Matrix Effects of Fourteen Organophosphorus Pesticides Residues in Nine Kinds of Vegetable Matrices

The matrix effects of 14 organophosphorus pesticides in 9 kinds of vegetables matrices were preliminarily studied by gas chromatography/flame photomet- ric detection（FPD） in the paper. The matrix effects of 14 organophosphoms pesticides in 9 kinds of vegetable matrices at 0.05, 0.1 and 0.2 mg/L were compared, respectively. The results showed that matrix enhancement effect and matrix attenuation effect existed in all cases, while matrix effects did not have strong correlation with concentrations of pesticides, but were related to species of vegetables and structure and polarity of pesticides.

Research Progress on Detection Techniques of Fungicide Residues in Chinese Chives

Chinese chive is a kind of medicinal and edible plant,with many diseases,and chemical fungicides are usually used for control.In order to find out the risk of pesticide residues in Chinese chives,this paper summarized relevant literatures published in recent years,and sorted out and analyzed the types of pesticides used and detection techniques of common diseases in Chinese chives.

Rapid screening of 420 pesticide residues in fruits and vegetables using ultra high performance liquid chromatography combined with quadrupole-time of flight mass spectrometry

A new method for screening and identification 420 pesticide residues in fruits and vegetables by ultra-performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry(UPLC-Q-TOF/MS)were developed.The samples were extracted with acetonitrile/acetic acid(99:1,V/V),and clean-up by SinChERS-Nano(single-step,cheap,effective,rugged,safe,nano)column,determined by UPLC-Q-TOF/MS.The accurate mass database and MS/MS database which contains 420 pesticides were established,the automatic retrieval of detection results was carried on according to the accurate mass,retention time,isotope ratio,ion fragment information,and so on.Method verification was performed on leeks samples.The results showed that 420 pesticides had good linearity in the range of 0.1-100μg/L,and the correlation coeffificients(R2)was greater than 0.990.The limits of detections(LODs)and limits of quantifications(LOQs)of 420 pesticides were in range of 0.05-2.0 and 0.1-5.0μg/L,respectively.The average spike recoveries at 3 levels were 70.1%to 119.7%,and the relative standard deviations(RSD)were lower than 20%(n=6).With this method,a survey of pesticide residues was conducted for 110 samples of 10 different fruits and vegetables,which provided scientific data for ensuring pesticide residue safety of the fruits and vegetables consumed daily by the public.This method was simple,sensitive and accurate,and could be used for rapid screening of 420 pesticide residues in fruits and vegetables.

Regional selection of insecticides and fungal biopesticides to control aphids and thrips and improve the forage quality of alfalfa crops

The efficacies of biological and conventional chemical insecticides against two major insect pests of alfalfa(aphids and thrips)were compared in three sites across China’s alfalfa belt.In addition,the persistence of the residues of chemical insecticides in alfalfa and their influence on the quality of alfalfa hay were examined.Efficacy varied among the different biological and chemical insecticides.The chemical insecticides were significantly more effective than biopesticides in a short time-frame.The efficacy period of biopesticides was significantly longer than that of chemical insecticides,and the corrected mortality rate of aphids in all regions was above 50%at 14 days after application.The analysis of pesticide residues showed that the residual doses of all the pesticides were within the allowed ranges after the safe period.The acid detergent fiber and neutral detergent fiber contents in alfalfa hay were higher and the protein content was lower in chemical insecticide treatments than in biopesticide treatments in Hebei.The relative feeding value of alfalfa hay treated with Metarhizium anisopliae IPP330189 was the highest among the treatments.Compared with chemical insecticides,the yield of alfalfa hay was higher in the biopesticides treatments.Biopesticides show a stronger control effect on insect populations and also a better improvement in the quality of alfalfa hay than chemical insecticides.This study provides a basis for exploring and developing a comprehensive control regime for alfalfa insect pests in the different alfalfa-growing regions in China,and for reducing chemical insecticide usage and improving forage quality.

Detection and Analysis of Pesticide Residues in Chinese Chives and Risk Assessment of Dietary Intake

[Objectives]This study was conducted to understand the status of pesticide residues and dietary intake risk of Chinese chives in Tangshan area. [Methods] Sixty eight kinds of pesticide residues in 415 Chinese chive samples collected from Tangshan area were qualitatively and quantitatively determined by high-performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS) and gas chromatography(GC) in 2020. [Results] The results showed that 41 kinds of pesticide residues were detected in the 415 Chinese chive samples, and the detection rate was 69.4%(288/415), and there was a combination of pesticides in many samples. According to the National Food Safety Standard―Maximum Residue Limits of Pesticides in Food(GB 2763-2019), the residues of 12 pesticides exceeded the maximum residue limits(MRLs), and the unqualified rate was 38.07%(158/415). The highest detection rate of clothianidin was 41.20%(171/415), but there was no MRL in GB 2763-2019. The next was procymidone, the detection rate of which was 35.42%(147/415), and the over-standard rate was 30.12%(125/415). Forbidden and restricted pesticides were detected in some samples. According to the dietary exposure risk assessment, the NEDI/ADI values were all less than 1 and the intake risk was within acceptable range. In Tangshan area, the types of pesticides used in Chinese chive production are complex, and there are risks of multi-residue pollution and use of banned and restricted pesticides and unregistered pesticides. It is suggested that routine monitoring of pesticide residues and management of pesticide use should be strengthened to ensure the quality and safety of agricultural products. [Conclusions] This study provides a theoretical basis for the safe production of Chinese chive and the standardized and rational use of pesticides.

Assessment of the Pesticides Utilization and the Pesticide Residues Presence in Fresh and Tomato Products for the Tomato Supply Chain in Rwanda

Pesticide residues are either natural or synthetic and are found in most edible products such as fresh fruits, vegetables, meat and other processed products. Excess of these pesticides’ residues is unsafe for consumption due to regulatory measures. Thus, it is beneficial to assess the level of residues of pesticides in the food diet in order to improve the standard of living of the population. This study intends to assess the pesticide usage and residue levels of selected pesticides in fresh tomatoes in the supply chain of Rwanda. The results of the study confirm that there are around 10 brands of pesticides used in Rwanda. 58.97% of the surveyed people around the country are males and 71.79% of farmers apply rockets as the main pesticide. More than 22% of surveyed farmers affirmed to consume the raw or/and unwashed tomatoes. This study revealed that the residues of the active ingredients contained in the pesticides are accumulated in unwashed tomatoes and the quantity of such residues is shown in this study. Deltamethrin was 0.64 ± 0. 009 mg·kg?1 in tomatoes collected in Rusizi district, cypermethrin 1.1435 ± 0. 0375 mg·kg?1 in tomatoes collected from Gisagara District, mancozeb residues was 0.620 ± 0.000 mg·kg?1 in tomatoes collected from Rusizi district. The results of the study also show that pesticide residues are not found in the washed tomatoes. Therefore, the detection of pesticide residues in unwashed tomatoes in some samples indicates the malpractice of residues among farmers in Rwanda. Also, consumers eating the unwashed fresh tomatoes are recommended to wash the tomatoes before use.

A Rapid Determination of 30 Prohibited Pesticide Residues in Lycii Fructus by UPLC-MS/MS

Prohibited pesticide residues have become one of the main factors affecting the quality and safety of Lycii Fructus,However,rarely studies focus on the rapid determination of these residues.Here,a total of 30 kinds of prohibited pesticide residues were determined by ultra-performance liquid chromatography tandem triple quadrupole mass spectrometry(UPLC-MS/MS)in five different process ways.Pretreatment methods,chromatographic separation and detection conditions in mass spectrometry were all optimized accordingly.Among the five different pretreatment methods,the first and third solid phase extraction failed to provide high recoveries of sulfosulfuron compounds(both lower than 60%).Recovery of chlorphenamidine by the Quick Easy Cheap Effective Rugged and Safe multiresidue method(QuEChERS)was lower than 60%,which did not meet the requirements of trace determination.The concentrations of 30 prohibited pesticides residues treated by straightforward and solid phase extraction showed good linearity in their corresponding ranges,with correlation coefficients over 0.99.The average recoveries of straightforward ranged from 78.13%to 110.9%,while RSD ranged from 1.3%to 16.9%,albeit poor purification was observed.The recovery yield from solid phase extraction was between 67.75%and 103.08%with RSD value from 0.8%to 14.0%,which met the requirements of trace determination,this method has good precision and stability.These results could be employed to other Traditional Chinese Medicines(TCMs)in detecting prohibited pesticide residues.

Rapid Screening of Pesticide Residues in Strawberry Based on HPLC-QTOF/MS SWATH Acquisition Mode

[Objectives]The paper was to establish a rapid screening method of pesticide residues in strawberry based on HPLC-QTOF/MS SWATH acquisition mode.[Methods]The strawberry sample was extracted with acetonitrile,purified with anhydrous magnesium sulfate,sodium chloride and primary secondary amine(PSA)powder,and then loaded on the machine.The full information spectrum was collected by positive ion mode and screened by comparing with the spectrum library,and 20 kinds of pesticide residues were quantitatively analyzed.[Results]The detection limits of 20 pesticide residues were 0.0002-0.0100 mg/kg,and they showed good linearity in the range of 0.0005-0.1000μg/mL(R 2≥0.995).The recoveries ranged from 62.8%to 106.3%.[Conclusions]This method is rapid,simple,sensitive and non-targeted,and can be used for rapid screening of multiple pesticide residues in strawberry.

Multiple Pesticide Residues in Bananas Sold in Tangshan City and Dietary Risk Assessment

[Objectives]This study was conducted to investigate the pesticide residue status of bananas in Tangshan area and the dietary intake risk of consumers.[Methods]High-performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS)was applied to detect 70 pesticide residues in 191 batches of banana samples extracted from Tangshan area,and chronic and acute risk assessments were conducted.[Results]Among the 191 batches of bananas,172 batches of samples were detected to contain agrochemicals,with a detection rate of 90.05%.Seventeen agrochemicals were detected,accounting for 24.29%of the total agrochemicals tested.There was a phenomenon of multiple pesticide residues in a single sample,and high detection rates were found in carbendazim(49.21%),prochloraz(41.88%),pyraclostrobin(34.03%)and imidacloprid(30.37%).According to GB 2763-2021 National Food Safety Standards—Maximum Residue Limits for Pesticides in Food,the over-standard rate of imidacloprid was 17.8%;and the chronic and acute dietary risks of the 17 pesticide residues were all less than 100%.[Conclusions]The pesticide residues in bananas consumed by consumers on a daily basis do not pose unacceptable dietary risks.

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides （OCPs） were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX （DDD, DDE and DDT） had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p＇-（DDD＋DDE）/DDT in soils under three land usages were： paddy field 〉 tree land 〉 fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p＇-（DDD＋DDE）/DDT 〉1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.

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).

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.

A novel thermal biosensor based on enzyme reaction for pesticides measurement

A novel thermal biosensor based on enzyme reaction for pesticides detection has been developed. This biosensor is a flow injection analysis system and consists of two channels with enzyme reaction column and identical reference column, which is set for eliminating the unspecific heat. The enzyme reaction takes place in the enzyme reaction column at a constant temperature(40℃) realized by a thermoelectric thermostat. Thermosensor based on the thermoelectric module containing 127 serial BiTe-thermocouples is used to monitor the temperature difference between two effluents from enzyme reaction column and reference column. The ability of this biosensor to detect pesticides is demonstrated by the decreased degree of the hydrolytic heat in two types of thermosensor mode. The hydrolytic reaction is inhibited by 36% at 1 mg/L DDVP and 50 % at 10 mg/L DDVP when cell-typed thermosensor is used. The percent inhibition is 30% at 1 mg/L DDVP and 42% at 10 mg/L DDVP in tube-typed thermosensor mode. The detection for real sample shows that this biosensor can be used for detection of organophosphate pesticides residue.

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.

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.

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.

Simultaneous determination of 15 pesticide residues in Chinese cabbage and cucumber by liquid chromatography-tandem mass spectrometry utilizing online turbulent flow chromatography

In this experiment,a liquid chromatography tandem mass spectrometry method was built to determine 15 pesticide residues in Chinese cabbage and cucumber samples based on online turbulent flow chromatography purification.After modified quick,easy,cheap,effective,rugged,and safe(QuEChERS)extraction,extracts were directly injected to the TLX(TurboFlow Liquid Xcalibur)system and brought to TurboFlow™columns for on-line purification and then transferred to analytical column for further separation and analysis.TurboFlow™columns types,transfer flow rate,and transfer time were optimized.Limits of detection and limits of quantification of the method obtained for 15 pesticide residues were ranged between 0.2–1.0μg/kg and 0.5–2.0μg/kg in Chinese cabbage and cucumber samples.Recoveries of pesticide residues were in range of 75.3%–103.7%.Matrix effects for 15 pesticides were in range of 5.6%–106.6%.The developed method has been successfully used for the determination of 15 pesticide residues in real samples.

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.

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.

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.