Searching the most appropriate sample pretreatment for the elemental analysis of wines by inductively coupled plasma-based techniques

Different sample preparation methods were evaluated for the simultaneous multielement analysis of wine samples by inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). Microwave-assisted digestion in closed vessel, thermal digestion in open reactor, and direct sample dilution were considered for the determination of Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Y, Mo, Cd, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Tl, Pb, and Bi in 12 samples of red wine from Valencia and Utiel-Requena protected designation of origin. ICP-MS allows the determination of 17 elements in most of the samples, and using ICP-OES, a maximum of 15 elements were determined. On comparing the sample pretreatment methodology, it can be concluded that the three assayed procedures provide comparable results for the concentration of Li, Na, Mg, Al, K, Ca, Mn, Fe, Zn, and Sr by ICP-OES. Furthermore, ICP-MS data found for Cu, Pb, and Ba were comparable. Digestion treatment provides comparable values using both total decomposition in open system and microwave-assisted treatment for Cu by ICP-OES and for Cr, Ni, and Zn by ICP-MS. Open vessel total digestion provides excess values for Cr, Mn, Fe, and Zn by ICP-OES and defect values for Se. However, direct measurement of diluted wine samples provided uncomparable results with the digestion treatment for Mn, Cu, Pb, Zn, Ba, and Bi by ICP-OES and for Mg, Cr, Fe, Ni, and Zn by ICP-MS. Therefore, it can be concluded that microwave-assisted digestion is the pretreatment procedure of choice for elemental analysis of wine by ICP-based techniques.     

Evaluation of the sorption process for imidacloprid and diuron in eight agricultural soils from southern Europe using various kinetic models

Kinetic studies are of great concern for understanding the processes and parameters involved in the sorption of pollutants by soils. Sorption kinetics of imidacloprid and diuron in eight soils of different characteristics, with very low organic carbon content were investigated. Pseudosecond-order kinetic reactions closely correlate with the experimental kinetic (R(2) > 0.98) in all soils. The sorbed amount of diuron was higher than that for imidacloprid. The low OC content of these soils correlated neither with the sorbed amount nor with the kinetic parameters for both pesticides. Imidacloprid sorption was correlated with silt and sand content and cation exchange capacity (CEC); meanwhile for diuron, no correlation was found. Thus, sorption kinetics take place throughout different mechanisms related mainly to the chemical character of the pesticides. Sorption kinetic parameters determined using three of the four models selected (pseudosecond-order kinetic reactions, Elovich equation, and Weber-Morris models) have been shown to be worthy to distinguish the process controlling the sorption kinetic of both pesticides.     

Stir bar sorptive extraction combined with GC-MS analysis and chemometric methods for the classification of South African Wines according to the volatile composition

A simple method for the analysis of major wine volatiles and semivolatiles by stir bar sorptive extraction in combination with thermal desorption and gas chromatography-mass spectrometry (SBSE-TD-GC-MS) was developed. Significant experimental parameters such as extraction time, temperature, salt addition, pH, and thermal desorption parameters were optimized to provide a sensitive and robust analytical method. The method provided good repeatability (%RSD < 10%) for 38 major wine volatile compounds, including alcohols, acids, esters, phenols, aldehydes, ketones, and lactones. Quantitative data for 62 South African red and white wines were used to study the suitability of major volatile data for the differentiation of wine samples according to grape variety or cultivar. Principal component analysis (PCA) and cluster analysis (CA) showed that most of the variation in volatile composition between wine samples could be ascribed to differences in wine age, wood contact, and fermentation practices. Despite the contribution of these factors, discriminant analysis (DA) was successfully applied to the classification of red and white wine samples according to cultivar.     

Study of some physicochemical and functional properties of quinoa (chenopodium quinoa willd) protein isolates

The amino acid composition and the physicochemical and functional properties of quinoa protein isolates were evaluated. Protein isolates were prepared from quinoa seed by alkaline solubilization (at pH 9, called Q9, and at pH 11, called Q11) followed by isoelectric precipitation and spray drying. Q9 and Q11 had high levels of essential amino acids, with high levels of lysine. Both isolates showed similar patterns in native/SDS-PAGE and SEM. The pH effect on fluorescence measurements showed decreasing fluorescence intensity and a shift in the maximum of emission of both isolates. Q9 showed an endotherm with a denaturation temperature of 98.1 degrees C and a denaturation enthalpy of 12.7 J/g, while Q11 showed no endotherm. The protein solubility of Q11 was lower than that of Q9 at pH above 5.0 but similar at the pH range 3.0-4.0. The water holding capacity (WHC) was similar in both isolates and was not affected by pH. The water imbibing capacity (WIC) was double for Q11 (3.5 mL of water/g isolate). Analysis of DSC, fluorescence, and solubility data suggests that there is apparently denaturation due to pH. Some differences were found that could be attributed to the extreme pH treatments in protein isolates and the nature of quinoa proteins. Q9 and Q11 can be used as a valuable source of nutrition for infants and children. Q9 may be used as an ingredient in nutritive beverages, and Q11 may be used as an ingredient in sauces, sausages, and soups.     

A Greener UV and Peroxide-Based Chemical Oxygen Demand Test

Water quality assessment typically includes the determination of chemical oxygen demand (COD) by oxidation of organic matter with Cr(VI) in an acidic medium followed by digestion. Unfortunately, the required reagents are harmful and the reaction times are rather long. We investigated earlier the use of H₂O₂ as a more environmentally friendly oxidizing agent to replace the hazardous chromates. In the present study, we have furthered this possibility by incorporating the use of H₂O₂ in the presence of UV light. A protocol has been devised and tested with standards and real samples that replaces toxic Cr(VI), halves the amount of silver sulfate required, and greatly reduces the necessary reaction time, thus yielding a faster and more environmentally sound method.     

Weed abundance and soil seedbank responses to tillage systems in continuous maize crops

Weed abundance in crops undergoes frequent changes, often due to changes in tillage practices. Annual species, with quick germination, a short vegetative stage, profuse seed production and long-lived seeds become problematic under zero-tillage systems. Portulaca oleracea L. and Amaranthus blitoides L. are widespread weeds in the Mediterranean area, prominent in irrigated crops. We studied the total weed abundance in the field, and specifically these two species (Portulaca oleracea and Amaranthus blitoides) with high frequency of occurrence in monoculture maize, from 2012 to 2014, in the field and soil seedbank. Results showed significant differences between zero-tillage (ZT) and conventional tillage (CT) systems on total weed abundance and relative abundance of Portulaca oleracea. Total weed abundance decreased in ZT plots (from 136 plants m^?2 to 25 and 46 plants m^?2, in 2013 and 2014 respectively). The same trend was observed in Portulaca oleracea recorded in ZT plots, but the abundance of Amaranthus blitoides did not vary in this system. Weed seedling germination and weed seed numbers both of total weed seedbank and Portulaca oleracea, were greater in ZT plots compared to CT, regarding Amaranthus blitoides seedling germination and seed count, the values did not increase with ZT, in continuous maize crops.     

Fate of phosphorus in soil during a long‐term fertilization experiment in Finland

Accumulation and depletion of soil phosphorus (P) was studied in a long‐term (37 y) field experiment in Southern Finland. The loam soil had a high pH (7.5–7.7) due to an earlier liming. Spring barley, spring wheat, oat, and ryegrass, grown in rotation, were annually fertilized with 0, 32, or 67 kg P ha^?1 y^?1 (P₀, P₁, and P₂K) and sufficient N. The average dry matter grain yield 2,600 kg ha^?1 of the P₀ plots increased by about 500 kg ha^?1 at P₁ treatment and another 600 kg ha^?1 by P₂K. Soil samples were collected in 1978 (beginning), 1995, 2005, and 2015. According to the Chang and Jackson sequential extraction, the P₂K and P₁ treatments increased the inorganic soil P by 732 and 32 kg P ha ^?1 in 37 years, respectively, while the P₀ plots were depleted by –459 kg P ha ^?1. The P₂K treatment increased all four P fractions, extracted with NH₄Cl (easily soluble), NH₄F (Al‐P), NaOH (Fe‐P), and H₂SO₄ (Ca‐P). Continuous depletion (P₀) decreased the NH₄Cl‐P and NH₄F‐P pools, NaOH‐P and H₂SO₄‐P pools remaining stable. None of the P pools changed significantly at P₁. The remarkable gap between the measured change and the balance for the P₂K and P₁ treatments cannot be explained solely by lateral soil movement, meaning that a significant proportion of the applied P was lost either in surface runoff or transported below the investigated depth of 40 cm. Despite large P applications, the degree of P saturation reached only 20% in the P₂K topsoil, assuming a 50% reactivity of Fe and Al oxides. As derived from sorption isotherms, a high EPC₀ (i.e., equilibrium P concentration at zero net P sorption or desorption) of 1.30 mg L^?1 had been built up in the P₂K treatment, while in the P₁ treatment EPC₀ (0.33 mg L^?1) had remained unchanged and P depletion (P₀) had caused a decrease to 0.12 mg L^?1. These results demonstrate that P sorption and desorption properties respond strongly to both P fertilization and null fertilization treatments and that in a long‐term field experiment only a low proportion of the residual fertilizer P can be recovered from soil.     

Irrigation scheduling of plastic greenhouse vegetable crops based on historical weather data

Irrigation scheduling based on the daily historical crop evapotranspiration (ET_h) data was theoretically and experimentally assessed for the major soil-grown greenhouse horticultural crops on the Almería coast in order to improve irrigation efficiency. Overall, the simulated seasonal ET_h values for different crop cycles from 41 greenhouses were not significantly different from the corresponding values of real-time crop evapotranspiration (ET_c). Additionally, for the main greenhouse crops on the Almería coast, the simulated values of the maximum cumulative soil water deficit in each of the 15 consecutive growth cycles (1988–2002) were determined using simple soil-water balances comparing daily ET_h and ET_c values to schedule irrigation. In most cases, no soil-water deficits affecting greenhouse crop productivity were detected, but the few cases found led us to also assess experimentally the use of ET_h for irrigation scheduling of greenhouse horticultural crops. The response of five greenhouse crops to water applications scheduled with daily estimates of ET_h and ET_c was evaluated in a typical enarenado soil. In tomato, fruit yield did not differ statistically between irrigation treatments, but the spring green bean irrigated using the ET_h data presented lower yield than that irrigated using the ET_c data. In the remaining experiments, the irrigation-management method based on ET_h data was modified to consider the standard deviation of the inter-annual greenhouse reference ET. No differences between irrigation treatments were found for productivity of pepper, zucchini and melon crops.     

Use of stem diameter variations to detect plant water stress in tomato

The sensitivity of stem diameter variations (SDV) measured with linear variable transducer (LVDT) sensors as indicators of plant water status in tomato was evaluated. Two tomato crops were grown sequentially in a sandy loam soil in an unheated plastic greenhouse. These were an autumn–winter tomato crop (autumn crop) and a spring–summer tomato crop (spring crop). One drying cycle of 61 days was imposed to the autumn crop in winter at 92 days after transplanting (DAT). Two drying cycles, each of 29 days, were applied to the spring crop, to young (58 DAT) and mature plants (121 DAT). For each drying cycle, four replicate plots did not receive irrigation, and four were well watered. During each drying cycle, LVDT sensors continuously measured SDV, and daily measurements were made of leaf (Ψ _leaf) and stem water potential (Ψ _stem). SDV data was interpreted using the SDV-derived indices, maximum daily shrinkage (MDS) and stem growth rate (SGR). The response of SDV-derived indices to water deficit differed with (1) climatic conditions during stress imposition and (2) crop age. In the winter drying cycle of the autumn crop, the responses of the SDV-derived indices to soil drying were relatively small and slower than Ψ _leaf and Ψ _stem. Under warmer conditions, the SDV-derived indices were much more responsive to soil drying. In rapidly growing young plants, where SDV was characterized by high SGR and small MDS, SGR was the most sensitive SDV-derived index. In more mature plants with little stem growth, MDS was the most sensitive SDV-derived index. In mature plants grown in warm to hot conditions, MDS (1) responded at a similar time or earlier than Ψ _leaf and Ψ _stem and (2) had larger “signal” values (ratio of values from unwatered to control plants) than Ψ _leaf and Ψ _stem. However, there was appreciably more “noise” (coefficient of variation, CV) associated with the SDV-derived indices, giving lower “sensitivity” values, determined from “signal” to “noise” ratios, than for Ψ _leaf and Ψ _stem. Regression analysis between MDS of well-watered plants and climatic variables gave best results for a linear relationship between MDS and daily maximum vapor pressure deficit. There were strong linear relationships between MDS and Ψ _leaf for each drying cycle. The slopes of these relationships differed with crop age indicating that there was no constant relationship between MDS and Ψ _leaf for a whole season. Overall these results demonstrated that MDS and SGR can be sensitive indicators of the water status of tomato crops under conditions of moderate to high evaporative demand. However, the variability associated with the SDV-derived indices and the changing MDS–Ψ _leaf relationship with crop age represent major issues regarding the development of irrigation scheduling protocols for tomato.