Research Progress of QuEChERS Pretreatment Technique in the Detection of Multiple Pesticide Residues

The QuEChERS extraction technique is a pretreatment technique that has been rapidly applied in recent years and is widely used in the field of pesticide residues with many advantages. This technique is based on solid phase extraction (SPE), which uses the interaction between adsorbent and impurities in the matrix to achieve the purpose of purification. The method has easier operation and better purification effect than SPE. In this paper, the research progress of the QuEChERS technique in pesticide residue detection in different fields in recent years and its future development were reviewed, hoping to provide reference for further development and utilization of the QuEChERS technique in pesticide residue detection in the future.

Determination of 14 Organophosphorus Pesticide Residues in Mutton by Gel Permeation Chromatography-Gas Chromatography-Mass Spectrometry(GPC-GC-MS)

[Objectives]This study was conducted to purify mutton samples by gel permeation chromatography(GPC).[Methods]Fourteen organophosphorus pesticide residues in samples were qualitatively and quantitatively analyzed by gas chromatography-mass spectrometry(GC-MS)in selective ion scanning mode(SIM).[Results]The organophosphorus pesticide standard solutions showed good linearity in the mass concentration range of 0.1-10.0μg/ml with correlation coefficients(r)not lower than 0.999,and the detection limits(S=3 N)ranged from 0.01 to 0.05 mg/kg.The average recovery values were in the range of 80.2%-99.7%,with relative standard deviations(RSDs,n=3)in the range of 1.8%-6.3%,at the addition levels of 0.5,1.0 and 2.0 mg/kg.[Conclusions]The method is simple,sensitive and accurate,and can be used for the determination of organophosphorus pesticide residues in mutton.

Determination of 2 Amides Pesticide Residues in Agricultural Products by Terahertz Time-domain Spectroscopy

[Objective] The aim was to explore the application of terahertz （THz） technique in pesticide recognition and residue determination. [Method] THz far-infrared spectral characteristics of 2 herbicides （butachlor and metolachlor） were measured by THz time-domain spectroscopy （THz-TDS） under conditions of room temperature and nitrogen,meanwhile their refractive index and absorption coefficient between 0.2 and 2.2 THz were calculated by using models based on Fresenl equations. [Result] The 2 pesticides both had a series of different characteristic absorption peaks between 0.2 and 2.2 THz,respectively. Their molecular structures were similar,but there were great difference in absorption and refractive index spectrum between them. [Conclusion] THz-TDS technique is feasible to detect pesticide residues,especially there is a greater advantage in identifying the structure of similar substances.

Simultaneous Determination of Four Pesticide Residues in Fruit Juice by HPLC

[Objective] This study was conducted to develop a system for simultaneous determination of imidacloprid, diflubenzuron, thiabendazole and carbendazim in fruit juice by HPLC. [Method] Using acetonitrile as the extraction solvent, the pesticides in fruit juice were purified through a NH2 solid phase extraction （SPE） cartridge, then detected by HPLC. [Result] There was a good linear relationship between the peak area and the concentrations of imidacloprid, diflubenzuron, thiabendazole and carbendazim in a range of 0.05-5.0 μg/ml, and the linear correlation coefficient varied in a range of 0.999 0-0.999 8; the limit of detection for imidacloprid, diflubenzuron, thiabendazole and carbendazim was 0.003, 0.005, 0.003 and 0.007 mg/kg, respectively. The recovery rate of imidacloprid, diflubenzuron, thiabendazole and carbendazim standards added at three levels （0.1, 0.5 and 1.0 mg/kg） ranged from 82% to 107%, with RSD less than 4.5%. [Conclusion] The sensitivity, accuracy and precision of this method were able to meet the requirements for pesticide residue analysis.

Determination of 10 Pyrethroids Pesticide Residues in Rice by GC-MS-MS

[Objective] A method was developed for the determination of 10 pyrethroids pesticide residues in rice by GC-MS-MS. [Method] Pyrethroids were extracted with acetonitrile, followed by a salting-out step with anhydrous magnesium sulfate and sodium chloride, cleaned up by florisil solid phase extraction （SPE） cartridge, and determined by multiple reaction monitoring mode. [Result] The method showed good linearity over the range of 0.010-0.500 mg/L for 10 pyrethroid pesticide with correlation coefficients over 0.99. The detection limits were 0.005 -0.010 mg/kg. The method was validated by analyzing samples spiked with 0.05, 0.10, 0.20 mg/kg of 10 pyrethroid pesticides, respectively. The average recoveries in rice ranged from 75.0-115.5%, and the relative standard deviations （RSD） were between 3.9%-6.9%. [Conclusion] The method is easy, accurate and reliable, which can meet the requirement for the simultaneous determination and confirmation of pyrethroid pesticide residues in rice.

Investigation and Analysis of Pesticide Residues in Citrus from Parts of Hubei Province

The analysis of pesticide residues in Citrus from Yichang, Danjiangkou, Zigui and Xingshan in Hubei Province was accomplished by UPLC-MS and GC-MS. The results showed that the detection rate of pesticide residues in Citrus reticulate was 91.9%. The detection rate of banned pesticides was 1.6%. The detection rate of restricted pesticides was 9.5%. The detection rate of allowed pesticides was 68.3%. The detection rate of unregistered pesticides was 15.9%. The pesticide used in citrus was relatively common. Because of the banned and restricted pesticides were both in the control degree, on the whole, the quality and security of Citrus reticulata was safe.

Study on Pesticide Residues of Phorate and Emamectin Benzoate in Cauliflower with Ball Well Protected

In order to study the difference between cauliflower varieties with ball well protected and unprotected in terms of pesticide residue and its causes, Jinpin 70, a new male sterile cauliflower variety with ball well protected, and Xuebao with ball unprotected were sprayed with high-toxic pesticide phorate and efficient bio-pesticide emamectin benzoate at a regular dose to investigate the impact of different cauliflower varieties on the pesticide residue. The results showed that from the 3rd to the 5th day after spraying, phorate and emamectin benzoate residues in Jinpin 70 with ball well protected reduced by 76.47%-87.65% and 67.86%-80.82% re- spectively compared with Xubao, and decreased by 9.23%-81.82% and 57.14%- 79.84% respectively compared with Jinpin 70 with ball unprotected. The results above demonstrates that inner leaves of cauliflower with ball well protected can prevent the ball from being polluted by phorate and emamectin benzoate, thereby improving its edible safety.

Study on Prediction of Pesticide Residues Based on Fuzzy System

This study was aimed to do the prediction of pesticide residues based on fuzzy system. Taking chlorpyrifos as an example, the Mathematic Fuzzy System was established by using the MRL values （maximum residue limits of all kinds of pesticides in food） of the Matlab Fuzzy Toolbox to analyze and predict the degra- dation degree of pesticide residues of the same crop at different time periods of bagging treatment, with the aim to provide some theoretical guidances for solving practical problems in real life.

Risk assessment and ranking of pesticide residues in Chinese pears

The presence of pesticide residues in pears is a serious health concern. This study presents the results from a 2-year investigation （2013-2014） that used gas chromatography, GS/MS and UPLC/MS-MS to measure the levels of 104 pesti- cides in 310 pear samples. In 93.2% of the samples, 43 pesticides were detected, of which the maximum residue levels （MRLs） were exceeded in 2.6% of the samples. Multiple residues （two to eight compounds） were present in 69.7% of the samples; one sample contained nine pesticides and one sample contained 10. Only 6.8% of the samples did not contain residues. To assess the health risks, the pesticide residue data have been combined with daily pear consumption data for children and adult populations. A deterministic model was used to assess the chronic and acute exposures based on the Joint Meeting on Pesticide Residues （JMPR） method. A potential acute risk was demonstrated for children in the case of bifenthrin, which was found to be present at 105.36% of the acute reference dose （ARfD） value. The long- term exposure of the Chinese consumer to pesticide residues through the consumption of raw pears was far below the acceptable daily intake （ADI） criterion. Additionally, the matrix ranking scheme was used to classify risk subgroups of pesticides and pear samples. In general, 95.5% of samples were deemed to be safe and nine pesticides were classified as being of a relatively high risk. The findings indicated that the occurrence of pesticide residues in pears should not be considered a serious public health problem. Nevertheless, a more detailed study is required for vulnerable consumer groups, especially children. Continuous monitoring of pesticides in pears and tighter regulation of pesticide residue standards are recommended.

Analysis of pesticide residues in commercially available chenpi using a modified QuEChERS method and GC-MS/MS determination

To ensure the safety of the commercially available chenpi,a convenient and fast analytical method was developed for the determination of 133 pesticide residues in chenpi using gas chromatography-tandem mass spectrometry(GC-MS/MS).In this study,different extraction solvents,redissolution solvents and adsorbents were tested according to the recovery and purification effect to obtain a modified QuEChERS method.The samples were extracted with acetonitrile.During the clean-up step,octadecyl-modified silica(C18)and graphitized carbon black(GCB)were selected,and aminopropyl(NH2)was used instead of primary secondary amine(PSA)because of its weaker ion exchange capacity which had little effect on the recovery of ditalimfos.Samples were quantified by matrix-matched calibration with internal standards.All pesticides showed good linearity in the respective range,both with values of r2>0.99.The average recoveries of the pesticides spiked samples ranged from 70.0% to 112.2% with the RSDs of 0.2%–14.4%.The modified QuEChERS method was validated and applied to twenty real samples.Five pesticides were found in eight batches,but no pesticide exceeded the maximum residue limits(MRL,MRL reference to European commission).

Organochlorine pesticide and heavy metal residues in some edible biota collected from Quanzhou Bay and Xinghua Bay,Southeast China

In order to assess the contamination of edible marine organisms in Quanzhou and Xinghua Bays, Fujian Province, China, concentrations of organochlorine pesticides （hexachlorocyclohexane isomers or HCHs and dichlorodiphenyltrichloroethane isomers/derivatives or DDTs） and heavy metals （Cu, Pb, Zn, As, Cr, Cd, Ni and Hg） in 13 species collected from different sites in the hays were analyzed by GC-ECD and ICP-MS. The concentration of the sum of DDTs exceeded that the sum of HCHs in the samples. Most of the organisms showed higher levels of DDTs than the first level criterion （10 ng/g） for marine biological quality in China （GB 18421-2001） but conformed to the first level criterion （20 ng/g） for HCHs. The estimated mean daily uptake of pesticides was below the level for minimal risk to the consumers. The levels of Cd, As and Pb in most organisms from both bays were markedly elevated and above the recommended legal limits for human consumption. Our results showed the need for routine monitoring of marine species contamination to ensure public and environmental health.

Management of pesticide residues in China

This paper reviewed management of pesticide residues in China including laws and regulations, the supervision system, the standard system, and the quality and safety of agricultural products. The process of establishment and internationalization of standards for pesticide residues were also discussed. Results indicate that the progress of the management of pesticide residues has been steadily made in China. However, the following aspects which refer to updates to regulations, supervising efficiency, standard system, risk assessment, international cooperation and communication, should be further improved. China should draw lessons from international experience, and then establish its own management system, which focuses on pesticides controls by strictly following relevant laws and technical standards to ensure the quality and safety of agricultural products.

Effects of Two Composted Plant Pesticide Residues,Incorporated with Trichoderma viride,on Root-Knot Nematode in Balloonflower

Plant pesticide residues, such as chinaberry （Melia toosendan） residue and sand cypress （Sabina vulgaris） residue, are pesticidal plant materials discarded after the bioactive ingredient has been extracted with organic solvents. The only option for botanical pesticide residue utilization has been as landfill. Chinaberry residue （CBR） and sand cypress residue （SCR） were collected and composted in Yangling, Shaanxi Province, China. We studied the effects of chinaberry residue compost （CBRC）, CBRC incorporated with Trichoderma viride （CBRCT）, sand cypress residue compost （SCRC）, and SCRC incorporated with T. viride （SCRCv） on the root-knot nematode, Meloidogyne incognita, infesting the balloonflower （Platycodon grandiflorum）. Bioassay results indicated that stock solutions of the CBRCT and SCRCT extracts significantly inhibited egg hatching and caused high larval mortality, followed in degree by the CBRC and SCRC extracts. The CBR and SCR extracts caused very low inhibition of eggs and larvae. Supplementing potting mixtures with these four composts reduced the severity of root galling and increased the proportion of marketable roots. The severity of root galling decreased and the average weight of the marketable roots increased with an increase in all the composts when supplemented at rates from 5 to 30%. CBR- and SCR-supplemented pot soils also inhibited the nematodes, but CBR and SCR applied to the soil had a phytotoxic effect and inhibited balloonflower growth. Supplementing field soil with the composts reduced the severity of root galling and the populations of southern root-knot nematodes in the soil. CBRCT and SCRCT clearly enhanced the average weight of the marketable roots by 30.45 and 26.64%, respectively. Continuous supplementation with CBRCT or SCRCT in the same field significantly enhanced the control of the root-knot nematode, and the populations of nematodes continued to decrease with second inoculations. The populations of total Trichoderma spp. were distinctly enhanced and were maintained at high levels for a long time in the supplemented soils.

Simultaneous Determination of 8 Pesticide Residues in Green Tea Based on Gas Chromatography-mass Spectrometry

To improve pesticide residues detection efficiency in tea, simultaneous de- termination of eight pesticide residues in green tea was developed based on gas chromatography-mass spectrometry （GC-MS）. The results showed that, - detected by the GC-MS under following conditions： acetonitrile as extraction and elution solvent, activated carbon and PSA tandem column as the stationary phase, elution volume of 12 ml the relationship between peak area and concentration of each residue （ametryn in the range of 0-100 pg/L, napropamide in the range of 0-10 000 gg/L, other pesticides in the range of 0-1 000 tJg/L） were linearly related, and their corre- lation coefficients were all greater than 0.999. The recovery rate the pesticides added to tea sample at legal concentration limits ranged from 73.6% to 116.8%, and the relative standard deviation from 1.47% to 15.58%. The new method we de- veloped is sensitive, specific and anti-interference, and thus provides test basis for the development of pesticide matrix reference materials in tea.

Simultaneous determination of 74 pesticide residues in Panax notoginseng by QuEChERS coupled with gas chromatography tandem mass spectrometry

This study established a method for the simultaneous determination of 74 pesticide residues in Panax notoginseng by QuEChERS pretreatment method coupled with GC-MS/MS,and carried out pesticide residue analysis on 20 batches of market samples in China.The samples were extracted with acetonitrile,cleaned up with primary secondary amine(PSA)and octadecylsilane(C18)and determined by GC-MS/MS in multiple reaction monitoring(MRM)mode.Matrix-matched calibration was recommended to combat the matrix effect.A good linearity was observed in the range of 10−500 ng/mL with correlation coefficients≥0.9950.The mean recoveries for most of the pesticides were in the range of 70%−120%with RSD<20%.The limits of detection ranged 0.28–2.00μg/kg,while the limits of quantification were 0.94–6.65μg/kg.Following the application of“top-down”approach,the expanded measurement uncertainty for all the analytes was<30%.The proposed method was successfully applied to determine pesticide residues in 20 market samples in China,where 9 pesticides were detected and quintozene exceeded the criteria domestically and abroad.

Determination of Eight Organophosphorus Pesticide Residues in Pepper by QuEChERS-Gas Chromatography

[ Objectives] This study was conducted to establish a QuEChERS-gas chromatography method for determination of eight kinds of organophosphorus pesticide residues in pepper. [Methods] The samples were extracted by acetonitrile, and anhydrous magnesium sulfate was used for salting out. The extracts were then purified by dispersive solid phase extraction combining with GCB, C18 and PSA. Samples were analyzed by FPD detector. External standard was used as quantitive method. [ Results] The detection limits were in the range of 0. 001 -0. 008 mg/kg, the average recoveries ranged from 83.5% to 101.2% , and the relative standard deviation （RSD） of the eight organophosphorus pesticide residues were below 5%. [ Conclusions] The method is simple, quick, easy and effective for the determination of pepper.

Evaluation of Heavy Metals and Pesticide Residues in Dendrobium officinale Produced in Guangxi

[Objectives]To establish a method for the determination of heavy metals and pesticide residues in Dendrobium officinale produced in Guangxi and its culture substrate.[Methods]The contents of five heavy metals(Pb,Cd,As,Hg and Cu)were determined by the atomic absorption spectrophotometric(AAS)method;residues of 9 organochlorine pesticides(α-BHC,β-BHC,γ-BHC,δ-BHC,p,p′-DDT,p,p′-DDE,p,p′-DDD,o,p′-DDT and pentachloronitrobenzene)were determined by gas chromatography(GC).[Results]The contents of five heavy metals in the medicinal materials of D.officinale produced in Guangxi were 0.96,0.21,0.021 mg/kg,and not detected,and 0.35 mg/kg.The contents of five heavy metals in the culture substrate were 0.03,0.19,0.21,0.004 and 1.80 mg/kg,respectively;the content of 9 organochlorine pesticide residues in the sample was not detected.[Conclusions]The detection results of heavy metal content and organochlorine pesticide residues in D.officinale produced in Guangxi and its substrate are consistent with the limit requirements of the Chinese Pharmacopoeia.This experiment is expected to provide reliable data reference for ensuring the safety of the drug resources of D.officinale in Guangxi.

Determination of Organochlorine and Nitrogen Containing Pesticide Residues in Water,Sediments and Fish Samples by Reverse Phase High Performance Liquid Chromatograph

With high performance liquid chromatography, the concentrations of α-endosulfan, DDE, parathion methyl, isoproturon, atrazine, carbaryl and carbofuran were determined in farmed raised fish Labeo rohita of two weight groups. All these pesticide residues were detected in fish meat samples. All these pesticide residues except isoproturon were identified in soil sediments, whereas all these pesticide residues except isoproturon, carbaryl and DDE were also present in water samples. DDT, heptachlor, β-endosulfan, chlorpyrifos, dimethoate, captan, cypermethrin, chlorobromuron and chlorotoluron were absent in all samples of water, sediments and fish flesh. The pesticide residues levels were in order of parathion methyl 〉 DDE 〉 carbofuran 〉 atrazine 〉 α-endosulfan 〉 isoproturan 〉 carbaryl. The concentrations of pesticides were higher in fish weighing 800 -1 300 g than in those weighing 250 -750 g. The DDE was remained highest in sediments, while that was not detected in water samples. The pesticides （endosulfan, parathion methyl, atrazine and carbofuran） had crossed their MRL values （0.001 μg/g） in water samples.

Pesticide residues in bayberry(Myrica rubra)and probabilistic risk assessment for consumers in Zhejiang,China

As pesticide residues in bayberry has raised serious concern from the public in China, a monitoring survey was carried out during 2013–2014 and 157 samples were analyzed in total. Twenty-three pesticides were detected among the 44 pesticides analyzed and at least one pesticide was detected in 63% of 99 samples. Whereas 45.6% of samples were found with two or more pesticide residues, and 23.6% of samples with four or more pesticide residues. Probabilistic risk assessments indicated that estimated daily intake（EDI） of cyhalothrin at the P97.5th percentile level is 1.11 times larger than the acceptable daily intake（ADI） for children, the estimated short-term intake（ESTI） at the P97.5th percentile level is 1.9 and 1.78 times larger than the acute reference dose（ARf D） for adult and children, respectively, indicating the potential risk concern from pyrethroids. EDI of the pesticides with anti-androgenic effects ranged from 0.15–2.46 of ADI, the probability of exposure exceeding the ADI was 7.1 and 31.1% for adults and children, respectively, the probability of exposure of pyrethroids exceeding the ADI was 3.8% for children. Exposures for other pesticides and groups were below 1.0. Because the co-occurrence of frequency of cyhalothrin and cypermethrin was 9.55%, the combinations of pesticides detected with anti-androgenic effects has not been found in the present monitoring, the results indicate that the pesticide residues in bayberry will not constitute serious public health risk, however, they are significant for the management of pesticide use on bayberry and dietary health risk in China.

Variability of Pesticide Residues in Vegetables from the Marketplaces in Jinan City

In order to provide technological support for risk estimation of pesticide residues taken from vegetables, the residues of pesticide in vegetables in Jinan City, China, were investigated. Moreover, the variability of pesticide residues in vegetables was explored, and the variability factor was calculated. The level of pesticide residue was studied by statistical method. The variability factor was calculated using the Harrell-Davis method in accordance with principles recommended by the JMPR. In addition, the procedure of evaluation was validated according to the principles laid down by the JMPR （Joint Meeting on Pesticide Residues）. The detection rate of pesticide residues in all marketplace samples was less than 20% in Jinan City. The unqualified rate of vegetables was low （0.6%）. The chlorothalonil was found as the pesticide with the highest rate of detection. The vegetables with the highest rate of pesticide residues detected were leafy vegetables. The relationship between variability factor and mean value of concentrations of contaminations was expressed by the formula, v=4.9×Cmean. The pesticide residues in vegetables from Jinan City is low. The evaluated variability factor is larger than that the value recommended by the JMPR, however, less than the default value used for acute intake assessment of pesticide residues in UK in most cases.