Monitoring and Risk Assessment of Pesticide Residues in Fishery Products Using GC-MS/MS in South Korea.

The aim of this study was to assess the risk of pesticide contamination in aquaculture and its impact on fishery products. We conducted an assessment of 300 samples collected from nine regions in South Korea, including various types of seafood, such as freshwater fish, marine fish, crustaceans, and shellfish. Pesticide residues in seafood were analyzed using GC-MS/MS after sample preparation using a modified QuEChERS method, revealing the presence of eight pesticides (4,4'-DDE, 4,4'-DDT, boscalid, isoprothiolane, oxadiazon, pendimethalin, thifluzamide, and trifluralin) across seven fish species (carp, far eastern catfish, crucian carp, eel, Chinese muddy loach, mirror carp, and sea bass). Following the grouping of DDE with DDT, a risk assessment of fishery products was conducted. After the estimated daily intake (EDI) of fish was calculated and compared with the acceptable daily intake (ADI), the health risk index (HI, %ADI) of the detected pesticides was evaluated and found to be 1.07% or lower. The results suggest that the consumption of domestically farmed fish products in South Korea poses minimal health risks associated with pesticide residues.

Determination of 57 pesticide residues in fishery products by GC tandem mass spectrometry combined with QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction.

An analytical method using GC-MS/MS combined with quick, easy, cheap, effective, rugged, and safe extraction was developed to determine 57 pesticides in fishery products. The limits of detection and quantification (LOD and LOQ, respectively) of the analytical method ranged between 0.91 and 2.12 ng/g wet mass and 3 and 7 ng/g wet mass, respectively. Moreover, the linearity of the calibration curves was acceptable (R2 > 0.99). The relative pesticide recoveries ranged between 53.87 and 127.2%, and reproducibility ranged between 0.25 and 10.87%. The pesticide residues in brown seaweed, eel, flatfish, shrimp, and abalone samples were analyzed using the developed analytical method, and the results indicate that most samples were not contaminated by the 57 target pesticides, except low levels (< 10 ng/g) of 1,1-dichloro-2,2-bis(4-chlorophenyl)ethene, alachlor, ametryn, isoprothiolane, and prometryn in several samples.

Effect of rice milling, washing, and cooking on reducing pesticide residues.

The effects of milling, washing, and cooking on etofenprox, flubendiamide, and tebufenozide levels in brown and polished rice were investigated by HPLC using a UV detector. The reduction rates of etofenprox, flubendiamide, and tebufenozide after milling were 68.74-93.16%, 64.49-90.25%, and 69.74-92.58%, respectively, 11.64-41.44%, 31.36-65.37%, and 31.61-73.79%, respectively, after washing brown rice, and 30.85-82.08%, 52.13-83.05%, and 43.04-83.89%, respectively, after washing polished rice. The residue levels of the three pesticides in brown rice decreased after electric and pressure cooking by 56.49 and 54.41%, 75.80 and 73.42%, and 70.01 and 71.27%, respectively, and the corresponding levels in polished rice decreased after electric and pressure cooking by 85.58 and 85.82%, 86.70 and 87.06%, and 89.89 and 89.68%, respectively. In conclusion, various processing methods decrease the residual levels of etofenprox, flubendiamide, and tebufenozide in rice.

Reduction in residual cyantraniliprole levels in spinach after various washing and blanching methods.

Pesticides are used to protect crops from pests and diseases. However, as many pesticides are toxic to humans, it is necessary to assess methods that can remove pesticide residues from agricultural products before human consumption. Spinach is consumed immediately after a relatively simple washing and heating process in the Republic of Korea. Cyantraniliprole is used as a systemic insecticide during spinach cultivation, which means it might remain in the crop after processing. Consequently, it is important to assess whether residues can be reduced to levels that are harmless to the human body after processing. This study investigated lowering the residual cyantraniliprole levels in spinach after washing and blanching. The amount of cyantraniliprole residue in the spinach samples sprayed with cyantraniliprole during cultivation was analyzed using ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The time of each washing and blanching method was set at 1, 3, and 5 min. The residual levels of cyantraniliprole decreased by 15.1-54.6% and 60.1-93.5% based on the washing and blanching methods employed. The most effective washing method to lower residual cyantraniliprole levels was steeping with a neutral detergent, resulting in cyantraniliprole reduction by 42.9-54.6%. When spinach was blanched after steeping washing with a neutral detergent, the largest removal rates of 77.9 and 91.2% were observed after 1 and 3 min of blanching, respectively. Blanching for 5 min after steeping and running washing exhibited the highest reduction rate of 93.5%. Therefore, a considerable amount of cyantraniliprole residue in spinach could be removed by washing or blanching. Based on the results of this study, blanching after steeping washing can be implemented as an effective method of lowering pesticide concentrations in spinach and other crops, thereby reducing their potential toxicity to humans upon consumption.

Correction: Residual characteristics of etofenprox in the processing stages of rice cakes and cookies.

[This corrects the article DOI: 10.1371/journal.pone.0255751.].

Recent Advances in the Recognition Elements of Sensors to Detect Pyrethroids in Food: A Review.

The presence of pyrethroids in food and the environment due to their excessive use and extensive application in the agriculture industry represents a significant threat to public health. Therefore, the determination of the presence of pyrethroids in foods by simple, rapid, and sensitive methods is warranted. Herein, recognition methods for pyrethroids based on electrochemical and optical biosensors from the last five years are reviewed, including surface-enhanced Raman scattering (SERS), surface plasmon resonance (SPR), chemiluminescence, biochemical, fluorescence, and colorimetric methods. In addition, recognition elements used for pyrethroid detection, including enzymes, antigens/antibodies, aptamers, and molecular-imprinted polymers, are classified and discussed based on the bioreceptor types. The current research status, the advantages and disadvantages of existing methods, and future development trends are discussed. The research progress of rapid pyrethroid detection in our laboratory is also presented.

Residual characteristics of etofenprox in the processing stages of rice cakes and cookies.

The changes in residual amounts of an insecticide (etofenprox) in processed rice cakes and cookies were investigated in this study. Test samples were sprayed with etofenprox during rice cultivation, and brown rice samples were dipped in a pesticide solution to investigate the effects of washing and processing. A multiresidue method for multiclass pesticides was employed for etofenprox analysis using a high-performance liquid chromatography-ultraviolet detector setup. Etofenprox was not detected in polished rice that was processed into rice cakes and cookies. The etofenprox residue levels were 2.13 mg/kg in each processing stage of brown rice products that were dipped in 400 mg/kg etofenprox solutions. The residual amounts of etofenprox in washed/polished rice and rice flour obtained by grinding were 1.25 and 0.77 mg/kg, respectively. The residual levels were 0.38 mg/kg in rice cakes prepared by cooking rice flour in a steamer for 20 min (a decrease of 82.1% compared to that in polished rice), 0.47 mg/kg in rice cookies baked in an oven for 20 min (a decrease of 78.0%), and 0.21 mg/kg in fried rice cookies (a decrease of 90.2%). Overall, the residual levels of etofenprox decreased in a range of 40-100% during the processing of rice cakes and cookies.

Onsite/on-field analysis of pesticide and veterinary drug residues by a state-of-art technology: A review.

Pesticides and veterinary drugs are generally employed to control pests and insects in crop and livestock farming. However, remaining residues are considered potentially hazardous to human health and the environment. Therefore, regular monitoring is required for assessing and legislation of pesticides and veterinary drugs. Various approaches to determining residues in various agricultural and animal food products have been reported. Most analytical methods involve sample extraction, purification (cleanup), and detection. Traditional sample preparation is time-consuming labor-intensive, expensive, and requires a large amount of toxic organic solvent, along with high probability for the decomposition of a compound before the analysis. Thus, modern sample preparation techniques, such as the quick, easy, cheap, effective, rugged, and safe method, have been widely accepted in the scientific community for its versatile application; however, it still requires a laboratory setup for the extraction and purification processes, which also involves the utilization of a toxic solvent. Therefore, it is crucial to elucidate recent technologies that are simple, portable, green, quick, and cost-effective for onsite and infield residue detections. Several technologies, such as surface-enhanced Raman spectroscopy, quantum dots, biosensing, and miniaturized gas chromatography, are now available. Further, several onsite techniques, such as ion mobility-mass spectrometry, are now being upgraded; some of them, although unable to analyze field sample directly, can analyze a large number of compounds within very short time (such as time-of-flight and Orbitrap mass spectrometry). Thus, to stay updated with scientific advances and analyze organic contaminants effectively and safely, it is necessary to study all of the state-of-art technology.

Curcumin and genistein coloaded nanostructured lipid carriers: in vitro digestion and antiprostate cancer activity.

To increase the oral bioavailability of curcumin and genistein, we fabricated nanostructured lipid carriers (NLCs), and the impact of these carriers on bioaccessibility of curcumin and genistein was studied. Entrapment efficiency was more than 75% for curcumin and/or genistein-loaded NLCs. Solubility of curcumin and/or genistein in simulated intestinal medium (SIM) was >75% after encapsulating within NLCs which otherwise was <20%. Both curcumin and genistein have shown good stability (≥85%) in SIM and simulated gastric medium (SGM) up to 6 h. Coloading of curcumin and genistein had no adverse effect on solubility and stability of each molecule. Instead, coloading increased loading efficiency and the cell growth inhibition in prostate cancer cells. Collectively, these results have shown that coloaded lipid based carriers are promising vehicles for oral delivery of poorly bioaccessible molecules like curcumin and genistein.

Simultaneous determination of orysastrobin and its isomers in rice using HPLC-UV and LC-MS/MS.

Orysastrobin is a new strobilurin-type fungicide to control leaf and panicle blast and sheath blight in rice. An analytical method was developed to determine the residues of orysastrobin and its two isomers, the main metabolite F001 and the major impurity F033, in hulled rice by the use of high-performance liquid chromatography with ultraviolet photometry (HPLC-UV) and liquid chromatography with tandem mass spectrometry (LC-MS/MS). All compounds were extracted with acetone from hulled rice samples. The extract was diluted with saline water, and an extraction step using dichloromethane/n-hexane partition was used to recover analytes from the aqueous phase. An n-hexane/acetonitrile partition and Florisil column chromatography were employed to further remove interfering coextractives prior to instrumental analysis. An octadecylsilyl column was successfully applied to identify orysastrobin and its isomers in sample extracts. Net recovery rates of orysastrobin, F001, and F033 from fortified samples ranged from 80.6 to 114.8% using HPLC-UV and LC-MS/MS. Relative standard deviations for the analytical methods were all <20%, and the quantification limits of the method were in the 0.002-0.02 mg/kg range. The proposed methods were reproducible and sufficiently accurate to evaluate the terminal residue of orysastrobin and its isomers in rice.

Simultaneous determination of three acidic herbicide residues in food crops using HPLC and confirmation via LC-MS/MS.

2,4-D, dicamba and 4-CPA with auxin-like activity have been intensively used in agriculture, for the control of unwanted broadleaf weeds. An analytical method involving HPLC coupled with UVD was developed for the simultaneous analysis of these three analytes in Chinese cabbage, apple and pepper fruits (representative non-fatty samples) and brown rice and soybean (representative fatty samples) using liquid-liquid partitioning and column cleanup procedures. The residues were confirmed via tandem mass spectrometry (MS/MS) in ion electrospray ionization (ESI) mode. The standard curves were linear over the range of the tested concentrations (0.25-10 microg/mL), as shown by a marked linearity in excess of 0.9999 (r(2) ). The average recoveries (mean, n = 3) ranged from 94.30 to 102.63 in Chinese cabbage, from 94.76 to 108.47 in apple, from 97.52 to 102.27 in pepper, from 76.19 to 101.90 in brown rice, and from 74.60 to 107.39 in soybean. The relative standard deviations (RSDs) were <9% in all tested matrices. The limits of detection and quantitation were 0.006 and 0.02 mg/kg, respectively. Samples purchased from local markets were analyzed to evaluate the applicability of the methods developed herein. The concentration of the 2,4-D residue was measured at 0.102 mg/kg in the soybean sample; however, this level is exactly the same MRL set by the Korea Food and Drug Administration. This developed method deserves full and complete consideration, as it clearly displays the sensitivity, accuracy and precision required for residue analysis of 2,4-D, dicamba and 4-CPA in food crops.

Simultaneous determination of phoxim and its photo-transformation metabolite residues in eggs using liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

The principal objective of this study was to develop an appropriate, sensitive, and selective method for the simultaneous quantitative determination of phoxim and its photo-transformation product, O,O-diethyl alpha-cyanobenzylideneamino-thiophosphonate (DCTP) in both chicken and quail eggs. Eggs (1 g) were blended with anhydrous magnesium sulfate (1 g) for sample pretreatment and extracted with acetonitrile. The extracts were then further purified with SPE silica gel tubes deactivated with trimethylamine. Residues were analyzed via a reversed phase-liquid chromatography-tandem mass spectrometry (RP-LC-MS/MS) in positive-ion electrospray ionization (ESI) mode. Tebufenozide was utilized as an internal standard for the quantification of phoxim and its metabolite residues. The identification and quantification of analytes were based on ion transitions monitored by multiple reaction monitoring (MRM). LC-MS/MS analysis was performed from 0.02 to 1 mg kg(-1) and correlation coefficients (r(2)) ranging from 0.998 to 0.999 were obtained for both analytes in blank egg extracts. The relative standard deviations (RSDs) of intra- and inter-day variations ranged from 2.1% to 6.7% and from 2.8% to 6.4% for phoxim and DCTP in chicken and quail eggs. At all levels of fortification (0.02, 0.05, and 0.125 mg kg(-1)), the recoveries fell within a range of 81.3% to 93.6% for phoxim and 83.3% to 90.1% for DCTP. The matrix effect was <2%, due to the partial dilution of the sample. Decision limits (CCalpha) and detection capabilities (CCbeta) were in the range of 0.0005-0.0044 and 0.0054-0.0224 mg kg(-1), respectively. The method was evaluated further by analyzing real samples purchased from markets. All chicken and quail egg samples were free from residues of the target compounds.