Comparison of univariate and multivariate calibration for the determination of micronutrients in pellets of plant materials by laser induced breakdown spectrometry

The application of laser induced breakdown spectrometry (LIBS) aiming the direct analysis of plant materials is a great challenge that still needs efforts for its development and validation. In this way, a series of experimental approaches has been carried out in order to show that LIBS can be used as an alternative method to wet acid digestions based methods for analysis of agricultural and environmental samples. The large amount of information provided by LIBS spectra for these complex samples increases the difficulties for selecting the most appropriated wavelengths for each analyte. Some applications have suggested that improvements in both accuracy and precision can be achieved by the application of multivariate calibration in LIBS data when compared to the univariate regression developed with line emission intensities. In the present work, the performance of univariate and multivariate calibration, based on partial least squares regression (PLSR), was compared for analysis of pellets of plant materials made from an appropriate mixture of cryogenically ground samples with cellulose as the binding agent. The development of a specific PLSR model for each analyte and the selection of spectral regions containing only lines of the analyte of interest were the best conditions for the analysis. In this particular application, these models showed a similar performance. but PLSR seemed to be more robust due to a lower occurrence of outliers in comparison to the univariate method. Data suggests that efforts dealing with sample presentation and fitness of standards for LIBS analysis must be done in order to fulfill the boundary conditions for matrix independent development and validation. (C) 2009 Elsevier B.V. All rights reserved.

Evaluation of laser induced breakdown spectrometry for the determination of macro and micronutrients in pharmaceutical tablets

The aim of this work is to demonstrate the feasibility of laser induced breakdown spectrometry (LIBS) for the determination of macro and micronutrients in multielement tablets. The experimental setup was designed by using a laser Q-switch (Nd:YAG, 10 Hz, lambda = 1064 nm) and the emission signals were collected by lenses into an optical fiber coupled to an echelle spectrometer equipped with a high-resolution intensified charge coupled device (ICCD). Tablets were cryogenically ground and thereafter pelletized before LIBS analysis. Calibration curves were made by employing samples and mixtures of commercial multielement tablets with binders at different ratios. Best results were achieved by using the following experimental conditions: 29 J cm(-2) laser fluence, 165 mm lens to sample distance (f = 200 mm), 2.0 mu s delay time, 5.0 mu s integration time and 5 accumulated laser pulses. In general, the results obtained by the proposed LIBS procedure were in agreement with those obtained by ICP OES from the corresponding acid digests and coefficients variation of LIBS measurements varied from 2 to 16%. The metrological figures of merit indicate that LIBS fits for the intended purposes, and can be recommended for the analysis of multielement tablets and similar matrices aiming the determination of Ca, Cu, Fe, Mg, Mn, P and Zn.

Evaluation of laser induced breakdown spectroscopy for the determination of micronutrients in plant materials

Laser induced breakdown spectroscopy (LIBS) has been evaluated for the determination of micronutrients (B, Cu, Fe, Mn and Zn) in pellets of plant materials, using NIST, BCR and GBW biological certified reference materials for analytical calibration. Pellets of approximately 2 mm thick and 15 mm diameter were prepared by transferring 0.5 g of powdered material to a 15 mm die set and applying 8.0 tons cm(-2). An experimental setup was designed by using a Nd:YAG laser operating at 1064 nm (200 mJ per pulse, 10 Hz) and an Echelle spectrometer with ICCD detector. Repeatability precision varied from 4 to 30% from measurements obtained in 10 different positions (8 laser shots per test portion) in the same sample pellet. Limits of detection were appropriate for routine analysis of plant materials and were 2.2 mg kg(-1) B, 3.0 mg kg(-1) Cu, 3.6 mg kg(-1) Fe, 1.8 mg kg(-1) Mn and 1.2 mg kg(-1) Zn. Analysis of different plant samples were carried out by LIBS and results were compared with those obtained by ICP OES after wet acid decomposition. (C) 2009 Elsevier B.V. All rights reserved.

Optimization and validation of a LIBS method for the determination of macro and micronutrients in sugar cane leaves

Laser induced breakdown spectrometry (LIBS) was applied for the determination of macro (P, K, Ca, Mg) and micronutrients (B, Cu, Fe, Mn and Zn) in sugar cane leaves, which is one of the most economically important crops in Brazil. Operational conditions were previously optimized by a neuro-genetic approach, by using a laser Nd:YAG at 1064 nm with 110 mJ per pulse focused on a pellet surface prepared with ground plant samples. Emission intensities were measured after 2.0 mu s delay time, with 4.5 mu s integration time gate and 25 accumulated laser pulses. Measurements of LIBS spectra were based on triplicate and each replicate consisted of an average of ten spectra collected in different sites (craters) of the pellet. Quantitative determinations were carried out by using univariate calibration and chemometric methods, such as PLSR and iPLS. The calibration models were obtained by using 26 laboratory samples and the validation was carried out by using 15 test samples. For comparative purpose, these samples were also microwave-assisted digested and further analyzed by ICP OES. In general, most results obtained by LIBS did not differ significantly from ICP OES data by applying a t-test at 95% confidence level. Both LIBS multivariate and univariate calibration methods produced similar results, except for Fe where better results were achieved by the multivariate approach. Repeatability precision varied from 0.7 to 15% and 1.3 to 20% from measurements obtained by multivariate and univariate calibration, respectively. It is demonstrated that LIBS is a powerful tool for analysis of pellets of plant materials for determination of macro and micronutrients by choosing calibration and validation samples with similar matrix composition.

Anthropometric evaluation and micronutrients intake in patients submitted to laparoscopic Roux-en-Y gastric bypass with a postoperative period of ≥1 year

Backgroung - Bariatric surgery is indicated as the most effective treatment for morbid obesity; the Roux-en-Y gastric bypass (RYGB) is considered the procedure of choice. However, nutritional deficiency may occur in the postoperative period as a result of reduced gastric capacity and change in nutrients absorption in the gastrointestinal tract. The prescription of vitamin and mineral supplementation is a common practice after RYGB; however, it may not be sufficient to prevent micronutrient deficiencies. The aim of this study was to quantify the micronutrient intake in patients undergoing RYGB and verify if the intake of supplementation would be enough to prevent nutritional deficiencies. Methods - The study was conducted on 60 patients submitted to RYGB. Anthropometric, analytical, and nutritional intake data were assessed preoperatively and 1 and 2 years postoperatively. The dietary intake was assessed using 24-h food recall; the values of micronutrients evaluated (vitamin B12, folic acid, iron, and calcium) were compared to the dietary reference intakes (DRI). Results - There were significant differences (p < 0.05) between excess weight loss at the first and second year (69.9 ± 15.3 vs 9.6 ± 62.9 %). In the first and second year after surgery, 93.3 and 94.1 % of the patients, respectively, took the supplements as prescribed. Micronutrient deficiencies were detected in the three evaluation periods. At the first year, there was a significant reduction (p < 0.05) of B12, folic acid, and iron intake. Conclusions - Despite taking vitamin and mineral supplementation, micronutrient deficiencies are common after RYGB. In the second year after surgery, micronutrient intake remains below the DRI.

Micronutrients intake associated with DNA damage assessed by in a human biomonitoring study

Nutrition science has evolved into a multidisciplinary field that applies molecular biology and integrates individual health with the epidemiologic investigation of population health. Nutritional genomics studies the functional interaction of food and its components, macro and micronutrients, with the genome at the molecular, cellular, and systemic level. Diet can influence cancer development in several ways, namely direct action of carcinogens in food that can damage DNA, diet components (macro or micronutrients) that can block or induce enzymes involved in activation or deactivation of carcinogenic substances. Moreover, inadequate intake of some molecules involved in DNA synthesis, repair or methylation can influence mutation rate or changes in gene expression. Several studies support the idea that diet can influence the risk of cancer; however information concerning the precise dietary factor that determines human cancer is an ongoing debate. A lot of epidemiological studies, involving food frequency questionnaires, have been developed providing important information concerning diet and cancer, however, diet is a complex composite of various nutrients (macro and micronutrients) and non-nutritive food constituents that makes the search for specific factors almost limitless.

ERICA: intake of macro and micronutrients of Brazilian adolescents

ABSTRACT OBJECTIVE To describe food and macronutrient intake profile and estimate the prevalence of inadequate micronutrient intake of Brazilian adolescents. METHODS Data from 71,791 adolescents aged from 12 to 17 years were evaluated in the 2013-2014 Brazilian Study of Cardiovascular Risks in Adolescents (ERICA). Food intake was estimated using 24-hour dietary recall (24-HDR). A second 24-HDR was collected in a subsample of the adolescents to estimate within-person variability and calculate the usual individual intake. The prevalence of food/food group intake reported by the adolescents was also estimated. For sodium, the prevalence of inadequate intake was estimated based on the Tolerable Upper Intake Level (UL). The Estimated Average Requirement (EAR) method used as cutoff was applied to estimate the prevalence of inadequate nutrient intake. All the analyses were stratified according to sex, age group and Brazilian macro-regions. All statistical analyses accounted for the sample weight and the complex sampling design. RESULTS Rice, beans and other legume, juice and fruit drinks, breads and meat were the most consumed foods among the adolescents. The average energy intake ranged from 2,036 kcal (girls aged from 12 to 13 years) to 2,582 kcal (boy aged from14 to 17 years). Saturated fat and free sugar intake were above the maximum limit recommended (< 10.0%). Vitamins A and E, and calcium were the micronutrients with the highest prevalence of inadequate intake (> 50.0%). Sodium intake was above the UL for more than 80.0% of the adolescents. CONCLUSIONS The diets of Brazilian adolescents were characterized by the intake of traditional Brazilian food, such as rice and beans, as well as by high intake of sugar through sweetened beverages and processed foods. This food pattern was associated with an excessive intake of sodium, saturated fatty acids and free sugar.

Accumulation of micronutrients by sweet sorghum under field conditions

Samples of two cultivars of sweet sorghum (Brandes and Rio) grown on a Dark Red Latosol (Latossolo Roxo, Barra Bonita, SP.) were collected at intervals of 20 days during their life cycle and the contents of micronutrients were determined by routine procedures. Usually the physiological stages in which the rate of absorption was higher were not the same for both varieties.

Deficiency symptoms and uptake of micronutrients by castor bean grown in nutrient solution

Castor bean is a nutrient-demanding species, but there is still little information on its micronutrient requirements. The objectives of this study were to evaluate the effects of levels of B (2.5, 12.5 and 25.0 µmol L-1), Cu (0.05, 0.25 and 0.50 µmol L-1), Mn (0.2, 1.0 and 2.0 µmol L-1) and Zn (0.2, 1.0 and 2.0 µmol L-1) in a nutrient solution on plant B, Cu, Mn and Zn concentrations and uptake, vegetative growth and fruit yield of castor bean "Iris", grown in greenhouse. The experiment was arranged in a completely randomized block design with three replicates. The first deficiency symptoms were observed for B, followed by Zn, Cu and Mn. The main changes in the cell ultrastructure due to lack of B were thickening of the cell walls and middle lamellae, distorted chloroplasts and tightly stacked thylakoids, besides the absence of starch grains. The Mn, Zn and Cu deficiencies led to disruption of chloroplasts, disintegration of thylakoids and absence of amyloplasts. The concentration and uptake of B, Cu, Mn, and Zn in castor bean plants increased with micronutrient supply in the solution. Fruit yield was drastically reduced by B and Mn deficiencies. On the other hand, the dry matter yield of the shoot and root of castor bean plants was not. In the treatment with full nutrient solution, the leaves accumulated 56 and 48 % of the total B and Mn taken up by the plants, respectively, and the seeds and roots 85 and 61 % of the total Cu and Zn taken up, respectively. This shows the high demand of castor bean Iris for B and Mn for fruit yield.

Fertilization with filter cake and micronutrients in plant cane

The response of sugarcane to application of micronutrients is still not very well known. In view of the need for this information, the aim of this study was to evaluate the application of the micronutrients Zn, Cu, Mn, Fe, B, and Mo to plant cane in three soils, with and without application of filter cake. This study consisted of three experiments performed in the State of São Paulo, Brazil, (in Igaraçu do Tiete, on an Oxisol; in Santa Maria da Serra, on an Entisol, both in the 2008/2009 growing season; and in Mirassol, on an Ultisol, in the 2009/2010 growing season) in a randomized block design with four replications with a 8 x 2 factorial combination of micronutrients (1 - no application/control, 2 - addition of Zn, 3 - addition of Cu, 4 - addition of Mn 5 - addition of Fe, 6 - addition of B, 7 - addition of Mo, 8 - Addition of Zn, Cu, Mn, Fe, B, and Mo) and filter cake (0 and 30 t ha-1 of filter cake) in the furrow at planting. The application of filter cake was more efficient than of Borax in raising leaf B concentration to sufficiency levels for sugarcane in the Entisol, and it increased mean stalk yield in the Oxisol. In areas without filter cake application, leaf concentrations were not affected by the application of Zn, Cu, Mn, Fe, B, and Mo in the furrow at planting; however, Zn and B induced an increase in stalk and sugar yield in micronutrient-poor sandy soil.

Nutrient extraction and exportation by common bean cultivars under different fertilization levels: II - micronutrients

Where the level of agricultural technology is higher, common bean cultivars with a higher yield potential possibly require greater amounts of micronutrients. In Brazil however, there is a lack of information about the micronutrient extraction and exportation by the main grown cultivars. The objective of this study was to evaluate micronutrient (B, Cu, Fe, Mn, and Zn) extraction and exportation by common bean cultivars Pérola and IAC Alvorada, under different levels of NPK fertilization, on a dystroferric Red Nitosol, in Botucatu, São Paulo State, Brazil. The experiment was arranged in a randomized complete block (split plot) design with four replications. The plots consisted of six treatments based on a 2 x 3 factorial model, represented by two cultivars and three NPK levels (PD0 - 'Pérola' without fertilization, PD1 - 'Pérola' with 50 % of recommended fertilization, PD2 - 'Pérola' with 100 % of recommended fertilization, AD0 - 'IAC Alvorada' without fertilization, AD1 - 'IAC Alvorada' with 50 % of recommended fertilization, and AD2 - 'IAC Alvorada' with 100 % of recommended fertilization) and subplots sampled seven times during the cycle. Higher levels of NPK fertilization increased micronutrient extraction by both cultivars, and treatments with 100 % of recommended NPK fertilization extracted on average 167 g B, 58 g Cu, 1,405 g Fe, 1,213 g Mn and 211 g Zn per hectare. Regardless of the treatment, the highest demand period for B, Cu, Fe, Mn and Zn in both cultivars occurred at the R7 stage (pod formation), i.e. 42 to 55 days after emergence (DAE). The amount of B, Cu, Fe, Mn and Zn exported depended mainly on the level of NPK fertilization used, with values per hectare ranging from 38 to 90 g of B, 12 to 26 g of Cu, 222 to 568 g of Fe 234 to 467 g of Mn, and 40 to 96 g of Zn.

HEAVY METALS AND MICRONUTRIENTS IN THE SOIL AND GRAPEVINE UNDER DIFFERENT IRRIGATION STRATEGIES

Soils under natural conditions have heavy metals in variable concentrations and there may be an increase in these elements as a result of the agricultural practices adopted. Transport of heavy metals in soil mainly occurs in forms dissolved in the soil solution or associated with solid particles, water being their main means of transport. In this context, the aim of this study was to evaluate the heavy metal and micronutrient content in the soil and in the grapevine plant and fruit under different irrigation strategies. The experiment was carried out in Petrolina, PE, Brazil. The treatments consisted of three irrigation strategies: full irrigation (FI), regulated deficit irrigation (RDI), and deficit irrigation (DI). During the period of grape maturation, soil samples were collected at the depths of 0-10, 10-20, 20-40, 40-60, and 60-80 cm. In addition, leaves were collected at the time of ripening of the bunches, and berries were collected at harvest. Thus, the heavy metal and micronutrient contents were determined in the soil, leaves, and berries. The heavy metal and micronutrient contents in the soil showed a stochastic pattern in relation to the different irrigation strategies. The different irrigation strategies did not affect the heavy metal and micronutrient contents in the vine leaves, and they were below the contents considered toxic to the plant. In contrast, the greater availability of water in the FI treatment favored a greater Cu content in the grape, which may be a risk to vines, causing instability and turbidity. Thus, adoption of deficit irrigation is recommended so as to avoid compromising the stability of tropical wines of the Brazilian Northeast.

Influence of micronutrients on dry matter yield and interaction with other nutrients in annual crops

The objective of this work was to determine the influence of Zn, Mn and Cu on shoot dry matter yield and uptake of macro and micronutrients in upland rice, common bean and corn. Six greenhouse experiments were conducted using a Dark Red Latosol (Typic Haplusthox). Treatments consisted of application of Zn at 0, 5, 10, 20, 40, 80 and 120 mg kg-1, of Mn at 0, 10, 20, 40, 80, 160, 320 and 640 mg kg-1 and of Cu application at 0, 2, 4, 8, 32, 64 and 96 mg kg-1. Zinc increased yield of rice, Mn increased yields of corn and bean and Cu improved yields of rice and bean. Uptake of N, Ca, and Cu in rice was decreased by zinc treatment. In common bean, uptake of N, Mg, and Cu was increased by zinc application, whereas, uptake of P was decreased. Manganese increased uptake of Mg, Zn and Fe and decreased uptake of Ca, in corn. Uptake of K, Zn and Mn was increased and uptake of P and Cu was decreased by Mn application, in bean. Copper had positive and negative interactions in the uptake of macro and micronutrients, depending on crop species and nutrients involved.

Characterization of nutrient deficiency in Hancornia speciosa Gomes seedlings by omitting micronutrients from the nutrient solution

Hancornia speciosa Gomes (Mangaba tree) is a fruit tree belonging to the Apocynaceae family and is native to Brazil. The production of seedlings of this species is limited by a lack of technical and nutritional expertise. To address this deficiency, this study aimed to characterize the visual symptoms of micronutrient deficiency and to assess growth and leaf nutrient accumulation in H. speciosa seedlings supplied with nutrient solutions that lack individual micronutrients. H. speciosa plants were grown in nutrient solution in a greenhouse according to a randomized block design, with four replicates. The treatments consisted of a group receiving complete nutrient solution and groups treated with a nutrient solution lacking one of the following micronutrients: boron (B), copper (Cu), iron (Fe), manganese (Mn), zinc (Zn), and molybdenum (Mo). The visual symptoms of nutrient deficiency were generally easy to characterize. Dry matter production was affected by the omission of micronutrients, and the treatment lacking Fe most limited the stem length, stem diameter, root length, and number of leaves in H. speciosa seedlings as well as the dry weight of leaves, the total dry weight, and the relative growth in H. speciosa plants. The micronutrient contents of H. speciosa leaves from plants receiving the complete nutrient solution treatment were, in decreasing order, Fe>Mn>Cu>Zn>B.