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1.
The antioxidant activity of wines obtained from grapes treated with six fungicides (famoxadone, fenhexamid, fluquinconazole, kresoxim-methyl, quinoxyfen and trifloxystrobin) was investigated. Two field trials in triplicate were carried out for each formulation of the fungicide at the recommended dose of the manufacturer. The first trial was carried out under good agricultural practices (GAP), following the recommended pre-harvest interval, and the second one under critical agricultural practices (CAP) that involves treating the same field just before the harvest. The residue levels were determined by gas and liquid chromatography coupled to mass detectors (GC-MS and LC-MS). The antioxidant activity was determined in the wines obtained from the thirteen trials including one control, six from treated grapes obeying the pre-harvest interval, and six from grapes treated at the day of harvest or at most unfavorable conditions. Elimination of 40–100% of the initial fungicide residues present in grapes was observed during the wine-making process. It can be inferred from the results that the use of these fungicides did not produce any decrease of the antioxidant activity in the wines (7.19 ± 0.22 mmol Trolox/L for the blank wine versus a range of 6.45 ± 0.82 mmol Trolox/L to 10.06 ± 0.59 mmol Trolox/L for the treated wines) at the pre-harvest interval and most unfavorable conditions. Nevertheless, the presence of famoxadone, kresoxim-methyl and quinoxyfen increased the antioxidant activity and this was directly related to their residue levels in the grapes. Also, the wine phenolic composition was altered in variable intensity by the presence of the fungicide residues.  相似文献   

2.
The persistence and dissipation kinetics of trifloxystrobin and tebuconazole on onion were studied after application of their combination formulation at a standard and double dose of 75 + 150 and 150 + 300 g a.i. ha?1. The fungicides were extracted with acetone, cleaned-up using activated charcoal (trifloxystrobin) and neutral alumina (tebuconazole). Analysis was carried out by gas chromatograph (GC) and confirmed by gas chromatograph mass spectrometry (GC-MS). The recovery was above 80% and limit of quantification (LOQ) 0.05 mg kg?1 for both fungicides. Initial residue deposits of trifloxystrobin were 0.68 and 1.01 mg kg?1 and tebuconazole 0.673 and 1.95 mg kg?1 from standard and double dose treatments, respectively. Dissipation of the fungicides followed first-order kinetics and the half life of degradation was 6–6.6 days. Matured onion bulb (and field soil) harvested after 30 days was free from fungicide residues. These findings suggest recommended safe pre-harvest interval (PHI) of 14 and 25 days for spring onion consumption after treatment of Nativo 75 WG at the standard and double doses, respectively. Matured onion bulbs at harvest were free from fungicide residues.  相似文献   

3.
The effects of six clarification agents [egg albumin, blood albumin, bentonite + gelatine, charcoal, polyvinylpolypyrrolidine (PVPP) and silica gel] on the removal of residues of three fungicides (famoxadone, fluquinconazole and trifloxystrobin) applied directly to a racked red wine, elaborated from Monastrell variety grapes from the D.O. Region of Jumilla (Murcia, Spain) were studied. The clarified wines were filtered with 0.45 μ m nylon filters to determine the influence of this winemaking process in the disappearance of fungicide residues. Analytical determination of fluquinconazole and trifloxystrobin was performed by gas chromatography with electron captor detector (ECD), while that of famoxadone using an HPLC equipped with a diode array detector (DAD). Generally, trifloxystrobin is the fungicide that is the lowest persistent one in wines, except in the egg albumin study whereas, the most persistent one is fluquinconazole. The elimination depends on the nature of the active ingredient, though the water stability in the presence of light within it has more influence than the solubility and polarity of the product itself. The most effective clarifying agents were the charcoal and PVPP. The silica gel and bentonite plus gelatine were not enough to reduce considerably the residual contents in the wine clarified with them. In general terms, filtration is not an effective step in the elimination of wine residues. The greatest removal after filtration is obtained in wines clarified with egg albumine and bentonite plus gelatine, and the lowest in those clarified with PVPP.  相似文献   

4.
The effects of six clarification agents [egg albumin, blood albumin, bentonite + gelatine, charcoal, polyvinylpolypyrrolidine (PVPP) and silica gel] on the removal of residues of three fungicides (famoxadone, fluquinconazole and trifloxystrobin) applied directly to a racked red wine, elaborated from Monastrell variety grapes from the D.O. Region of Jumilla (Murcia, Spain) were studied. The clarified wines were filtered with 0.45 microm nylon filters to determine the influence of this winemaking process in the disappearance of fungicide residues. Analytical determination of fluquinconazole and trifloxystrobin was performed by gas chromatography with electron captor detector (ECD), while that of famoxadone using an HPLC equipped with a diode array detector (DAD). Generally, trifloxystrobin is the fungicide that is the lowest persistent one in wines, except in the egg albumin study whereas, the most persistent one is fluquinconazole. The elimination depends on the nature of the active ingredient, though the water stability in the presence of light within it has more influence than the solubility and polarity of the product itself. The most effective clarifying agents were the charcoal and PVPP. The silica gel and bentonite plus gelatine were not enough to reduce considerably the residual contents in the wine clarified with them. In general terms, filtration is not an effective step in the elimination of wine residues. The greatest removal after filtration is obtained in wines clarified with egg albumine and bentonite plus gelatine, and the lowest in those clarified with PVPP.  相似文献   

5.
Contaminants belonging to various classes, as polychlorobiphenyls, polycyclic aromatic hydrocarbons, organochlorine pesticides, organophosphorous pesticides, pyrethroid insecticides, fungicides, herbicides, synergists, carbamates, acaricides and insect growth regulators were simultaneously analysed by GC-MS/MS in 118 Italian and Tunisian culinary herbs and spices. The results obtained in Italian samples shown that laurel samples were the most contaminated with the presence of 15 residues on 140, whereas in rosemary (max value of 35?ng/g for cis-chlorfenyvinphos) and oregano (max value of 118.16?ng/g for ethion) some occasional residues can be observed, but always lower than the maximum residue levels; all the others samples shown no contamination. Among Tunisian samples, only rosemary contains a notably high content of pollutants exceeded the EU maximum residue limits (i.e., alachlor and phosalone with level of 359.2 and 43.3?ng/g, respectively), while oregano was determined to be free of contaminant residues. Considering the comparison among the different organic pollutants in Italian and Tunisian spices and herbs evaluated and the differences observed in this study a harmonization of regulation on contaminant residues in herbs and spices for human consumption should be needed, considering their increased use in diet and cooking.  相似文献   

6.
This investigation was undertaken to determine whether active ingredients (AIs) of currently recommended plant protection products (PPPs) could be transferred to beehives from apple and pear trees. A field trial was carried out with apple trees of Ligol and Idared variety, and pear trees of Conference variety. For pest and diseases control of fungal origin, recommended PPPs were applied. Samples of flowers from the above-mentioned varieties of fruit trees, of bees, brood and honey from beehives located in their direct neighborhood were collected regularly and analyzed for the presence of lambda-cyhalothrin (an insecticide) and cyprodinil, captan, fluopyram, kresoxim-methyl, penthiopyrad and trifloxystrobin (fungicides). In samples of flowers of Ligol variety, fluopyram residues (on average 0.621 µg single flower?1) were at the highest levels, whereas in samples of pear flowers of Conference variety, and in flowers of Idared variety, captan residues (on average, respectively, 0.705 and 165.7 µg single flower?1). In samples of bees and honey, residues of five AIs were detected, and in brood six AIs, whereby in each case captan residues prevailed, respectively, up to 585.2, 51.52 and 126.5 µg kg?1 bees and honey. In the honey, significantly larger residues of captan were found out than maximum residue level (MRL) for this AI – 103.04% MRL. In the case of any AI, the daily intake did not exceed 0.002% acceptable daily intake (ADI).  相似文献   

7.
This study aimed to investigate the residues, kinetics and dissipation patterns of kresoxim-methyl, (E)-methoxyimino[α-(o-tolyloxy)-o-tolyl]acetate, and trifloxystrobin, methyl(E)-methoxyimino-{(E)-α[1-(α,α,α-trifluoro-m-tolyl)ethylideneaminooxy]-o-tolyl}acetate”. A simple and sensitive liquid chromatography-ultraviolet detection (LC-UV) method combined with the ‘Quick Easy Cheap Effective Rugged and Safe' (QuEChERS) protocol was developed to quantify the levels of kresoxim-methyl and trifloxystrobin residues in citrus. More than 97% of the kresoxim-methyl and trifloxystrobin deposists gradually dissipated from the citrus peels within 15 days. The half-lives of kresoxim-methyl and trifloxystrobin in the peels were in the ranges of 2.63–2.66 d and 3.12–3.15 d, respectively, and the pattern of decline in the peels followed first-order kinetics. The kresoxim-methyl and trifloxystrobin residues in the pulp dissipated below the detectable level of 0.01 mg kg?1 after 9 days. Kresoxim-methyl and trifloxystrobin were easily decomposed (T1/2 < 30 d), and the observed dissipation patterns could support the application of these two fungicides in the postharvest storage of citrus fruits.  相似文献   

8.
Flubendiamide is a new insecticide that has been found to give excellent control of lepidopterous pests of tomato. This study has been undertaken to develop an improved method for analysis of flubendiamide and its metabolite des-iodo flubendiamide and determine residue retention in tomato and soil. The analytical method developed involved extraction of flubendiamide and its metabolite des-iodo flubendiamide with acetonitrile, liquid-liquid partitioning into hexane-ethyl acetate mixture (6:4, v v?1) and cleanup with activated neutral alumina. Finally the residues were dissolved in gradient high pressure liquid chromatography (HPLC) grade acetonitrile for analysis by HPLC. The mobile phase, acetonitrile-water at 60:40 (v v?1) proportion and the wavelength of 235 nm gave maximum peak resolution. Using the above method and HPLC parameters described, nearly 100 % recovery of both insecticides were obtained. There was no matrix interference and the limit of quantification (LOQ) of the method was 0.01 mg kg?1. Initial residue deposits of flubendiamide on field-treated tomato from treatments @ 48 and 96 g active ingredient hectare?1 were 0.83 and 1.68 mg kg?1, respectively. The residues of flubendiamide dissipated at the half-life of 3.9 and 4.4 days from treatments @ 48 and 96 g a.i. ha?1, respectively and persisted for 15 days from both the treatments. Des-iodo flubendiamide was not detected in tomato fruits at any time during the study period. Residues of flubendiamide and des-iodo flubendiamide in soil from treatment @ 48 and 96 g a.i. ha?1 were below detectable level (BDL, < 0.01 mg kg?1) after 20 days. Flubendiamide completely dissipated from tomato within 20 days when the 480 SC formulation was applied at doses recommended for protection against lepidopterous pests.  相似文献   

9.
To estimate the variability of pesticide residue levels present in cauliflower units, a total of 142 samples were collected from a field trial of a cooperative farmer, and 120 samples were collected from different market places in Thessaloniki, Greece. The collected samples were extracted using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction technique, and the residues were determined by liquid chromatography–tandem mass spectrometry. The developed method was validated by evaluating the accuracy, precision, linearity, limit of detection (LOD), and limit of quantification (LOQ). The average recoveries for all the analytes, derived from the data of control samples fortified at 0.01, 0.05, 0.1, and 0.2 mg/kg, ranged from 74 to 110% with a relative standard deviation of ≤8%. The correlation coefficient (R2) was ≥0.997 for all the analytes using matrix-matched calibration standards. The LOD values ranged from 0.001 to 0.003 mg/kg, and the LOQ was determined at 0.01 mg/kg for all the sought analytes. The matrix effect was found to be at a considerable level, especially for cypermethrin and deltamethrin, amounting to +90% and +145%, respectively. For the field samples, the unit-to-unit variability factors (VFs) calculated for cypermethrin and deltamethrin were 2.38 and 2.32, respectively, while the average VF for the market basket samples was 5.11. In the market basket samples, residues of cypermethrin, deltamethrin, chlorpyrifos, and indoxacarb were found at levels ≥LOQ and their respective VFs were 7.12, 5.67, 5.28, and 2.40.  相似文献   

10.
A granular formulation of terbufos (Counter 15G) was added in-furrow at time of planting of wheat and barley. Foliage collected at several times was analyzed for total terbufos residues as terbufoxon sulfone. Maximum residues from application of 1.5 and 3.0 kg/ha were 7.4 and 10.6 ppm, respectively, in wheat foliage samples collected 10 days postseeding. Wheat foliage collected at 53 days postseeding had residues averaging 0.32 and 0.58 ppm from the 1.5 and 3.0 kg/ha applications, respectively. In 1985 residues in barley were consistently less than in wheat in 1985 with 4.4 and 7.0 ppm detected in foliage collected 10 days post application from the 1.5 and 3.0 kg/ha applications, respectively and 0.21 and 0.34 ppm detected at 53 days. Grain samples had 0.01 ppm or less residue at harvest. Straw samples had up to 0.75 ppm total terbufos residues at harvest.  相似文献   

11.
This investigation was undertaken to compare the dissipation pattern of flubendiamide in capsicum fruits under poly-house and open field after giving spray applications at the recommended and double doses of 48 g a.i. ha?1 and 96 g a.i. ha?1. Extraction and purification of capsicum fruit samples were carried out by the QuEChERS method. Residues of flubendiamide and its metabolite, des-iodo flubendiamide, were analyzed by high-performance liquid chromatography–photodiode array, and confirmed by liquid chromatography–mass spectrometry/mass spectrometry. Limit of quantification of the method was 0.05 mg kg?1, and recovery of the insecticides was in the range of 89.6–104.3%, with relative standard deviation being 4.5–11.5%. The measurement uncertainty of the analytical method was in the range of 10.7–15.7%. Initial residue deposits of flubendiamide on capsicum fruits grown under poly-house conditions were (0.977 and 1.834 mg kg?1) higher than that grown in the field (0.665 and 1.545 mg kg?1). Flubendiamide residues persisted for 15 days in field-grown and for 25 days in poly-house-grown capsicum fruits. The residues were degraded with the half-lives of 4.3–4.7 and 5.6–6.6 days in field and poly-house respectively. Des-iodo flubendiamide was not detected in capsicum fruits or soil. The residues of flubendiamide degraded to below the maximum residue limit notified by Codex Alimentarius Commission (FAO/WHO) after 1 and 6 days in open field, and 3 and 10 days in poly-house. The results of the study indicated that flubendiamide applied to capsicum under controlled environmental conditions required longer pre-harvest interval to allow its residues to dissipate to the safe level.  相似文献   

12.
Polycyclic musks (HHCB, AHTN, ADBI, AHDI, ATII) and a metabolite of HHCB (HHCB-lactone) were analyzed in sewage sludge samples within the framework of a monitoring network in Switzerland. Mean values in stabilised sludge from 16 wastewater treatment plants were 20.3 mg/kg d.m. for HHCB, 7.3 mg/kg d.m. for AHTN and 1.8 mg/kg d.m. for HHCB-lactone, respectively. Contents of ADBI, AHDI and ATII were between 0.1 and 1.8 g/kg d.m. The results show that polycyclic musks origin mainly from private households and that loads from craft industry, industry and atmospheric deposition are negligible. The technology of wastewater treatment and sludge processing seems to be of minor importance for degradation processes of polycyclic musks. The calculated input in wastewater of polycyclic musks is lower by a factor of 5-7 than the estimates based on use volumes. This discrepancy might be explained by degradation processes, other emission pathways than wastewater or inappropriate estimation of production volumes.  相似文献   

13.
Residues of chlorantraniliprole in rice field ecosystem   总被引:4,自引:0,他引:4  
Zhang JM  Chai WG  Wu YL 《Chemosphere》2012,87(2):132-136
The fate of chlorantraniliprole was studied in rice field ecosystem, and a simple and reliable analytical method was developed for determination of chlorantraniliprole in soil, rice straw, paddy water and brown rice. Chlorantraniliprole residues were extracted from samples with acetonitrile. The extract was cleaned up with QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method, and determined by high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The average recoveries were 76.9-82.4% from soil, 83.6-89.3% from rice straw, 95.2-103.1% from paddy water and 84.9-87.7% from brown rice. The relative standard deviation was less than 15%. The limits of detection (LODs) of chlorantraniliprole calculated as a sample concentration (S/N ratio of 3) were 0.012 μg L(-1) for paddy water, 0.15 μg kg(-1) for soil, brown rice and rice straw. The results of the kinetics study of chlorantraniliprole residue showed that chlorantraniliprole degradation in soil, water and rice straw coincided with C=0.01939e(-0.0434t), C=0.01425e(-0.8111t), and C=1.171e(-0.198t), respectively; the half-lives were about 16.0 d, 0.85 d and 3.50 d, respectively. The degradation rate of chlorantraniliprole in water was the fastest, followed by rice straw. The final residues of chlorantraniliprole on brown rice were lower than maximum residue limit (MRL) of 0.02 mg kg(-1) after 14 d Pre-Harvest Interval (PHI). Therefore, a dosage of 150 mL a.i.hm(-2) was recommended, which could be considered as safe to human beings and animals.  相似文献   

14.
The impact of fungicides triadimefon and propiconazole on soil bacterial populations from a strawberry field was investigated. Two fungicides were applied to the soil at concentrations of 10 mg/kg or 100 mg/kg with soil water contents 20.2% (fresh soil water content) or 26.0% (field capacity). Changes in bacterial communities were assessed using DNA extraction, polymerase chain reaction (PCR) amplification of the 16S rDNA and denaturing gradient gel electrophoresis (DGGE). High performance liquid chromatography (HPLC) was utilized to detect the residue of fungicides in soils. The results showed that propiconazole was more persistent than triadimefon in soils, and the two soil water contents did not cause significant differences in dissipation rates between the two fungicides. A high concentration of propiconazole could inhibit the existence of soil microbes while one of triadimefon might induce the microbial population in the first stage. From unweighted pair-group method using arithmetic averages (UPGMA) dendrograms, the effect of triadimefon and propiconazole at the two applied concentrations on a soil bacterial community could be long term. After triadimefon was applied for 60 days and propiconazole for 75 days, the compositions of microbial communities were not recovered. From the viewpoint of environmental protection, it was of significant importance to pay more attention not only to the residues of pesticide but also to the change in soil microbial communities.  相似文献   

15.
This paper describes the determination of 3,5-DCA in commercial composts, a common metabolite in a class of fungicides, and dicarboximides (Vinclozolin, Chlozolinate, Iprodione, Procymidone) which are commonly used in agriculture. The extracts, obtained in acetonitrile by sonication, are analysed by HPLC/DAD without clean-up. This method has shown several advantages: reduced manipulation of samples, good recovery (80-90%) and good reproducibility (RSD% <7). The limit of detection (DL) of the analytical method has been estimated as 15 microg/kg for the common metabolite, and 35-145 microg/kg for the four fungicides in the matrices.  相似文献   

16.
A method using liquid chromatography and a single mix-mode solid-phase extraction cleanup for the simultaneous analysis of thiabendazole [2-(1,3-thiazol-4-yl)-1H-benzoimidazole], carbendazim [(methyl N-(1H-benzoimidazol-2-yl)-carbamate)] and 2-aminobenzimidazole (1H-benzimidazol-2-amine) in concentrated fruit juices is described. The three fungicides were isolated from the samples and concentrated by solid-phase extraction on Oasis MCX cartridges. The determination was performed by liquid chromatography with a diode array, detecting at 288 nm. In this method, the average recoveries from blank control juice samples spiked in a concentration range of 0.01–0.10 mg/kg were in the range of 81–95%, with relative standard deviations below 8%. Detection limits and limits of quantification were 4 μ g/kg and 10 μ g/kg, respectively, for each fungicide. Real juice samples were analyzed by the proposed method. The results were compared to those from liquid chromatography-tandem mass spectrometry.  相似文献   

17.
Determination of acaricide residues of flumethrin, tau-fluvalinate, coumaphos, and amitraz in honey and beeswax was carried out using a rapid extraction method utilizing C-18 SPE cartridges and an analytical method utilizing GC with ECD, NPD, and MSD detectors for the four acaricides. Recovery percentages from the extraction method ranged from 90-102%, while the minimum detection levels ranged from 0.01-0.05 mg/kg for the acaricides. Nine of the 21 analyzed samples were found to be contaminated with the acaricides tau-fluvalinate and coumaphos. Neither flumethrin nor amitraz was detected in any of the honey or wax samples. Coumaphos was found only in honey samples in which two samples exceeded the tolerance levels set by EPA and EC regulations. It has not been detected in beeswax. Five honey samples and eight beeswax samples were found to be contaminated with tau-fluvalinate. One of the wax samples was contaminated with a relatively high residue of tau-fluvalinate and contained above 10 mg/kg.  相似文献   

18.
Trichoderma species, the causal agents of green mould disease, induce great losses in Agaricus bisporus farms. Fungicides are widely used to control mushroom diseases although green mould control is encumbered with difficulties. The aims of this study were, therefore, to research in vitro toxicity of several commercial fungicides to Trichoderma isolates originating from Serbian and Bosnia-Herzegovina farms, and to evaluate the effects of pH and light on their growth. The majority of isolates demonstrated optimal growth at pH 5.0, and the rest at pH 6.0. A few isolates also grew well at pH 7. The weakest mycelial growth was noted at pH 8.0–9.0. Generally, light had an inhibitory effect on the growth of tested isolates. The isolates showed the highest susceptibility to chlorothalonil and carbendazim (ED50 less than 1 mg L?1), and were less sensitive to iprodione (ED50 ranged 0.84–6.72 mg L?1), weakly resistant to thiophanate-methyl (ED50 = 3.75–24.13 mg L?1), and resistant to trifloxystrobin (ED50 = 10.25–178.23 mg L?1). Considering the toxicity of fungicides to A. bisporus, carbendazim showed the best selective toxicity (0.02), iprodione and chlorothalonil moderate (0.16), and thiophanate-methyl the lowest (1.24), while trifloxystrobin toxicity to A. bisporus was not tested because of its inefficiency against Trichoderma isolates.  相似文献   

19.
In the present study, a new sensitive and simple kinetic-spectrophotometric method for the determination of the insecticide diflubenzuron [1-(4-chlorophenyl)-3-(2,6-diflubenzoil)urea] is proposed. The method is based on the inhibited effect of diflubenzuron on the oxidation of sulphanilic acid (SA) by hydrogen peroxide in phosphate buffer in presence Cu(II) ion. Diflubenzuron was determined with linear calibration graph in the interval from 0.31 to 3.1 μg mL?1 and from 3.1 to 31.0 μg mL?1. The optimized conditions yielded a theoretical detection limit of 0.18 μg mL?1 corresponding to 0.036 mg kg(-1)mushroom sample based on the 3S(b) criterion. The RSD is 5.03-1.83 % and 2.81-0.71 % for the concentration interval of diflubenzuron 0.31-3.1 μg mL?1 and 3.1-31.0 μg mL?1, respectively. The reaction was followed spectrophotometrically at 370 nm. The kinetic parameters of the reaction are reported, and the rate equations are suggested. The developed procedure was successfully applied to the rapid determination of diflubenzuron in spiked mushroom samples of different mushroom species. The HPLC method was used like a comparative method to verify results.  相似文献   

20.
Levels of eggshell thinning, and organochlorine residues in egg contents, blood plasma of adults and juveniles, tissue samples, and prey species were determined for a population of migratory Peregrine Falcons (Falco peregrinus tundrius) breeding in the Canadian Arctic. Temporal trends were assessed by comparing data collected during 1991-1994, with data from 1982-1986, for the same population. Shells (n=54) from 1991-1994 averaged 15% thinner than eggs produced prior to the introduction of DDT. No improvement in shell thickness was detected between decades. Mean DDE residue levels in eggs showed a decline from 7.6 mg kg (1982-1986) to 4.5 mg kg (1991-1994), but there was no significant change in SigmaPCB residues. Moreover, the proportion of clutches with eggs exceeding critical SigmaPCB, DDE, and dieldrin residue levels (10%) did not change between decades. Relative to Greenland and Alaskan populations, F. p. tundrius at Rankin Inlet show high levels of organochlorine contamination and little reduction in residues over the last decade. These Tundra Peregrines continue to be exposed to organochlorines in Latin America; however, results also link relatively high levels in the study population with waterfowl species that do not leave Canada in winter.  相似文献   

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