Xiaohu Wu

Simultaneous determination of four neonicotinoid insecticides residues in cereals, vegetables and fruits using ultra-performance liquid chromatography/tandem mass spectrometry

A rapid multi-residue analytical method was developed for the determination of four nicotinoid insecticides (thiacloprid, thiamethoxam, clothianidin, and dinotefuran) in cereals, vegetables and fruits using QuEChERS method and ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The samples were extracted by acetonitrile and subsequently cleaned up using primary secondary amine (PSA) and graphitized carbon black (GCB) prior to UPLC-MS/MS analysis. The determination of the target compounds was achieved in less than 2.5 min using an electrospray ionization source in positive ion mode (ESI+). The method showed good linearity in the concentration range of 0.01–1 mg L−1 with correlation coefficients >0.999. Recovery studies were performed at three fortification levels of 0.01, 0.05, and 0.5 mg kg−1 in blank rice, wheat, cucumber, tomato, cabbage, apple, and peach samples. The overall average recoveries ranged from 82.7% to 103.4% with intra-day relative standard deviations (RSDr) which ranged between 1.3% and 7.9% and inter-day RSD (RSDR) from 3.9% to 11.6%, respectively. The limits of detection (LOD) were below 0.68 μg kg−1, while the limits of quantification (LOQ) were 0.71–2.26 μg kg−1. The developed analytical method provides a basis for monitoring neonicotinoid insecticide residues in cereals, vegetables and fruits.

Simultaneous determination of oxathiapiprolin and two metabolites in fruits, vegetables and cereal using a modified quick, easy, cheap, effective, rugged, and safe method and liquid chromatography coupled to tandem mass spectrometry.

An effective and rapid analytical method for the simultaneous determination of a new fungicide oxathiapiprolin and its metabolites (IN-E8S72 and IN-WR791) residues in fruits (grape, watermelon, watermelon peel), vegetables (cucumber, tomato, potato) and cereal (wheat) was developed by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) using the modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction concept. Three target compounds were extracted from all matrices with 1% (V/V) formic acid aqueous solution and acetonitrile then cleaned by dispersive solid phase extraction (dSPE) with octadecylsilane (C18) and graphitized carbon black (GCB). The determination of the target compounds was achieved within a 5.1min run time by using an UPLC HSS T3 column connected to an electrospray ionization source (ESI, positive ion mode) for oxathiapiprolin and the negative mode for the two metabolites. The method showed excellent linearity (R(2)>0.9904) for target compounds. The limit of detection (LOD) for the three compounds ranged from 0.5μgkg(-1) to 7.5μgkg(-1) and the limits of quantitation (LOQ) were 1μgkg(-1) and 10μgkg(-1) for oxathiapiprolin and the metabolites, respectively. The mean recoveries from seven matrices ranged from 81.5 to 110.7%, with intra-day relative standard deviations (RSDr) in the range of 0.8-12.0% for all three test compounds. The inter-day RSDR were less than 14.5% for all of the recovery tests. The method was successfully applied for simultaneous analysis of oxathiapiprolin and its metabolites in actual trial samples, indicating its effectiveness in investigating oxathiapiprolin and its metabolites in the food.

Response of microbial community to a new fungicide fluopyram in the silty-loam agricultural soil.

The impacts of fluopyram on a soil microbial community were studied at three application rates: at the recommended field rate (T1, 0.5mg/kg soil), three-fold recommended field rate (T3, 1.5mg/kg soil) and ten-fold recommended field rate (T10, 5mg/kg soil). Soil samples were taken after 7, 15, 30, 45, 60 and 90 days of application to determine the fluopyram residue and microbial properties (i.e., basal respiration, substrate-induced respiration, microbial biomass carbon, microbial community function and structure). The half-lives of the fluopyram at levels of 0.5, 1.5 and 5mg/kg in soil were calculated to be 64.2, 81.5 and 93.6 days, respectively. The results demonstrated that fluopyram treatment (T1, T3 and T10) decreased microbial biomass C but increased the basal respiration, substrate-induced respiration, and ecophysiological indices (qCO2). Average well color development (AWCD) represents the oxidative capacity of soil microorganisms cultivated in the BIOLOG micro-plates and usually indicates the overall microbial metabolic capacity. The BIOLOG results revealed that the AWCD in the soil treated with 1.5 and 5mg/kg fluopyram (T3 and T10) was significantly lower than that of the control during the incubation period. A similar variation in the diversity indices (Simpson index and McIntosh index) was observed. Phospholipid fatty acid (PLFA) analysis revealed that the addition of fluopyram decreased the total amount of PLFAs, bacterial biomass (both Gram-positive (GP) bacteria and Gram-negative (GN)), fungal biomass, the ratios of the GN/GP and fungi/bacteria at all incubation times. Principal component analyses (PCA) suggested that the addition of fluopyram shifted the soil microbial community structure and function. Hence, fluopyram has a harmful effect on overall soil microbial activity, and changed soil microbial community structure and function.

Simultaneous determination of organophosphorus pesticides in fruits and vegetables using atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry

This paper describes the application of atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry for the simultaneous determination of organophosphorus pesticides in apple, pear, tomato, cucumber and cabbage. Soft ionization with atmospheric pressure ionization source was compared with traditional electron impact ionization (EI). The sensitivity of GC coupled to atmospheric pressure ionization (APGC) for all the analytes was enhanced by 1.0-8.2 times. The ionization modes with atmospheric pressure ionization source was studied by comparing the charge-transfer and proton-transfer conditions. The optimized QuEChERs method was used to pretreat the samples. The calibration curves were found linear from 10 to 1000μg/L, obtaining correlation coefficients higher than 0.9845. Satisfactory mean recovery values, in the range of 70.0-115.9%, and satisfactory precision, with all RSDr <19.7% and all RSDR values <19.5% at the three fortified concentration levels for all the fifteen OPPs. The results demonstrate the potential of APGC-QTOF-MS for routine quantitative analysis of organophosphorus pesticide in fruits and vegetables.

Supercritical fluid chromatography–tandem mass spectrometry-assisted methodology for rapid enantiomeric analysis of fenbuconazole and its chiral metabolites in fruits, vegetables, cereals, and soil

Here, we developed a rapid and robust supercritical fluid chromatography-tandem mass spectrometry (SFC-MS/MS) method for simultaneous detection of fenbuconazole and its chiral metabolites in fruit, vegetable, cereal, and soil. Baseline separation of six stereoisomers was achieved on an amylose tris-(3,5-dimethylphenylcarbamate)-coated chiral column in 4.0min using a mobile phase composed of CO2/ethanol (flow rate of 1.8mL/min). Ionisation efficiency and sensitivity was optimized with a post-column compensation solvent (0.1% formic acid/methanol). Target analytes were extracted with acetonitrile and purified using dispersive solid phase extraction sorbents. Six stereoisomers at three concentrations (5, 50, and 250µg/kg) achieved satisfactory recoveries (76.3-104.6%) with RSDs≤11.5% Excellent linearities (R2≥0.9963) and the limits of quantification (LOQs, 0.13-3.31μg/kg) were established for all six stereoisomers. Results show that the proposed method is suitable for routine detection of six stereoisomers of fenbuconazole and its chiral metabolites in food and environmental samples.

Simultaneous determination of three strobilurin fungicide residues in fruits, vegetables and soil by a modified quick, easy, cheap, effective, rugged (QuEChERS) method coupled with gas chromatography-tandem mass spectrometry

A gas chromatography-tandem mass spectrometry (GC-MS/MS) method followed by a modified quick, easy, cheap, effective, rugged (QuEChERS) method for the analysis of three strobilurin fungicide residues (picoxystrobin, kresoxim-methyl and trifloxystrobin) in fruits, vegetables and soil was developed and validated. The three fungicides were extracted with ethyl acetate and cyclohexane (v/v = 1/1), and subsequently cleaned up using a combination of primary secondary amine and graphitized carbon black prior to GC-MS/MS analysis. The three fungicides were qualitatively determined using the multiple reaction monitoring mode with two ion transitions measured for each fungicide and evaluation by collision tests, and were determined quantitatively using the external standard method. Recovery studies were performed at three fortification levels of 0.005, 0.05, and 0.5 mg kg−1 in blank cucumber, tomato, apple, grape and soil samples. The overall average recoveries ranged from 87% to 112%, with intra-day relative standard deviations (RSDs) of 0.9% to 10.5% and inter-day RSD of 0.7% to 12.2%, respectively. The calculated limits of detection and quantification were typically below 0.006 and 0.019 μg kg−1 for GC-MS/MS. The results of the method validation confirm that this proposed method is easy and reliable for the determination of residues of strobilurin fungicides in fruits, vegetables and soil.

Effects of myclobutanil on soil microbial biomass, respiration, and soil nitrogen transformations.

A 3-month-long experiment was conducted to ascertain the effects of different concentrations of myclobutanil (0.4 mg kg(-1) soil [T1]; 1.2 mg kg(-1) soil [T3]; and 4 mg kg(-1) soil [T10]) on soil microbial biomass, respiration, and soil nitrogen transformations using two typical agricultural soils (Henan fluvo-aquic soil and Shanxi cinnamon soil). Soil was sampled after 7, 15, 30, 60, and 90 days of incubation to determine myclobutanil concentration and microbial parameters: soil basal respiration (RB), microbial biomass carbon (MBC) and nitrogen (MBN), NO(-)3-N and NH(+)4-N concentrations, and gene abundance of total bacteria, N2-fixing bacteria, fungi, ammonia-oxidizing archaea (AOA), and ammonia-oxidizing bacteria (AOB). The half-lives of the different doses of myclobutanil varied from 20.3 to 69.3 d in the Henan soil and from 99 to 138.6 d in the Shanxi soil. In the Henan soil, the three treatments caused different degrees of short-term inhibition of RB and MBC, NH(+)4-N, and gene abundance of total bacteria, fungi, N2-fixing bacteria, AOA, and AOB, with the exception of a brief increase in NO(-)3-N content during the T10 treatment. The MBN (immobilized nitrogen) was not affected. In the Shanxi soil, MBC, the populations of total bacteria, fungi, and N2-fixing bacteria, and NH(+)4-N concentration were not significantly affected by myclobutanil. The RB and MBN were decreased transitorily in the T10 treatment. The NO(-)3-N concentrations and the abundance of both AOA and AOB were erratically stimulated by myclobutanil. Regardless of whether stimulation or suppression occurred, the effects of myclobutanil on the two soil types were short term. In summary, myclobutanil had no long-term negative effects on the soil microbial biomass, respiration, and soil nitrogen transformations in the two types of soil, even at 10-fold the recommended dosage.

Atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry for simultaneous determination of fifteen organochlorine pesticides in soil and water.

In this study, the application of atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry (APGC-QTOF-MS) has been investigated for simultaneous determination of fifteen organochlorine pesticides in soil and water. Soft ionization of atmospheric pressure gas chromatography was evaluated by comparing with traditional more energetic electron impact ionization (EI). APGC-QTOF-MS showed a sensitivity enhancement by approximately 7-305 times. The QuEChERs (Quick, Easy, Cheap, Effective, Rugged, and Safe) method was used to pretreat the soil samples and solid phase extraction (SPE) cleanup was used for water samples. Precision, accuracy and stability experiments were undertaken to evaluate the feasibility of the method. The results showed that the mean recoveries for all the pesticides from the soil samples were 70.3-118.9% with 0.4-18.3% intra-day relative standard deviations (RSD) and 1.0-15.6% inter-day RSD at 10, 50 and 500 μg/L levels, while the mean recoveries of water samples were 70.0-118.0% with 1.1-17.8% intra-day RSD and 0.5-12.2% inter-day RSD at 0.1, 0.5 and 1.0 μg/L levels. Excellent linearity (0.9931 ≦ r(2)≤ 0.9999) was obtained for each pesticides in the soil and water matrix calibration curves within the range of 0.01-1.0mg/L. The limits of detection (LOD) for each of the 15 pesticides was less than 3.00 μg/L, while the limit of quantification (LOQ) was less than 9.99 μg/L in soil and water. Furthermore, the developed method was successfully applied to monitor the targeted pesticides in real soil and water samples.

Determination of Sulfoxaflor in Animal Origin Foods Using Dispersive Solid-Phase Extraction and Multiplug Filtration Cleanup Method Based on Multiwalled Carbon Nanotubes by Ultraperformance Liquid Chromatography/Tandem Mass Spectrometry

In the present study, a rapid analytical method was developed to determine the residue of sulfoxaflor in milk, pork, eggs, porcine liver, porcine kidney, porcine fat, and chicken. The dispersive solid-phase extraction (d-SPE) and multiplug filtration cleanup (m-PFC) based on multiwalled carbon nanotubes (MWCNTs) were compared for sulfoxaflor in the above matrix and then detected by ultraperformance liquid chromatography coupled with tandem mass spectrometry. The analyte was eluted within 5 min using a Waters Acquity UHPLC HSS T3 column under ESI(+) conditions. The limits of detection were 1 μg kg(-1) for all of the matrices. Good linearities of sulfoxaflor were obtained in the range of 1-100 μg L(-1), and the correlation coefficients (R(2)) were higher than 0.9988 in all matrices. The average recoveries of the target compound were between 75.5% and 114.9%, and the intraday and interday relative standard deviation values were <14%. Both methods have purification ability. While considering the cost of analysis and the applicability of the method, d-SPE was selected to purify the samples in the present study. The method was successfully used to analyze the residue of sulfoxaflor in foods of animal origin.

Effects of hexaconazole application on soil microbes community and nitrogen transformations in paddy soils

The ecological risks of widely used hexaconazole on soil microbes remain obscure. Thus, a 3-month-long experiment using two typical paddy soils in China (red soil and black soil) was conducted to assess the effects of hexaconazole (0.6 (T1) and 6 (T10) mgkg-1 soil) on the overall microbial biomass, respiratory activity, bacterial abundance and community structure, and nitrogen transformations. Soil was sampled after 7, 15, 30, 60, and 90days of incubation. The half-lives of the two doses of hexaconazole varied from 122 to 135d in the black soil and from 270 to 845d in the red soil. Both dosages of hexaconazole did not affect NH+4-N content, N2-fixing bacterial populations, total bacterial diversity, and community structure, but transitorily decreased the populations of total bacteria in both soil types. In the black soil, T10 negatively affected microbial biomass carbon (MBC) and soil basal respiration (RB), but transitorily increased NO-3-N concentration and ammonia-oxidizing bacteria populations, while T1 had almost no effect on most of the indicators. As for red soil, both concentrations of fungicide significantly, but transitorily, inhibited MBC and RB, while only T10 had a relatively long stimulatory effect on NO-3-N concentration and ammonia-oxidizing archaea populations. This study showed that over application of hexaconazole is indeed harmful to soil microorganisms and may reduce soil quality and increase the risk of nitrogen loss in paddy soils.