tests were within the maximum levels of up to 30% given for low spiking level (Commission, 2003). In conclusion, the validation results acquired verify the relevance of the developed analytical method for determination of the OCPs in shellfish and cephalopods, in terms of linearity, LOD, LOQ, accuracy, and precision.
Table 4.
Accuracy and precision for validation of 10 organochlorine pesticides in shellfish and cephalopods matrix (n = 3)
| Matrix type | OCPs | Intra-day | Inter-day | ||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Accuracy (%) | Precision (% CV) | Accuracy (%) | Precision (% CV) | ||||||||||
| 10 ng/g | 50 ng/g | 200 ng/g | 10 ng/g | 50 ng/g | 200 ng/g | 10 ng/g | 50 ng/g | 200 ng/g | 10 ng/g | 50 ng/g | 200 ng/g | ||
| Cephalopods | α-BHC | 79.8 | 96.7 | 109.5 | 4.3 | 3.3 | 6.8 | 97.8 | 101.0 | 104.6 | 22.1 | 5.1 | 2.0 |
| β-BHC | 107.0 | 87.8 | 91.2 | 5.2 | 8.3 | 9.0 | 109.6 | 93.4 | 96.3 | 17.7 | 5.7 | 8.9 | |
| γ-BHC | 91.4 | 106.0 | 84.0 | 4.2 | 3.1 | 2.9 | 107.6 | 101.0 | 90.8 | 20.8 | 6.6 | 8.9 | |
| δ-BHC | 99.0 | 101.5 | 105.3 | 4.5 | 6.8 | 3.9 | 89.4 | 95.1 | 103.5 | 14.1 | 14.4 | 11.0 | |
| Aldrin | 98.3 | 95.2 | 96.7 | 4.3 | 5.0 | 2.9 | 116.0 | 100.1 | 101.2 | 21.9 | 6.7 | 5.1 | |
| Dieldrin | 99.9 | 91.4 | 97.1 | 1.8 | 4.9 | 2.0 | 109.2 | 95.2 | 101.3 | 14.2 | 7.7 | 4.4 | |
| p,p′-DDE | 86.4 | 88.9 | 98.7 | 5.9 | 6.4 | 2.0 | 113.0 | 92.8 | 98.1 | 21.9 | 8.5 | 5.2 | |
| p,p′-DDD | 117.2 | 85.7 | 97.9 | 3.7 | 2.2 | 1.2 | 113.7 | 92.7 | 104.3 | 27.9 | 8.5 | 5.8 | |
| o,p′-DDT | 116.3 | 96.0 | 100.2 | 3.7 | 5.0 | 3.5 | 118.4 | 90.7 | 104.5 | 13.5 | 14.4 | 7.3 | |
| p,p′-DDT | 92.0 | 99.2 | 105.9 | 7.8 | 7.1 | 5.8 | 98.9 | 96.3 | 107.8 | 15.3 | 9.0 | 2.6 | |
| Shellfish | α-BHC | 117.4 | 99.4 | 84.7 | 1.2 | 5.3 | 7.7 | 102.7 | 100.9 | 90.1 | 18.6 | 5.7 | 10.8 |
| β-BHC | 102.4 | 102.8 | 97.2 | 3.2 | 2.5 | 1.8 | 104.8 | 102.6 | 96.2 | 17.2 | 2.5 | 1.9 | |
| γ-BHC | 83.5 | 109.4 | 109.8 | 3.0 | 8.0 | 3.0 | 93.3 | 99.5 | 98.1 | 21.2 | 0.3 | 9.1 | |
| δ-BHC | 90.5 | 115.2 | 111.9 | 7.1 | 1.0 | 4.1 | 108.2 | 102.4 | 102.5 | 27.5 | 11.3 | 10.4 | |
| Aldrin | 95.2 | 105.6 | 97.1 | 4.5 | 3.7 | 4.4 | 105.8 | 104.9 | 96.0 | 20.6 | 3.4 | 3.4 | |
| Dieldrin | 99.9 | 106.7 | 98.8 | 1.9 | 4.0 | 2.0 | 97.3 | 102.4 | 97.8 | 15.4 | 3.7 | 1.4 | |
| p,p′-DDE | 87.6 | 103.2 | 96.8 | 5.0 | 7.3 | 1.1 | 99.7 | 103.8 | 95.1 | 23.1 | 2.7 | 2.9 | |
| p,p′-DDD | 115.2 | 112.3 | 104.2 | 3.2 | 2.5 | 4.7 | 111.1 | 103.4 | 97.6 | 9.0 | 9.3 | 3.1 | |
| o,p′-DDT | 116.9 | 99.1 | 98.4 | 4.0 | 3.4 | 6.7 | 114.0 | 93.5 | 94.9 | 9.2 | 3.3 | 5.4 | |
| p,p′-DDT | 114.7 | 95.7 | 105.3 | 1.4 | 6.2 | 2.5 | 115.4 | 87.8 | 101.2 | 9.9 | 3.9 | 12.1 | |
Determination of OCPs concentration
The samples (n = 173) were initially divided into three major coast areas which are West Sea (Boryeong and Gunsan), East Sea (Gangneung), and South Sea (Tongyeong). Then, those samples were subdivided into two groups: shellfish and cephalopods. Table 5 shows the number of samples surveyed and those containing pesticide residues in each kind of fish. The OCP levels of all samples ranged from below to above the LOD.
Table 5.
Concentrations of 10 organochlorine pesticides detected in the South Korean peninsula shore samples (total samples: 173)
| Sampling are | Sample category | Sample name | N | α-BHC | β-BHC | γ-BHC | δ-BHC | Aldrin | Dieldrin | p,p′-DDE | p,p′-DDD | o,p′-DDT | p,p′-DDT |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| West sea | Shellfish | Venerupis philippinarum | 8 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. |
| Turbo cornutus | 3 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Meretrix lusoria | 13 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Anadara broughtonii | 8 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Atrina pectinata | 8 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Pectinidae | 8 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Haliotis | 2 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Tegillarca granosa | 1 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Arcida | 5 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Cepholopods | Octopus minor | 9 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | |
| Sepia esculenta | 8 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Todarodes pacificus | 1 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| East sea | Shellfish | Batillus cornutus | 6 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. |
| Gomphina melanaegis | 6 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Pectinidae | 6 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Neverita didyma | 6 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Meretrix lusoria | 6 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Haliotis | 6 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Arcida | 6 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Cepholopods | Enteroctopus dofleini | 8 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | |
| Todarodes pacificus | 8 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Octopus minor | 1 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| South sea | Shellfish | Venerupis philippinarum | 13 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. |
| Mytilus coruscus | 13 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Crassostrea gigas | 4 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | ||
| Cepholopods | Enteroctopus dofleini | 7 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | |
| Todarodes pacificus | 3 | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. |
N.D. not detected
OCPs in shellfish and cephalopods have been reported in various regions around the world. The DDT concentrations in shellfish samples ranged from 0.07 to 0.43 ng/g in Dalian, China (Yang et al., 2006), from 0.09 to 0.32 ng/g in Thailand (Boonyatumanond et al., 2002), from 0.1 to 0.2 ng/g in Cambodia, from 0.60 to 40 ng/g in India, from 0.10 to 3.1 ng/g in Indonesia, from 0.06 to 0.80 ng/g in Malaysia, from 0.07 to 4.2 ng/g in Philippines, 0.80–12.0 ng/g in Japan, and from 0.70 to 7.5 ng/g in South Korea (Monirith et al., 2003). DDT was not detected in cephalopod samples in Malaysia (Santhi et al., 2012). The BHC concentrations in shellfish matrices ranged from 0.35 to 0.54 ng/g in Tianjin (Yang et al., 2006), from 0.02 to 1.6 ng/g in Thailand (Boonyatumanond et al., 2002), from 0.01 to 0.1 ng/g in Indonesia, from 0.01 to 0.05 ng/g in Philippines, from 0.04 to 0.11 ng/g in Vietnam, from 0.20 to 0.60 ng/g in Japan, and from 0.10 to 1.0 ng/g in South Korea (Monirith et al., 2003). BHC was not detected in cephalopod samples in Taiwan (Sun et al., 2006), The aldrin/dieldrin concentration in shellfish ranged from 0.19 to 1.96 ng/g in China (Zhou et al., 2008), from 0.5 to 2.9 ng/g in Thailand (Boonyatumanond et al., 2002), from 0.14 to 2.01 ng/g in Egypt (Salem et al., 2014), from 0.69 to 0.89 ng/g in Nigeria (Osibanjo and Bamgbose, 1990), and from 0.48 to 0.53 ng/g in Italy (Giandomenico et al., 2013).
In this study, however, no OCPs were detected in the shellfish and cephalopod samples. In South Korea, DDT, along with aldrin, dieldrin, and BHC were registered and prohibited in the 1970s (Choi et al., 2012). Moreover, the concentration of OCPs in fish samples ranged from 0.84 to 27.0 ng/g (DDT), 0.38 to 5.60 ng/g (BHC) and 0.04 to 1.55 ng/g (dieldrin; Yim et al., 2005). Fish are at the top of the food chain in the aquatic environment, and due to the bioaccumulative nature of OCPs, fish suffer compound accumulation more easily than shellfish and cephalopods (Liu et al., 2010). Therefore, organisms in the pre-netting stage fishes inevitably have less accumulation of organochlorine compounds in sediments and seawater than fish (Choi et al., 2011).
Acknowledgements
This research was supported by the Grant (16162 MFDS 607) from Ministry of Food and Drug Safety and Chung-Ang University Graduate Research Scholarship in 2018.
Compliance with ethical standards
Conflicts of interest
The authors declare that they have no conflict of interest.
Footnotes
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