Spectroscopic quantification of soil phosphorus forms by 31p-nmr after nine years of organic or mineral fertilization

Long-standing applications of mineral fertilizers or types of organic wastes such as manure can cause phosphorus (P) accumulation and changes in the accumulated P forms in the soil. The objective of this research was to evaluate the forms of P accumulated in soils treated with mineral fertilizer or different types of manure in a long-term experiment. Soil was sampled from the 0-5 cm layer of plots fertilized with five different nutrient sources for nine years: 1) control without fertilizer; 2) mineral fertilizer at recommended rates for local conditions; 3) 5 t ha-1 year-1 of moist poultry litter; 4) 60 m³ ha-1 year-1 of liquid cattle manure and 5) 40 m³ ha-1 year-1 of liquid swine manure. The 31P-NMR spectra of soil extracts detected the following P compounds: orthophosphate, pyrophosphate, inositol phosphate, glycerophosphate, and DNA. The use of organic or mineral fertilizer over nine years did not change the soil P forms but influenced their concentration. Fertilization with mineral or organic fertilizers stimulated P accumulation in inorganic forms. Highest inositol phosphate levels were observed after fertilization with any kind of manure and highest organic P concentration in glycerophosphate form in after mineral or no fertilization.

Forms and accumulation of copper and zinc in a sandy typic hapludalf soil after long-term application of pig slurry and deep litter

Successive applications of pig slurry and pig deep litter may lead to an accumulation of copper (Cu) and zinc (Zn) fractions in the soil profile. The objective of this study was to evaluate the Cu and Zn forms and accumulation in a Sandy Typic Hapludalf soil after long-term application of pig slurry and deep litter. In March 2010, eight years after initiating an experiment in Braço do Norte, Santa Catarina (SC), Brazil, on a Sandy Typic Hapludalf soil, soil samples were collected from the 0-2.5, 2.5-5.0, 5-10 and 10-15 cm layers in treatments consisting of no manure application (control) and with applications of pig slurry and deep litter at two levels: the single and double rate of N requirement for maize and black oat succession. The soil was dried, ground in an agate mortar and analyzed for Cu and Zn contents by 0.01 mol L-1 EDTA and chemically fractionated to determine Cu and Zn. The applications of Pig deep litter and slurry at doses equivalent to 90 kg ha-1 N increased the contents of available Cu and Zn in the surface soil layer, if the double of this dose was applied in pig deep litter or double this dose in pig slurry, Cu and Zn migrated to a depth of 15 cm. Copper is accumulated mainly in the organic and residual fractions, and zinc preferentially in the fraction linked to clay minerals, especially in the surface soil layers.

Ammonia volatilization from coated urea forms

Nitrogen fertilization is a major component of the cost of agricultural production, due to the high cost and low efficiency of fertilizers. In the case of urea, the low efficiency is mainly due to losses by volatilization, which are more pronounced in cultivation systems in which plant residues are left on the soil. The objective of this work was to compare the influence of urea coated with sulfur or boric acid and copper sulfate with conventional N fertilizers on N volatilization losses in sugar cane harvested after stubble burning. The sources urea, sulfur-coated urea, urea coated with boric acid and copper sulfate, as well as nitrate and ammonium sulfate, were tested at amounts containing N rates of 120 kg ha-1 N. The integration of new technologies in urea fertilization can reduce N losses by volatilization. These losses were most reduced when using nitrate and ammonium sulfate. The application of a readily acidified substance (boric acid) to urea was more efficient in reducing volatilization losses and nutrient removal by sugar cane than that of a substance with gradual acidification (elemental sulfur).

Available content, surface runoff and leaching of phosphorus forms in a typic hapludalf treated with organic and mineral nutrient sources

The application of animal manure to soil can increase phosphorus availability to plants and enhance transfer of the nutrient solution drained from the soil surface or leached into the soil profile. The aim of this study was to evaluate the effect of successive applications of organic and mineral nutrient sources on the available content, surface runoff and leaching of P forms in a Typic Hapludalf in no-tillage systems. Experiment 1 was set up in 2004 in the experimental area of UFSM, in Santa Maria (RS, Brazil). The treatments consisted of: control (without nutrient application) and application of pig slurry (PS), pig deep-litter (PL), cattle slurry (CS), and mineral fertilizers (NPK). The rates were determined to meet the N crop requirements of no-tillage black oat and maize, grown in the 2010/2011 growing season. The soil solution was collected after each event (rain + runoff or leaching) and the soluble, particulate and total P contents were measured. In November 2008, soil was collected in 2 cm intervals to a depth of 20 cm, in 5 cm intervals to a depth of 40 cm, and in 10 cm intervals to a depth of 70 cm. The soil was dried and ground, and P determined after extraction by anion exchange resin (AER). In experiment 2, samples collected from the Typic Hapludalf near experiment 1 were incubated for 20, 35, 58, 73 and 123 days after applying the following treatments: soil, soil + PS, soil + PL, soil + CS and soil + NPK. Thereafter, the soil was sampled and P was analyzed by AER. The applications of nutrient sources over the years led to an increase in available P and its migration in the soil profile. This led to P transfer via surface runoff and leaching, with the largest transfer being observed in PS and PL treatments, in which most P was applied. The soil available P and P transfer via surface runoff were correlated with the amounts applied, regardless of the P source. However, P transfer by leaching was not correlated with the applied nutrient amount, but rather with the solution amount leached in the soil profile.

Forms of phosphorus in an oxisol under different soil tillage systems and cover plants in rotation with maize

Phosphorus fractions play a key role in sustaining the productivity of acid-savanna Oxisols and are influenced by tillage practices. The aim of this study was to quantify different P forms in an Oxisol (Latossolo Vermelho-Amarelo) from the central savanna region of Brazil under management systems with cover crops in maize rotation. Three cover crops (Canavalia brasiliensis, Cajanus cajan (L.), and Raphanus sativus L.) were investigated in maize rotation systems. These cover crops were compared to spontaneous vegetation. The inorganic forms NaHCO3-iP and NaOH-iP represented more than half of the total P in the samples collected at the depth of 5-10 cm during the rainy season when the maize was grown. The concentration of inorganic P of greater availability (NaHCO3-iP and NaOH-iP) was higher in the soil under no-tillage at the depth of 5-10 cm during the rainy season. Concentrations of organic P were higher during the dry season, when the cover crops were grown. At the dry season, organic P constituted 70 % of the labile P in the soil planted to C. cajan under no-tillage. The cover crops were able to maintain larger fractions of P available to the maize, resulting in reduced P losses to the unavailable pools, mainly in no-tillage systems.

Soil water erosion under different cultivation systems and different fertilization rates and forms over 10 years

The action of rain and surface runoff together are the active agents of water erosion, and further influences are the soil type, terrain, soil cover, soil management, and conservation practices. Soil water erosion is low in the no-tillage management system, being influenced by the amount and form of lime and fertilizer application to the soil, among other factors. The aim was to evaluate the effect of the form of liming, the quantity and management of fertilizer application on the soil and water losses by erosion under natural rainfall. The study was carried out between 2003 and 2013 on a Humic Dystrupept soil, with the following treatments: T1 - cultivation with liming and corrective fertilizer incorporated into the soil in the first year, and with 100 % annual maintenance fertilization of P and K; T2 - surface liming and corrective fertilization distributed over five years, and with 75 % annual maintenance fertilization of P and K; T3 - surface liming and corrective fertilization distributed over three years, and with 50 % annual maintenance fertilization of P and K; T4 - surface liming and corrective fertilization distributed over two years, and with 25 % annual maintenance fertilization of P and K; T5 - fallow soil, without liming or fertilization. In the rotation the crops black oat (Avena strigosa ), soybean (Glycine max ), common vetch (Vicia sativa ), maize (Zea mays ), fodder radish (Raphanus sativus ), and black beans (Phaseolus vulgaris ). The split application of lime and mineral fertilizer to the soil surface in a no-tillage system over three and five years, results in better control of soil losses than when split in two years. The increase in the amount of fertilizer applied to the soil surface under no-tillage cultivation increases phytomass production and reduces soil loss by water erosion. Water losses in treatments under no-tillage cultivation were low in all crop cycles, with a similar behavior as soil losses.

Phosphorus Forms in Ultisol Submitted to Burning and Trituration of Vegetation in Eastern Amazon

ABSTRACT The use of fire to prepare agricultural areas is a technique still used by small farmers in eastern Amazon. This type of management changes the dynamics of soil nutrients, especially phosphorus, which constitutes the most limiting nutrient for crop production in tropical soils. This study was carried out to evaluate changes in phosphorus forms in an Argissolo Amarelo Distrófico (Ultisol) submitted to burning and trituration of secondary forest in eastern Amazon. The evaluated systems were: slash-and-burn of vegetation; slash-and-mulch of vegetation; and secondary vegetation. The labile, moderately labile, moderately recalcitrant, available and total phosphorus fractions were assessed at the soil depths of 0.00-0.05, 0.05-0.10 and 0.10-0.20 m. The results showed a predominance of soluble P in acid (moderately labile P) over other forms in all management systems. The management systems influence the content and distribution of the forms of P, where the slash-and-mulch system presented the prevalence of the labile fraction, and the slash-and-burn system contained less labile forms. The slash-and-mulch system favored the accumulation of labile P and total organic P.

Development and validation of UV spectrophotometric method for determination of levofloxacin in pharmaceutical dosage forms

The objective of this research was to develop and validate an alternative analytical method for quantitative determination of levofloxacin in tablets and injection preparations. The calibration curves were linear over a concentration range from 3.0 to 8.0 μg mL-1. The relative standard deviation was below 1.0% for both formulations and average recovery was 101.42 ± 0.45% and 100.34 ± 0.85% for tablets and injection formulations, respectively. The limit of detection and limit of quantitation were 0.08 and 0.25 μg mL-1, respectively. It was concluded that the developed method is suitable for the quality control of levofloxacin in pharmaceuticals formulations.

Development and validation of a dissolution test with reversed-phase liquid chromatography analysis for rupatadine in tablet dosage forms

A dissolution test for in vitro evaluation of tablet dosage forms containing 10 mg of rupatadine was developed and validated by RP-LC. A discriminatory dissolution method was established using apparatus paddle at a stirring rate of 50 rpm with 900 mL of deaerated 0.01 M hydrochloric acid. The proposed method was validated yielding acceptable results for the parameters evaluated, and was applied for the quality control analysis of rupatadine tablets, and to evaluate the formulation during an accelerated stability study. Moreover, quantitative analyses were also performed, to compare the applicability of the RP-LC and the LC-MS/MS methods.

Simultaneous determination of gemifloxacin and diuretics in bulk, pharmaceutical dosage forms and human serum by RP-HPLC

An isocratic reversed phase high-performance liquid chromatographic (RP-HPLC) method has been developed for the simultaneous determination of gemifloxacin and diuretics (hydrochlorothiazide and furosemide) in bulk, dosage formulations and human serum at 232 nm. Chromatographic separation was achieved on Purospher Start C18 (250 mm x 4.6 mm, 5 µm) column using mobile phase, methanol: water: acetonitrile (70:25:5 v/v/v) adjusted to pH 3.0 via phosphoric acid 85% having flow rate of 0.8 mL min -1 at room temperature. Calibration curves were linear over range of 0.5-10 µg mL -1 with a correlation coefficient ± 0.999. LOD and LOQ were in the ranges of 0.75-2.56 µg mL -1. Intra and inter-run precision and accuracy results were 98.26 to 100.9.

Development and validation of a stability-indicating UPLC method for rosuvastatin and its related impurities in pharmaceutical dosage forms

The present work describes a novel stability-indicating reversed-phase ultra performance liquid chromatography method for the separation and quantification of rosuvastatin (RSV) and its related impurities in the pharmaceutical dosage forms under forced degradation conditions. An unknown degradation impurity detected in the acid degradation was identified by using quadrupole time-of-flight mass spectrometry. The chromatographic separation was carried out on C-18 column (100 x 2.1 mm, 1.7 μm) using isocratic elution with methanol and 0.1% trifluoroacetic acid (50:50). The total run time was 12 min within which RSV as well as all related impurities and degradation products were separated. The developed method was validated for RSV and related impurities in pharmaceutical dosage forms.

Spectrophotometric and spectrofluorimetric determination of some drugs containing secondary amino group in bulk drug and dosage forms via derivatization with 7-Chloro-4-Nitrobenzofurazon

Sensitive and selective spectrophotometric and spectrofluorimetric methods have been developed for determination of some drugs such as Pramipexole, Nebivolol, Carvedilol, and Eletriptan, which commonly contain secondary amino group. The subject methods were developed via derivatization of the secondary amino groups with 7-Chloro-4-Nitrobenzofurazon in borate buffer where a yellow colored reaction product was obtained and measured spectrophotometrically or spectrofluorimetrically. Concentration ranges were found as 2.0 to 250 μg mL-1 and 0.1 to 3.0 μg mL-1, for spectrophotometric and spectrofluorimetric study, respectively. The described methods can be easily applied by the quality control laboratories in routine analyses of these drugs in pharmaceutical preparations.

Simple and sensitive spectrophotometric methods for the analysis of mesalamine in bulk and tablet dosage forms

Three simple, sensitive, economical and reproducible spectrophotometric methods (A, B and C) are described for determination of mesalamine in pure drug as well as in tablet dosage forms. Method A is based on the reduction of tungstate and/or molybdate in Folin Ciocalteu's reagent; method B describes the reaction between the diazotized drug and α-naphthol and method C is based on the reaction of the drug with vanillin, in acidic medium. Under optimum conditions, mesalamine could be quantified in the concentration ranges, 1-30, 1-15 and 2-30 µg mL-1 by method A, B and C, respectively. All the methods have been applied to the determination of mesalamine in tablet dosage forms. Results of analysis are validated statistically.

Set-up of a method using LC-UV to assay mometasone furoate in pharmaceutical dosage forms

A reliable method using LC-UV to assay mometasone furoate (MF) in creams or nasal sprays using the same chromatographic conditions was set up. Methanol:water 80:20 (v/v) (1.0 mL min-1) was used as mobile phase. MF was detected at 248 nm and analyzed in a concentration range from 1.0 to 20.0 µg mL-1. The method provided acceptable theoretical plates, peak simmetry, peak tailing factor and peak resolution a short run (5 min). The method showed specificity, good linearity (r = 0.9999) and the quantification limit was 0.379 µg mL-1. Furthermore, the method was precise (RSD < 2.0%), accurate (recovery > 97%) and robust.

Isolation and quantitative HPLC-PDA analysis of lupeol in phytopharmaceutical intermediate products from Vernonanthura ferruginea (Less.) H. Rob.

Prior to obtain a standardized dried extract from V. ferruginea, lupeol was first time isolated from leaves and used as chemical maker. An analytical method using HPLC-PDA for lupeol determination in V. ferruginea intermediate products was developed using a C8 reverse-phase column, acetonitrile-acetic acid (99.99:0.01, v/v) as mobile phase at 0.8 mL min-1, oven temperature at 23-25 ºC, sample injection volume at 30 µL and detection at 210 nm. The method presented linearity from 10 to 160 µg mL-1, accuracy, precision, robustness and suitable sensitivity proving to be a useful tool to the obtainment process of lupeol standardized dried extracts of V. ferruginea.