An analytical method for the simultaneous determination of butachlor and benoxacor in wheat and soil

Butachlor is a chloroacetanilide herbicide successfully employed in weeding some important crops, and benoxacor is a safening compound able to induce the enzymatic mechanism of chloroacetanilide detoxification in plants. A practical method for a simultaneous detection of butachlor and benoxacor residues in wheat and in soil is described. The procedure can be performed by GC and HPLC. They were extracted with methanol and cleaned up by solid phase extraction (SPE). The analytes were satisfactorily separated via both GC and HPLC techniques, and no interferences were observed coming from plant or soil matrixes or reagents. The limit of quantitation was found to be 5.0 ng by GC and 20.0 ng by HPLC for butachlor and 2.5 ng by GC and 15.0 ng by HPLC for benoxacor. Butachlor recovery tests ranged from 85.4% to 91.7% in wheat shoots and 84.0% to 93.2% in soil; benoxacor recovery tests ranged from 86.5% to 90.8% in wheat shoots and 85.7% to 90.7% in soil. The reproducibility and the accuracy make this method a selective and sensitive tool for routine analyses.     

Predicting soil loss in central and south Italy with a single USLE-MM model

Purpose

The USLE-MM estimates event normalized plot soil loss, A_e,N, by an erosivity term given by the runoff coefficient, Q_R, times the single-storm erosion index, EI₃₀, raised to an exponent b₁?>?1. This modeling scheme is based on an expected power relationship, with an exponent greater than one, between event sediment concentration, C_e, and the EI₃₀/P_e (P_e = rainfall depth) term. In this investigation, carried out at the three experimental sites of Bagnara, Masse, and Sparacia, in Italy; the soundness of the USLE-MM scheme was tested.

Materials and methods

A total of 1192 (A_e,N, Q_REI₃₀) data pairs were used to parameterize the model both locally and considering all sites simultaneously. The performances of the fitted models were established by considering all erosive events and also by distinguishing between events of different severity.

Results and discussion

The b₁ exponent varied widely among the three sites (1.05–1.44) but using a common exponent (1.18) for these sites was possible. The A_e,N prediction accuracy increased in the passage from the smallest erosion events (A_e,N?≤?1 Mg ha^?1, median error =?3.35) to the largest ones (A_e,N?>?10 Mg ha^?1, median error =?1.72). The Q_REI₃₀ term was found to be usable to predict both A_e,N and the expected maximum uncertainty of this prediction. Soil erodibility was found to be mainly controlled by the largest erosion events.

Conclusions

Development of a single USLE-MM model appears possible. Sampling other sites is advisable to develop a single USLE-MM model for a general use.

     

Using Static and Dynamic Indicators to Evaluate Soil Physical Quality in a Sicilian Area

Both capacitive indicators derived from the water retention curve and dynamic measurements of the flow‐weighted mean pore radius, R₀, were used to assess the soil physical quality of two agricultural areas (cropland and olive orchard) and two natural areas (grassland and managed woodlot plantation) potentially subject to soil degradation. The overall idea of the study was to investigate whether a dynamic indicator quantitatively derived from hydraulic conductivity measurements could be used to supplement the traditionally applied capacitive indicators retrieved from water retention measurements. According to the available criteria, only the surface layer of the cropland site showed optimal soil physical quality. In the grassland and woodlot sites, the physical quality was deteriorated also as a consequence of compaction because of grazing. Overall, the physical quality was better in tilled than nontilled soils. The optimal soil in terms of capacitive indicators had hydraulic conductivity close to saturation that was intermediate among the different land uses, and it remained 1·3–1·9 times higher than that observed in the natural sites even when the largest pores emptied. A depth effect on R₀ was observed only when larger macropores were activated. It was suggested that water transmission parameters are more affected by changes in large pore domain. The plant available water content and Dexter's S‐index showed inverse statistically significant regressions with R₀. The empirical relationships were physically convincing given that, at increasing R₀, the contribution of macropores increases, water is transmitted faster below the root zone and the soil's ability to store water is reduced. Copyright © 2013 John Wiley & Sons, Ltd.     

Is earthworms' dispersal facilitated by the ecosystem engineering activities of conspecifics?

In this work, we documented the influence of earthworm's galleries on their speed of movements during dispersal events in the soil. We quantified, by using X-rays, the dispersal behaviour of earthworms in the soil. The observations were conducted in mesocosms in controlled conditions for 12?h. Our experiments revealed that during a dispersal sequence of a batch of individuals of the species Aporrectodea terrestris (Savigny 1826): (a) individuals used preferentially existing conspecifics' galleries, (b) individual velocity increased after each dispersal event and (c) the lag time before each dispersal event did not seem to be influenced by previous dispersers. Therefore, dispersal seems to be facilitated by conspecifics' activity, which strongly supports the hypothesis of a feedback between ecosystem engineers' activity and their dispersal speed.     

Natural occurrence of ochratoxin A and antioxidant activities of green and roasted coffees and corresponding byproducts

Ochratoxin A is an important mycotoxin that can enter the human food chain in cereals, wine, coffee, spices, beer, cocoa, dried fruits, and pork meats. Coffee is one of the most common beverages and, consequently, it has a potential risk factor for human health related to ochratoxin A exposure. In this study, coffee and corresponding byproducts from seven different geographic regions were investigated for ochratoxin A natural occurrence by HPLC-FLD, nutritional characterization, and antioxidant activities by spectrophotometric assay. The research focused on composition changes in coffee during the processing step "from field to cup". Costa Rica and Indian green coffees were the most contaminated samples, with 13 and 11 microg/kg, respectively, while the Ethiopian coffee was the least contaminated, with 3.8 microg/kg of ochratoxin A. The reduction of ochratoxin A contamination during the roasting step was comparable for any samples that were considered under the recommended level of 4 microg/kg. Total dietary fibers ranged from 58.7% for Vietnam and 48.6% for Ivory Coast in green coffees and ranged from 58.6% for Costa Rica to 61.2% for India in roasted coffee. Coffee silverskin byproduct obtained from Ivory Coast was the highest, with 69.2 and 64.2% of insoluble dietary fibers, respectively.     

Residue levels and storage decay control in Cv. Star Ruby grapefruit after dip treatments with azoxystrobin

Cv. Star Ruby grapefruit (Citrus paradisi Macf.) were subjected to a 3-min dip in water at room temperature (20 degrees C) or at 50 degrees C with or without 25, 50, or 100 mg/L azoxystrobin (AZX). Then, the fruits were subjected to cold quarantine at 2 degrees C and 90-95% relative humidity (RH) for 3 weeks and then stored for 5 weeks at 8 degrees C and approximately 85% RH and for another 2 weeks at 20 degrees C and 80% RH to simulate a 2-week marketing period (SMP). No AZX residues were detected in the albedo and pulp following treatments at 20 or 50 degrees C, the total amount of residues being recovered from the flavedo tissue. There was a relationship between the AZX uptake in fruit and the amount of fungicide employed at 20 or 50 degrees C. When AZX was applied to the fruit at 25 mg/L at 20 degrees C, the residue level averaged 0.11 mg/kg (active ingredient, whole fruit basis). This residue concentration increased by 50 and 75% when the application rate increased from 25 to 50 or 100 mg/L, respectively. A similar pattern of accumulation was detected in fruit subjected to treatments at 50 degrees C. However, treatments at 50 degrees C produced residue levels higher than the treatments at 20 degrees C, with increases ranging from 63 to 84%, for the same concentration. Storage conditions did not affect the amount of AZX residues in the fruit. Treatment at 50 or 100 mg/L at 20 degrees C reduced the incidence of moderate to severe chilling injury (CI). Water dips at 50 degrees C reduced the incidence and severity of CI to a very low extent, with no additional advantages when hot water was used in combination with AZX. Treatments with 50 or 100 mg/L of AZX at 20 degrees C produced beneficial effects in decay control similar to those of 25 mg/L AZX at 50 degrees C or hot water alone. Better results were achieved with 50 or 100 AZX at 50 degrees C, providing complete control of decay during cold storage and with negligible decay after SMP. It was concluded that when AZX was applied at 50 degrees C, low doses of fungicide and minimal residue levels in fruit were required to control the postharvest decay of grapefruit. This treatment does not impair fruit quality and offers very interesting prospects for large scale application, due to the reduced potential toxicity of AZX to nontarget organisms and to the environment.     

Free-radical-scavenging and antioxidant activities of secondary metabolites from reddened cv. Annurca apple fruits

Forty-three secondary metabolites were isolated and characterized from cv. Annurca apple fruit, an apple variety cultivated in the south of Italy. This apple cultivar undergoes a typical reddening treatment after collection. All of the compounds were characterized on the basis of their spectroscopic data. The compounds were tested for their radical-scavenging and antioxidant activities by measuring their capacity to scavenge DPPH* (2,2'-diphenyl-1-picrylhydrazyl radical), H2O2, and NO (nitric oxide) and to inhibit the formation of methyl linoleate conjugated diene hydroperoxides or TBARS (thiobarbituric acid reactive species).     

Relationship between virgin olive oil phenolic compounds and acrylamide formation in fried crisps

In this paper the relationship between virgin olive oil (VOO) phenol compounds and the formation of acrylamide in potato crisps was investigated. The phenol compositions of 20 VOO samples were screened by LC-MS, and 4 oils, characterized by different phenol compound patterns, were selected for frying experiments. Slices of potatoes were fried at 180 degrees C for 5, 10, and 15 min, and acrylamide content was determined by LC-MS. Results demonstrated that VOO phenolic compounds are not degraded during frying, and crisp color was not significantly different among the four VOOs. Acrylamide concentration in crisps increased during frying time, but the formation was faster in the oil having the lowest concentration of phenolic compounds. Moreover, the VOO having the highest concentration of ortho-diphenolic compounds is able to efficiently inhibit acrylamide formation in crisps from mild to moderate frying conditions. It was concluded that the use of ortho-diphenolic-rich VOOs can be proposed as a reliable mitigation strategy to reduce acrylamide formation in domestic deep-frying.     

High molecular weight glutenin subunits in some durum wheat cultivars investigated by means of mass spectrometric techniques

The primary structures of high molecular weight glutenin subunits (HMW-GS) of 5 Triticum durum Desf. cultivars (Simeto, Svevo, Duilio, Bronte, and Sant'Agata), largely cultivated in the south of Italy, and of 13 populations of the old spring Sicilian durum wheat landrace Timilia (Triticum durum Desf.) (accession nos. 1, 2, 3, 4, 7, 8, 9, 13, 14, 15, SG1, SG2, and SG3) were investigated using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) and reversed-phase high performance liquid chromatography/nanoelectrospray ionization mass spectrometry (RP-HPLC/nESI-MS/MS). M(r) of the intact proteins determined by MALDI mass spectrometry showed that all the 13 populations of Timilia contained the same two HMW-GS with 75.2 kDa and 86.4 kDa, whereas the other durum wheat cultivars showed the presence of the expected HMW-GS 1By8 and 1Bx7 at 75.1 kDa and 83.1 kDa, respectively. By MALDI mass spectrometry of the tryptic digestion peptides of the isolated HMW-GS of Timilia, the 1Bx and 1By subunits were identified as the NCBInr Acc. No AAQ93629, and AAQ93633, respectively. Sequence verification for HMW-GS 1Bx and 1By both in Simeto and Timilia was obtained by MALDI mass mapping and HPLC/nESI-MSMS of the tryptic peptides. The Bx subunit of Timila presents a sequence similarity of 96% with respect to Simeto, with differences in the insertion of 3 peptides of 5, 9, and 15 amino acids, for a total insertion of 29 amino acids and 25 amino acid substitutions. These differences in the amino acidic sequence account for the determined Δm of 3294 Da between the M(r) of the 1Bx subunits in Timilia and Simeto. Sequence alignment between the two By subunits shows 10 amino acid substitutions and is consistent with the Δm of 148 Da found in the MALDI mass spectra of the intact subunits.     

Chemical characterization and antioxidant properties of coffee melanoidins

Melanoidins, the brown polymers formed through Maillard reaction during coffee roasting, constitute up to 25% of the coffee beverages' dry matter. In this study chemical characterization of melanoidins obtained from light-, medium-, and dark-roasted coffee beans, manufactured from the same starting material, was performed. Melanoidins were separated by gel filtration chromatography and studied by MALDI-TOF mass spectrometry. Results showed that the amount of melanoidins present in the brews increased as the intensity of the thermal treatment increased, while their molecular weight decreased. The antioxidant activity of melanoidins isolated from the different brews was studied by using different methodologies. Melanoidins antiradical activity determined by ABTS(*)(+) and DMPD(*)(+) assays decreased as the intensity of roasting increased, but the ability to prevent linoleic acid peroxidation was higher in the dark-roasted samples. Data suggest that melanoidins must be carefully considered when the relevance of coffee intake in human health is studied.