Dissipation of pyrethroid residues in peppers,zucchinis, and green beans exposed to field treatments in greenhouses: evaluation by decline curves

Dissipation of seven pyrethroid insecticides under field conditions was evaluated on green beans, zucchinis, and peppers grown in experimental greenhouses (Almería, Spain). Pyrethroid residues were determined by high performance liquid chromatography using continuous on-line post-elution photoirradiation with fluorescence detection after dichloromethane extraction and cleanup on florisil phase cartridges. Mathematically defined decline curves were established by determining optimal relationships between pyrethroid residues and time. Different models were used to find these curves. The 1st-order model achieved the best adjustment to the experimental data in 42.9% of cases. The RF (root function) 1st-order model was the best in 33.3% of times. Each of the 1.5th- and 2nd-order models provided the best adjustment in a 9.5% of the cases. Finally, the RF 1.5th-order model was the most appropriate in only 4.8% of cases. Half-life times for these three vegetables were estimated from the optimal models. The preharvest intervals for the residues in these three vegetables was obtained, taking into account the maximum residue levels established by the existing legislation. They were all lower than the ones specified by the makers of commercial formulates, which ensures a safe enough consumption.     

Residue levels, decline curves, and plantation distribution of procymidone in green beans grown in greenhouse

Residue levels and degradation rates of procymidone residues were studied in green beans grown in a greenhouse. Experiments were planned to also assess the influence of planting density on the behavior of procymidone residues on this type of crop. The study was carried out in four random blocks considering three sub-blocks of different planting densities into each block. Plants were sprayed with Sumisclex 50 WP (1077.5 g of ai/ha) 52 days after the transplantation, and sampling was carried out daily during two different periods of 6 and 5 consecutive days, respectively, around the two harvest days (days 12 and 28 after the treatment). Residue levels of procymidone were determined by using the Luke extraction method and GC-NPD. The average residue levels of procymidone in the overall planting (mean of 12 determinations) were below 2 mg/kg (European maximum residue limit) for all the sampling days, obtaining values of 1.01 +/- 0.55 and 0.37 +/- 0.10 mg/kg, respectively, at the two harvest days. The decline behavior of procymidone residues in the overall plantation and in each block could be described as a pseudo-first-order reaction, obtaining half-life values (t(1/2)) of 10-11 days in all cases. The calculated residue level at the preharvest time (5 days) in the overall plantation was 1.7 mg/kg, but this value in the blocks depended on the block position along the greenhouse and ranged from 2.3 to 0.9 mg/kg. In this work, additional data on the residual behavior of the fungicide pyrazophos in green beans were also obtained.     

Pesticide residue levels in peppers grown in a greenhouse after multiple applications of pyridaben and tralomethrin

Residue levels of pyridaben and tralomethrin were determined in peppers grown in an experimental greenhouse, during a 4 week period in which up to four successive treatments with both pesticides were applied. In all cases, plants were sprayed with a mixture of pyridaben and tralomethrin at application rates of active ingredients of 140 and 36 g/ha, respectively. Sampling was carried out at 1, 3, 7, 8, 10, or 14 days after each multiple application, simulating the typical harvesting practices in greenhouse plantations. Residue levels of pyridaben and tralomethrin were determined by using ethyl acetate extraction and GC-ECD. During the study, residue levels in the plantation ranged between 0.22 and 0.04 mg/kg for pyridaben and between 0.09 and 0.02 mg/kg for tralomethrin, with median values of 0.14 and 0.06 mg/kg, respectively. These values represent 28 and 600%, respectively, of the corresponding maximum reside limits currently established in Spain. The application of an intensive washing process to the pepper samples did not lead to a significant reduction of the residue level of either pesticide. Likewise, no significant differences were found between the residue levels in the "edible" and "inedible" parts of the peppers.     

Disappearance of azoxystrobin, pyrimethanil, cyprodinil, and fludioxonil on tomatoes in a greenhouse

The disappearance of azoxystrobin, pyrimethanil, cyprodinil, and fludioxonil on tomatoes in greenhouse was studied. At the preharvest interval, except for cyprodinil, the pesticide residues were below the MRL fixed in Italy. The mechanism of disappearance studied with model systems shows that the decrease in residues was due to codistillation and photodegradation in pyrimethanil, to photodegradation in fludioxonil, and to evaporation and codistillation in cyprodinil. Azoxystrobin residues were stable during all experiments.     

Determination of bisphenol a and bisphenol B residues in canned peeled tomatoes by reversed-phase liquid chromatography

Bisphenol A (BPA) and bisphenol B (BPB) concentrations were determined in peeled canned tomatoes of different brands bought in Italian supermarkets. Tomato samples analyzed were packaged in cans coated with either epoxyphenolic lacquer or low BADGE enamel. A solid phase extraction (SPE) was performed on C-18 Strata E cartridge followed by a step on Florisil cartridge. Detection and quantitation were performed by a reversed phase high-performance liquid chromatography (RP-HPLC) method with both UV and fluorescence detection (FD). On the total of 42 tested tomato samples, BPA was detected in 22 samples (52.4%), while BPB was detected in 9 samples (21.4%). BPA and BPB were simultaneously present in 8 of the analyzed samples. The levels of BPA found in this study are much lower than the European Union migration limits of 3 mg/kg food and reasonably unable to produce a daily intake exceeding the limit of 0.05 mg/kg body weight, established by European Food Safety Authority.     

Effect of Mn on growth,modulation, and nitrogen fixation by soybeans grown in the greenhouse

Abstract

Soybean (Glycine max (L.) Merr. cv Bragg) plants were grown in the greenhouse using a low‐Mn Leefield sand amended with 0, 2.5, 5, 20 and 50 yg Mn/g. The plants were inoculated and were primarily dependent on symbiotically fixed N. Measurements of DTPA‐extractable soil Mn, soil pH, leaf tissue Mn, top weight, top N content, and nodule weight, volume and number were made at 27, 42, 56, 63 and 69 days after planting. The DTPA extrac‐tant was a good predictor of leaf tissue Mn giving a highly significant (P = 0.01) overall correlation coefficient of 0.704 for this comparison. Because of an unexpected decline in soil pH from 6.8 to 6.0 and an associated increase in DTPA‐extractable Mn from 0.14 to 0.24 yg/g during preparation and handling prior to the first harvest time, Mn in the leaf tissue of the controls was never less than 21 yg/g. Since this concentration of Mn is above the deficient level, no significant responses in top growth, nitrogen fixation or nodule measurements were obtained from the addition of low rates of Mn. The highest Mn rate was only mildly toxic in terms of top growth and top N content, producing leaf tissue having Mn concentrations ranging from 171 to 180 yg/g at the last three harvest periods.     

Effect of household processing and unit-to-unit variability of pyrifenox, pyridaben, and tralomethrin residues in tomatoes

Residue levels of pyrifenox, pyridaben, and tralomethrin were determined in unprocessed and processed tomatoes, grown in a experimental greenhouse, to evaluate the effect of three different household processes (washing, peeling, and cooking) and the "unit to unit" variability of these pesticides in tomatoes. The study was carried out on 11 greenhouse tomato samples collected during a 5 week period in which two successive treatments with the studied pesticides were applied. Residue levels in unprocessed and processed tomato samples were determined by means of ethyl acetate extraction and gas chromatography-electron capture detection determination. The washing processing factor results were 0.9 +/- 0.3 for pyridaben, 1.1 +/- 0.3 for pyrifenox, and 1.2 +/- 0.5 for tralomethrin, whereas the peeling processing factors were 0.3 +/- 0.2 for pyridaben and 0.0 +/- 0.0 for both pyrifenox and tralomethrin. The average loss of water in the tomato pure samples during the cooking process was approximately 50%; the cooking processing factors were 2.1 +/- 0.8 for pyridaben, 3.0 +/- 1.1 for pyrifenox, and 1.9 +/- 0.8 for tralomethrin. The unit-to-unit variability factors were determined on three different greenhouse samples analyzing 10 different units of unprocessed tomatoes from each sample. In all cases, the unit-to-unit variability factor results were within the range of 1.3-2.2.     

Boron nutrition and mobility,and its relation to the elemental composition of greenhouse grown root crops I. Rutabaga

Abstract

The nutrition and mobility of B, and its relation to the elemental composition of two cultivars of rutabaga (Brassica napus ssp. rapifera cv. Laurentian and Wilhelmsberger) plants were investigated in greenhouse experiments. Laurentian exhibited a greater response than Wilhelmsberger to continuing B deficiency as indicated by the severity in the roots of brown heart, of external roughness and elongation and of the decrease in B concentration. Signs of B deficiency were not found when the B contents of the root and young leaves were 27 and 56 ug g‐1 DM respectively. Root B levels of 14 and 17–20 μg g^‐1 gave moderate and slight internal signs of brown discoloration. Foliar applications of B partially restored the B concentrations of the roots; however, the mechanism of movement was unclear. The Mg, Mn and Zn contents of roots were the only elements that consistently increased and accumulated under B deficiency. The relative element composition of the root compared to the mature leaves is consistent with the root being supplied predominantly with nutrients by the phloem. Nutrient retranslocation was assessed from the ratio of element concentration in the roots or young leaves to that in the mature leaves. Although Mg, Mn and B exhibited limited mobility under adequate B nutrition they were translocated from mature leaves to younger tissues under B starvation. It is concluded that Wilheimsberger is by virtue of its greater capacity for the retranslocation of B to roots, less sensitive to B deficiency and the brown heart disorder.     

Boron nutrition and mobility,and its relation to the elemental composition of greenhouse grown root crops. II radish

Abstract

The elemental distribution between the leaves and roots of mature radish (Raphanus sativus cv Cherry Belle) plants grown in the greenhouse with various concentrations of nutrient solution B or Ca was determined to assess the role of phloem in the provision of nutrients to the root, and the retranslocation of B under deficient conditions. The relative composition and accumulation of elements in different parts, and the ratio of their concentrations in leaves:roots were used as a measure of their uptake, relative mobility and retranslocation. The data indicate that B, but not Ca is retranslocated in the phloem to the roots when that particular element was in short supply in the nutrient solution. B deficiency induced brown heart disorder in radish roots but the severity was dependent on the degree of deficiency below 28 μg g^‐l DM in the root. These symptoms were alleviated when the root B concentrations were enhanced by foliar applications of B. It is concluded that radish responded to B deficiency in a fashion similar to that reported previously for rutabaga and that it might serve as a time‐saving model system for examining the mechanisms responsible for brown heart in rutabaga.     

Effect of peach root residues,lime and supplemental nitrogen on survival and yield of peach trees in a decline area

Abstract

Supplemental N fertilization significantly increased survival and yield of Elberta peach trees growing in a severe decline area. There was a trend for supplemental N plus dolomitic lime to give further increases in tree survival and individual tree yields but did not significantly influence nutrient content of leaves. Trees did not respond to peach root residue applications.     

Gas-liquid chromatographic analysis of ethephon and fenoprop residues in apples and their decline before and after harvest.

Ethephon (2-chloroethylphosphonic acid) and fenoprop (2-(2,4,5-trichlorophenoxy) propionic acid) may be determined in the same apple sample. After extraction with methanol, 2 separate methylation procedures were required to quantitatively convert each compound. Ethephon was esterified with diazomethane and analyzed by a flame photometric detector in the P-mode. Fenoprop was esterified with boron trifluoride/methanol and analyzed by electron capture gas chromatography. Average recoveries were about 95% at 0.05 ppm for both compounds. The limit of detection was 0.05 ppm for ethephon and 0.01 ppm for fenoprop in a 1 g sample. The persistence of both compounds before and after harvest was studied. Ethephon and fenoprop were applied simultaneously to apple trees at the recommended concentrations of 300 and 20 ppm, respectively. Ethephon residues averaged 1.6, 0.75, and 0.4 ppm at 2 hr, 10 days, and after washing at 13 days, respectively. The corresponding fenoprop residues were 0.70, 0.025, and 0.024 ppm.     

Comparison of major and trace element concentrations in Danish greenhouse tomatoes (Lycopersicon esculentum Cv. Aromata F1) cultivated in different substrates

The concentration of major and trace elements was determined for tomato (Lycopersicon esculentumcv. Aromata F1) fruits grown in three different substrate systems. The systems were soil and rockwool irrigated with a normal nutrient solution and rockwool irrigated with a nutrient solution with elevated electrical conductivity (EC). At three harvest times, tomato fruits were analyzed for Ca, Cu, Fe, K, Mg, Mn, Na, P, S, Sr, and Zn by ICP-AES and for Cd, Cr, Mo, Ni, Pb, Sn, and V by HR-ICPMS. The concentrations of Ca, Cd, Fe, Mn, Mo, Na, Ni, Sr, and Zn were significantly different (p < 0.05) for tomato fruits grown on the different substrates. Between the harvest times different levels (p < 0.05) were shown for Ca, Cd, Fe, Mn Na, Ni, Sr, Zn Cu, K, Mg, P, Sn, and V. The concentration of Cd was >15 times higher and the concentration of Ca was 50-115% higher in soil-grown fruits than in rockwool-grown fruits. Principal component analysis applied on each harvest split the data into two groups. One group includes soil-grown fruits, and the other group includes rockwool-grown fruits with the two different nutrient solutions.     

Identification and synthesis of 2-heptanethiol, a new flavor compound found in bell peppers

2-Heptanethiol was identified for the first time as a constituent of red and green bell pepper extracts. The chemical structure of this new aroma compound was proposed on the basis of mass spectra and retention indices and confirmed by chemical synthesis and nuclear magnetic resonance spectroscopy measurements. Its aroma properties were described as sulfury, onion-like, and vegetable-like, reminiscent of bell pepper at lower concentrations, with an orthonasal detection threshold of 10 microg/L of water. No differences in odor note and threshold value were observed for the enantiomeric forms, which were prepared from enantiopure 2-heptanol by tosylation, followed by thioacetylation and reduction, giving the target thiol enantiomers.     

Antibiotic residues: regulations, tolerances, and detection in the European Economic Community.

The use of antimicrobial agents for growth promotion and therapy in the European Economic Community and the resulting public health problems are discussed. Methods for detection of residues based on microbiological criteria for acceptance are presented and evaluated.     

Arsenic,cadmium, and lead pollution and uptake by rice (<Emphasis Type="Italic">Oryza sativa</Emphasis> L.) grown in greenhouse

Purpose  

Hunan province is well-known for its extensive base-metal extraction and smelting industries. However, the legacies of excavation operations, transportation, and selective smelting activities within Hunan have resulted in the generation of large quantities of mine wastes, which will become the sources of metal contamination in the environment. Thus, there is an increasingly important health issue underlying the study of arable land pollution and transfer of As, Cd, and Pb in the paddy soil–rice system.     

Determination of novobiocin residues in milk, blood, and tissues by liquid chromatography

Residues of novobiocin in milk, blood, and tissues can be detected by microbiological tests but cannot be distinguished from other antibiotics. A simple liquid chromatographic (LC) method was developed for identification of residues. Tissues were blended and milk and blood serum were mixed with 0.2M NH4H2PO4. The mixture was deproteinized by adding aqueous methanol and filtering. The LC apparatus consisted of a variable wavelength detector, set at 340 nm, an automatic loop injector, and a C18 column with guard cartridge. The flow rate was 1 mL/min and the solvent mixture of 0.01M H3PO4-acetonitrile-methanol was programmed from 50 + 0 + 50 (0-1 min) to 20 + 80 + 0 (20 min). Novobiocin was concentrated directly by solid-phase extraction on the analytical column. Five or more 200 microL aliquots of the filtrate in water-methanol (1 + 1) (adjusted if necessary) were injected with the column solvent at 50 + 0 + 50. After the final injection, the program was run to completion. Recoveries were 90-100% with sensitivities of 0.05 ppm or less. The procedure should be adaptable for use with formulations and feeds.     

Gas-liquid chromatographic determination of kepone residues in finfish, shellfish, and crustaceans.

Finfish, shellfish, and crustacean samples are extracted with isopropanol and benzene; the extract is filtered and then concentrated. The extract, dissolved in hexane, is treated with oleum and extracted with aqueous alkali. The aqueous phase is acidified and extracted with petroleum ether-ethyl ether (1 + 1). The Kepone residue is determined by electron capture gas-liquid chromatography (GLC). Recoveries obtained by 8 laboratories from 15 species of finfish fortified at 0.02-0.23 ppm ranged from 37 to 107% with a mean +/- relative standard deviation of 79.4 +/- 14.5%. For oysters fortified at 0.01-0.10 ppm, recoveries range from 63 to 129% with a mean of 78.8 +/- 20.8%. For crustaceans fortified at 0.05-0.26 ppm, recoveries ranged from 52 to 110% with a mean of 78 +/- 16.4%. The approximate limits of quantitation for finfish and for shellfish and crustaceans are 0.02 and 0.05 ppm, respectively, under the GLC conditions used in this study.