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1.
ABSTRACT

An analytical method for the simultaneous determination of propiconazole isomers and tebuconazole residues in blueberries was developed using solid-phase microextraction (SPME) coupled to gas chromatography. Confirmation was performed by gas chromatography–mass spectrometry in selected-ion monitoring mode. The SPME fibre coating selected was CWX-DVB, and the pH was adjusted to 7 with NaOH. The method is selective with adequate precision and high accuracy and sensitivity. Recoveries ranged between 97.4% and 98.9% for all compounds; and detection and quantification limits were respectively 0.21 and 0.49 μg kg–1 for propiconazole I; 0.16 and 0.22 μg kg–1 for propiconazole II; and 0.16 and 0.48 μg kg–1 for tebuconazole. The degradation of these fungicides in blueberries followed first-order rate kinetics. The half-life times for flowering and fruit set applications were respectively 4.0 and 10.3 days for propiconazole I, 4.0 and 11.4 days for propiconazole II, and 3.5 and 12.4 days for tebuconazole.  相似文献   

2.
Azole fungicides: occurrence and fate in wastewater and surface waters   总被引:2,自引:0,他引:2  
The mode of action of azole compounds implies a potential to affect endocrine systems of different organisms and is reason for environmental concern. The occurrence and fate of nine agricultural azole fungicides, some of them also used as biocides, and four azole pharmaceuticals were studied in wastewater treatment plants (WWTPs) and lakes in Switzerland. Two pharmaceuticals (fluconazole, clotrimazole, 10-110 ng L(-1)) and two biocides (propiconazole, tebuconazole, 1-30 ng L(-1)) were consistently observed in WWTP influents. Loads determined in untreated and treated wastewater indicated thatfluconazole, propiconazole, and tebuconazole were largely unaffected by wastewater treatment, but clotrimazole was effectively eliminated (> 80%). Incubation studies with activated sludge showed no degradation for fluconazole and clotrimazole within 24 h, but strong sorption of clotrimazole to activated sludge. Slow degradation and some sorption were observed for tebuconazole and propiconazole (degradation half-lives, 2-3 d). In lakes, fluconazole, propiconazole, and tebuconazole were detected at low nanogram-per-liter levels. Concentrations of the pharmaceutical fluconazole correlated with the expected contamination by domestic wastewater, but not those of the biocides. Per capita loads of propiconazole and tebuconazole in lakes suggested additional inputs; for example, from agricultural use or urban runoff rainwater.  相似文献   

3.
本文旨在研究鲜切生菜制备过程中不同处理过程对五种农药残留的影响,并评估农药残留对人体的健康风险。通过开展田间试验研究三种杀虫剂(吡虫啉、虫酰肼、氯氰菊酯)和两种杀菌剂(戊唑醇、嘧菌酯)在模拟商用鲜切生菜处理条件下的耗散情况,采用基于乙腈的乙二胺-N-丙基硅烷(Primary secondary amine,PSA)填料分散固相萃取净化,气相色谱-串联质谱和液相色谱-串联质谱分析验证5种农药残留分析方法的可靠性并对农药残留进行检测。结果表明,5种农药残留在用次氯酸钠洗涤后均出现显著性下降(P<0.05),在切、清洗、离心脱水、冷藏保存时鲜切生菜中5种农药的加工因子均低于1,整个处理过程大大降低了农药残留水平。体外模拟胃肠环境下5种农药的生物可给性均未达到50%。不同添加水平下,生物可给性依次为:氯氰菊酯 > 嘧菌酯 > 戊唑醇 > 吡虫啉 > 虫酰肼,结合供试农药的每日容许摄入量(Allowable Daily Intake,ADI)值发现,对人体的健康风险而言,3种杀虫剂中虫酰肼最安全,吡虫啉比氯氰菊酯安全,而杀菌剂嘧菌酯比戊唑醇更安全。通过加工可去除生菜中的农药残留,降低膳食暴露量,对保障消费者的膳食安全具有积极意义。  相似文献   

4.
This work was done to demonstrate the opportunities provided by application of meta-analysis in plant pathology. It was a case study used to determine the effectiveness of foliar fungicides in minimising yield loss from a complex of yellow spot (Pyrenophora tritici-repentis) and septoria nodorum blotch (Stagonospora nodorum, teleomorph: Phaeosphaeria nodorum) (YS-SNB disease complex) on wheat in the northern grain-belt of Western Australia. Forty-seven datasets of experimental results from 14 growing seasons, using 18 varieties sprayed one to three times, predominantly with tebuconazole or propiconazole fungicides, were analysed. Across the datasets, the wheat yield gain from fungicide application was 297 kg ha?1 with a 95 % confidence interval of 11.6 kg ha?1. Significant yield gains resulted from single or multiple applications of fungicides. Both propiconazole and tebuconazole, increased yield of wheat affected by the YS–SNB disease complex, with yield gain from propiconazole being greater than that from tebuconazole. Yield response varied significantly among crop growing seasons. Meta-analysis was able to aggregate a large number of experimental results and answer important questions related to the variables that influenced those results; in this case the effectiveness of fungicides in minimising yield loss from the YS-SNB disease complex on wheat. It also identified areas where further research needs to be done. It is concluded that meta-analysis has the potential to contribute to similar analyses in other crop disease systems.  相似文献   

5.
A rapid, efficient, and environmentally friendly method using vortex-assisted ionic liquid dispersive liquid-liquid microextraction (VA-IL-DLLME) prior to high-performance liquid chromatography coupled with photodiode array detection (HPLC-PDA) has been developed for the determination of six triazole fungicides (triazolone, triadimenol, epoxiconazole, flusilazole, tebuconazole, and diniconazole) in various fruit juices. 1-Hexyl-3-methylimidazolium hexafluorophosphate ([C6MIM][PF6]) and acetonitrile were used as extraction and dispersive solvents, respectively. A single factor experiment was selected to obtain the significant variables from the several related parameters that could affect the extraction efficiencies, such as the volume of IL and acetonitrile, extraction time, centrifugation time, and salt addition. Under the optimum conditions, an excellent linearity with correlation coefficients higher than 0.997 was obtained. Enrichment factors and average recoveries in three concentration levels ranged from 51 to 72, and 71.0 to 104.5 %, respectively, and the relative standard deviations (RSDs) from 1.4 to 11.8 %. The limits of detection (LODs) (S/N?=?3) for the six triazole fungicides were between 0.4 and 6.7 μg L?1. The proposed method was successfully applied for the determination of trace amounts of triazole fungicides in various fruit juices including peach, apple, and orange juices.  相似文献   

6.
A total of 19 pesticide preparations were used according to agricultural practice in six trials in apple orchards. Using gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS), premature Golden Delicious apples collected 64, 50, 36 days before harvest and mature fruit were examined for residues of active ingredients. No residues of triflumuron, triazamate, chlorpyrifos, etofenprox, fenoxycarb, kresoxim-methyl, cyprodinyl, difenoconazole or thiram were detected in the first sampling. Also, the levels of chlorpyrifos-methyl, penconazole, tebuconazole and tolylfluanid dropped during the pre-harvest interval. Detectable residues of pyridaben, thiacloprid, trifloxystrobin and tetraconazole in harvested fruits were below 0.01 mg kg-1, which is the maximum concentration of residues acceptable by baby-food producers in any raw material. The only residues exceeding this concentration were captan and teflubenzuron. Based on the data, farmers can choose pesticides for optimal treatment of plants, while enabling growth of a safe crop suitable for baby-food production.  相似文献   

7.
本文建立了同时分离检测粮谷样品中4种三唑类杀菌剂的分子印迹固相萃取膜-高效液相色谱法。采用自制的联苯三唑醇分子印迹固相萃取膜对粮谷中的联苯三唑醇、三唑酮、烯唑醇和戊唑醇残留进行分离富集,并采用高效液相色谱法测定其在粮谷样品中的残留。试验对淋洗剂、洗脱剂的种类和用量以及检测条件进行了优化。以5 m L水为淋洗剂,3 m L甲醇为洗脱剂,使用C18色谱柱,以甲醇-水(体积比为82:18)溶液为流动相,紫外检测波长为210 nm,外标法定量。结果表明,4种杀菌剂平均回收率在84.2%~98.1%之间,相对标准偏差(RSDs)在1.2%~2.7%之间(n=5)。该分子印迹固相萃取膜不仅对样品净化效果好,而且对4种杀菌剂特异吸附能力强。该方法能高效、快速、灵敏检测粮谷样品中三唑类杀菌剂。  相似文献   

8.
The influence of five sterol biosynthesis-inhibiting (SBI) fungicides (cyproconazole, diniconazole, epoxiconazole, flutriafol, and tebuconazole) on the fermentation and quality of young ale beer was assessed. Fungicides were individually supplied to the brewer wort to obtain a concentration of 0.2 μg/ml. A noticeable influence of the fungicide residues on the fermentation rate was observed in all cases. From the third day onwards, the fermentation rate was low in all treated samples. At the end of fermentation (8 days), statistically significant differences (p < 0.05) were found for the extract and attenuation values, which were higher for all the samples treated with fungicides. As a consequence, a higher amount of residual sugars (mainly maltose and maltotriose) was found in the beer. No significant differences were found for the pH and the polyphenol content after fermentation among the blank and the treated samples, while the values of colour intensity (lower) and tint (higher) in the beer were statistically different.  相似文献   

9.
During 3 years of a monitoring programme, 522 samples of fresh apples, six brands of fruit purées and various types of fruit baby food prepared from these materials were analysed. Each sample was examined for the presence of 86 GC amenable pesticide residues. The reporting limits of the procedure employed for sample analyses were in the range 0.003-0.01 mg kg(-1). Pesticide residues were detected in 59.5% of the samples of fresh apples. However, maximum residue levels (European Union MRLs) were exceeded only in 1.4% of samples. The levels of residues in 'positive' fruit purées were substantially lower, overall with residues detected in 33% of samples. Fruit baby food represented the commodity with the lowest incidence of residues being detected in only 16% of samples. The 0.01 mg kg(-1) MRL was exceeded in 9% of these products. Multiple residues were found in 25% of fresh apples and in 10% of fruit purées. None of fruit baby food samples contained more than a single residue. Organophosphorus insecticides and fungicides representing phtalimides, sulphamides and dicarboximides were the most frequently found residues. To obtain more knowledge on the fate of residues during fruit baby food production, processing experiments employing apples with incurred residues (fenitrothion, phosalone and tolylfluanid) were conducted. Washing of apples did not significantly reduce the content of pesticides. Steam boiling followed by removal of peels/stems was identified as the most efficient steps in terms of residues decrease (phosalone) or complete elimination (fenitrothion and tolylfluanid).  相似文献   

10.
In this study, dispersive solid phase extraction (DSPE) combined with dispersive liquid–liquid microextraction (DLLME) method was developed for the determination of triazole fungicide residues in tea samples. DSPE with ODS C18, primary secondary amine, and florisil as sorbents was applied to clean up and minimize matrix interference from tea samples; it was followed with the enrichment of target compounds in the DLLME procedure and detection with liquid chromatography–tandem mass spectrometry (LC-MS/MS). The effects of various experimental parameters on the DSPE and DLLME procedures were studied systematically, such as the kinds and volume of sorbents, extraction and dispersive solvents, and extraction time. Under optimum conditions, the method was validated in a tea matrix. The matrix-matched calibration curves of three triazoles had good linearity in the range of 0.0125–50 μg kg?1, and the linear regression coefficients (r) ranged from 0.9998 to 0.9999. The limits of quantification (S/N?=?10) for penconazole, tebuconazole, and triadimenfon were 4.0, 7.8, and 31.6 ng kg?1, respectively. The intra-day and inter-day relative standard deviations varied from 3.6 to 18.6 %. Recoveries in three concentration levels were between 91 and 118 %. The obtained results show that the proposed DSPE-DLLME-LC-MS method has the potential to analyze trace fungicides in a complex sample matrix.  相似文献   

11.
The fate and behaviour of five sterol biosynthesis-inhibiting (SBI) fungicides (cyproconazole, diniconazole, epoxiconazole, flutriafol, and tebuconazole) during different stages of beermaking (malting, mashing and boiling) on laboratory scale was assessed. A significant correlation (> 0.93, < 0.05) was observed between amounts removed after steeping and the octanol/water partition coefficient (as log KOW) of the fungicides. Although in smaller proportion than steeping, germination and kilning were significant stages on the fungicide dissipation. The carryover after malting ranged from 30% to 40% of the initial residues on barley. After mashing, a substantial fraction was removed with the spent grains in all cases (36–49%) whereas a weak fall after boiling was observed for the fungicide residues (?2.5%). The calculated transfer factors (TFs) do not indicate a concentration effect after processing in any case (TFs < 1). Finally, after the storage of malt and spent grains (3 months) a slow fall in the residual content was observed.  相似文献   

12.
田金凤  尚远宏 《中国酿造》2021,40(3):177-180
该实验采用QuEChERS净化-超高效液相色谱-串联质谱法测定石榴、芒果、火龙果的5种三唑类杀菌剂残留。样品10.0 g经改进的QuEChERS方法进行前处理,采用ZORBAX SB-C18色谱柱分离,以4 mmol/L甲酸水溶液和甲醇为流动相进行梯度洗脱。质谱采用电喷雾离子源(ESI)和多反应监测(MRM)模式。5种三唑类杀菌剂的质量浓度为4.0~200.0 μg/L时,线性关系良好,相关系数(R2)>0.999,定量限(LOQ)为0.15~1.0 μg/kg,石榴、芒果、火龙果中5种三唑类杀菌剂加标回收率分别为87.7%~103.1%、80.5%~93.5%、81.6%~94.7%,相对标准偏差(RSD)(n=6)分别为4.1%~11.2%、3.8%~7.3%、4.3%~10.2%。说明该方法灵敏度及准确度良好,能满足石榴、芒果、火龙果(皮不可食的热带和亚热带水果)中5种三唑类杀菌剂残留检测的要求。  相似文献   

13.
Between 1986 and 1988, 306 composite samples of fruit representing eight commodities were collected from farm deliveries to the marketplace in Ontario, Canada. All samples were analysed for insecticides and fungicides. The analysis procedure included tests for organochlorine, organophosphorus, synthetic pyrethroid and methylcarbamate insecticides and dithiocarbamate, dicarboximide and organochlorine fungicides. The commodities tested included apples, blueberries, cherries, grapes, peaches, pears, raspberries and strawberries. In 14% of all fruit samples, pesticide residues were below the detection limits, which ranged between 0.005 and 0.02 mg/kg. A further 14% had total combined pesticide residues below 0.1 mg/kg. Total combined fungicide and insecticide residues ranged from 0.1 to 11 mg/kg in 72% of samples. Six different pesticides were in violation of maximum residue limits (MRL) on 11 (3.6%) of fruit samples. Captan exceeded the 5 mg/kg MRL in five samples and EBDC exceeded the 7 mg/kg MRL in two. Other violations included single fruit samples with dicofol, endosulphan, phosalone and iprodione above the MRL. Raw grapes harvested for wine contained residues of 10 pesticides and the number changed little following the crushing of the grapes; however, fermentation into wine significantly reduced residues. Six insecticides and four fungicides were present on the raw grapes and 4/105 were above the MRL. Following crushing, four insecticides and five fungicides were identified and 4/40 were above the MRL. In wine only three insecticides were identified and all were well below the MRL. Carbaryl appeared to be the most persistent, declining very little between raw grapes and wine.  相似文献   

14.
Pesticide residues survey in citrus fruits   总被引:3,自引:0,他引:3  
The use of pesticides is widespread in citrus fruits production for pre- and post-harvest protection and many chemical substances may be applied in order to control undesirable moulds or insects. A survey was carried out to evaluate levels of pesticide residues in citrus fruits. Two multiresidue analytical methods were used to screen samples for more than 200 different fungicides, insecticides and acaricides. A total of 240 samples of citrus fruits including lemon, orange, mandarin, grapefruit, lime, pomelo and kumquat were taken in various markets in the Geneva area during the year 2003. Ninety-five percent of the 164 samples issued from classical agriculture contained pesticides and 38 different compounds have been identified. This high percentage of positive samples was mainly due to the presence of two post-harvest fungicides, imazalil and thiabendazole, detected in 70% and 36% of samples respectively. Only three samples exceeded the Swiss maximum residue limits (MRLs). Fifty-three samples sold with the written indication “without post-harvest treatment” were also controlled. Among theses samples, three exceeded the Swiss MRLs for penconazole or chlorpyrifos and 18 (34%) did not respect the written indication since we found large amounts of post-harvest fungicides. Finally, 23 samples coming from certified organic production were analysed. Among theses samples, three contained small amounts of pesticides and the others were pesticides free.  相似文献   

15.
Three techniques of gas chromatography (GC) either with flame photometric-detector (FPD), electron capture detector (ECD), or with mass-spectrometry (MS) were applied for identification and quantification of pesticide residues on 45 samples of cucumber, tomatoes, and strawberries in fifteen locations in Gaza Governorates. GC-FPD analysis showed the presence of four different organo-phosphorus (OP) pesticides, their levels were very low and below maximum residue limits (MRL's). GC-ECD detected ten different pesticides at levels below the MRL's. Using the GC-MS technique, alpha and beta-endosulfan, chlorpyrifos, carbofuran, chlorfluazuron, triadimenol I and II, penconazole, coptafolmetabolite, pyrimethanil and iprodione were detected and confirmed on some samples of cucumber, tomatoes and strawberries. All GC-MS pesticide residues detected on tomato were below the MRL's except chlorfluazuron while on strawberry were below the MRL's except penconazole, chlorfluazuron and pyrimethanil, but on cucumber were slightly higher than the MRL's except alpha and beta-endosulfan. Also, statistical analysis of pesticide residues in all samples showed that most of the detected residues mean were significantly lower than the MRL's (p < 0.05). Generally, tomatoes showed the least number and level of pesticide residues by all the GC-techniques. On the other hand, strawberries showed greater number and levels of pesticide residues, particularly by the GC-MS technique. These results indicate that the protective period to elapse before harvesting should be increased especially on strawberry. The results also can help in risk assessment of consumers exposure to the expected pesticide residues.  相似文献   

16.
A graphene-based magnetic nanocomposites (G-Fe3O4 MNPs) was synthesized and used as the adsorbent for the extraction of some triazole fungicides (triadimefon, paclobutrazol, hexaconazole, myclobutanil, diniconazole, propiconazole, and tebuconazole) in cucumber, cabbage, and tomato samples prior to gas chromatography–mass spectrometry detection. Various experimental parameters affecting the extraction efficiencies, such as the amount of G-Fe3O4 MNPs, extraction time, pH and salt concentration of the sample solution, and desorption conditions were investigated. Under the optimized experimental conditions, the enrichment factors of the method for the analytes were in the range from 461 to 697. The signal response was linear in the range of 0.5–35.0 ng g?1 for all the analytes with the correlation coefficients ranging from 0.9810 to 0.9986. The limits of detection (S/N?=?3) of the method for the analytes were between 0.01 and 0.10 ng g?1. The recoveries of the method for the seven triazoles were in the range from 84.4 to 108.2 % with RSDs between 3.4 and 10.6 %.  相似文献   

17.
The fate of dinitroaniline herbicides (pendimethalin and trifluralin), organophosphous insecticides (fenitrothion and malathion), and pyrimidine (nuarimol) and triazole (myclobutanil and propiconazole) fungicides from barley to malt was determined. Several samples for residue analysis were taken after each stage of malting (steeping, germination and kilning). Pesticide residue analysis was carried out by GC/ITMS in selected ion monitoring mode. Pesticides decline along the process, although in different proportions. The carryover of residues after steeping was 45-85%. A good correlation (r > 0.92) was observed between percentages removed after steeping and the P(OW) values of pesticides. The amount remaining after malting ranged from 13 to 51% for fenitrothion and nuarimol, respectively. Steeping was the most important stage in the removal of pesticide residues (52%) followed by germination (25%), and kilning (drying and curing, 23%). During malt storage (3 months) the fall in pesticide residues was not significant. Applying the standard first-order kinetics equation (r > 0.95), the half-lives obtained for the pesticides during malt storage varied from 244 to 1533 days for myclobutanil and nuarimol, respectively.  相似文献   

18.
Many pesticides are chiral and consist of two or more enantiomers/stereoisomers, which may differ in biological activity, toxicity, effects on nontarget organisms, and environmental fate. In the last few years, several racemic compounds have been substituted by enantiomer-enriched or single-isomer compounds ("chiral switch"). In this context, the stereoselective degradation in soils is an important part of a benefit-risk evaluation, but the understanding of the environmental factors affecting the chiral preferences is limited. In this study, the stereoselective degradation of the fungicides epoxiconazole and cyproconazole was investigated in different soils, selected to cover a wide range of soil properties. The fungicides were incubated under laboratory conditions and the degradation and configurational stability of the stereoisomers were followed over time using enantioselective GC-MS with a gamma-cyclodextrin derivative as chiral selector. In alkaline and slightly acidic soils, the degradation of epoxiconazole was clearly enantioselective, whereas in more acidic soils, both enantiomers were degraded at similar rates (overall half-lives 78-184 d). The enantioselectivity, expressed as ES = (k(i) - k(j))/ (k(i) + k(j)), ranged from -0.4 in alkaline soils (faster degradation of enantiomer j) to approximately 0 in acidic soils (non-enantioselective), and showed a reasonably linear correlation with the soil pH. The four stereoisomers of cyproconazole (overall half-lives 5-223 d) were also degraded at different rates in the various soils, but only the stereoselectivities between epimers showed some correlations with pH, whereas enantioselectivities did not. Both fungicides were configurationally stable in soils, i.e., no enantiomerization or epimerization was observed. Correlations between pH and ES have previously been reported for other pesticides (metalaxyl, dichlorprop, mecoprop), but the presence or absence of such correlations is not obviously linked to the pathways of degradation. It can be assumed that different microorganisms and enzymes are involved in the primary degradation of these compounds, but on which level soil pH has an influence on ES remains to be investigated.  相似文献   

19.
Apples represent the main component of most fruit-based baby food products. Since not only fruit from organic farming, but also conventionally grown fruit is used for baby food production, the occurrence of pesticide residues in the final product is of high concern. To learn more about the fate of these hazardous compounds during processing of contaminated raw material, apples containing altogether 21 pesticide residues were used for preparation of a baby food purée both in the household and at industrial scale (in the baby food production facility). Within both studies, pesticide residues were determined in raw apples as well as in final products. Intermediate product and by-product were also analysed during the industrial process. Determination of residues was performed by a sensitive multi-detection analytical method based on liquid or gas chromatography coupled with mass spectrometry. The household procedure involved mainly the cooking of unpeeled apples, and the decrease of residues was not extensive enough for most of the studied pesticides; only residues of captan, dithianon and thiram dropped significantly (processing factors less than 0.04). On the other hand, changes in pesticide levels were substantial for all tested pesticides during apple processing in the industrial baby food production facility. The most important operation affecting the reduction of residues was removal of the by-products after pulping (rest of the peel, stem, pips etc.), while subsequent sterilisation has an insignificant effect. Also in this case, captan, dithianon and thiram were identified as pesticides with the most evident decrease of residues.  相似文献   

20.
目的 了解云南地区三七花、三七须根中丙环唑、噁霜灵、腈菌唑、醚菌酯、腐霉利、多菌灵、嘧霉胺、苯醚甲环唑、甲霜灵9种杀菌剂污染状况。方法 按照《云南省食品安全风险监测方案》中样品采集要求, 在云南8个地区采集62个样品。按照《国家食品污染物和有害因素风险监测工作手册》对多菌灵、嘧霉胺、苯醚甲环唑、甲霜灵进行检测及国家标准GB 23200.113-2018《食品安全国家标准植物源性食品中208种农药及其代谢物残留量的测定》对丙环唑、噁霜灵、腈菌唑、醚菌酯、腐霉利进行检测。结果 9种杀菌剂中, 苯醚甲环唑、嘧霉胺、甲霜灵、多菌灵超标率较高, 分别为16.1%, 14.0%, 12.9%, 4.84%。丙环唑、噁霜灵、腐霉利超标率为3.23%, 腈菌唑、醚菌酯未超标。结论 云南地区三七花、三七须根中杀菌剂污染超标率较高, 应采取措施加以控制。  相似文献   

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