New approach for direct analysis of opaque solutions with high content of suspended solids: Determination of calcium and phosphate in raw sugarcane juice.

This paper presents a new analytical approach for element concentration determination in samples containing significant concentrations of dissolved and suspended interferences. The proposed system enables to segregate of the complex matrix, species of interest from other interferences with a minimum requirement of reagents and energy. For this purpose, a new cleanup chamber design was implemented with cationic and anionic resins employed under membrane form and the tangential flow of the solution avoided the drawbacks commonly attributed to the packed and fluidized bed columns, such as the formation of preferred paths, increasing hydrodynamic pressure and clogging. The element concentration determination was colorimetrically performed with an automatic flow analysis system. The strategy was validated with the concentration determination of calcium and phosphorus in raw sugarcane juice. Quantification limit of 0.48 to calcium and 1.13 mg L-1 to phosphorus, linear range between 1 and 50 mg L-1, with RSD of 0.50 and 1.50% (n = 11) respectively.

Ethanol determination in fermented sugarcane substrates by a diffusive micro-distillation device.

The determination of ethanol in fermented substrates is an important parameter for monitoring the production of distilled beverage samples. The correct measurement of its content has a direct impact on the profitability of the process. In this work, a diffusive micro-distillation device (DMDD) is proposed that allows the determination of ethanol directly in the fermented or distilled beverages samples. The DMDD consists of a 5 mL plastic test tube containing a reagent solution of potassium dichromate and sulfuric acid, inserted into another 50 mL polyethylene tube containing the sample. This set is heated in a water bath for 15 min at 80 °C, providing the ethanol diffusion, which reacts with the receptor solution contained in the test tube. The chromium (III) produced by the oxidation reaction, is spectrophotometrically quantified at 589 nm. The proposed procedure has a linear range between 1 and 12% (v/v) with R2 = 0.999 and RSD = 3.8% and results in agreement with those obtained by the distillation-densitometry official method.

Synthesis and characterization of struvite derived from poultry manure as a mineral fertilizer.

Animal manure is an important source of nutrients for crop production, but environmental issues can restrict its direct use. Thermochemical processing these manures may be an alternative to concentrate nutrients and reduce the final volume for agriculture application. We aimed here to evaluate the viability of extracting nutrients from chicken manure using a thermochemical process which reduces the volume of transported nutrients, targeting phosphorus (P) recovery as precipitated struvite, without add external source of P. The extraction of nutrients from poultry manure was performed in water, followed by a thermochemical treatment of the solid phase by incineration and acidulation of the resulting ash. Struvite was produced from the acidified ash extract after supplementation with Mg and regulating the pH (~8.5) by KOH addition. The recovery efficiency of P from the poultry manure and incorporation into struvite was 90%. The final product was a multi-nutrient fertilizer with high macronutrient levels (P, K, Mg and S) and low micronutrient content when compared to fresh manure, as well as lower levels of heavy metals, potentially harmful for the environment. The precipitated product obtained here is composed of struvite-NH4 and struvite-K, alongside appreciable quantities of potassium sulphate and hydroxyapatite carbonate. Overall, we conclude that poultry manure represents a viable source of P and N for struvite production resulting in a nutrient-rich, pathogen-free inorganic fertiliser suitable for widespread use in agriculture.

An automatic titration setup for the chemiluminometric determination of the copper complexation capacity in opaque solutions.

An automatic titration setup exploiting flow analysis was proposed for the evaluation of the copper complexation capacity of highly opaque substances (milk and humic substances). The binary search approach was implemented in a flow-batch analyzer, in order to add the in-line selected titrant (e.g. copper ions) volumes to the sample. When the titration end-point was surpassed, the free metal ions catalyzed the reaction of luminol with hydrogen peroxide, yielding the chemiluminescence, which was quantified even in solutions of high opacity. Accuracy was assessed through addition/recovery tests involving classical complexing species (EDTA, DTPA and DTTC), and recoveries ranged from 96% to 115%. The proposed system requires low amounts of reagents and samples (0.42 mg of luminol, 82 µg H2O2, 1.10 mL of sample) per titration run, meaning ca. 12 mL of effluent per titration, and yields precise results (5% r.s.d.) at a sampling throughput of 43 h-1.

Fluidized particles in flow analysis: potentialities, limitations and applications.

In flow analysis, solid particles (sorbents, reagents or catalysts) have been used for e.g. analyte separation/concentration, sample clean-up, speciation analysis, enzymatic assays, analysis relying on slight soluble reagents, and kinetics studies related to adsorption/release of species. The particles are usually accommodated inside packed-bed mini-columns, cartridges or disks, but this geometry may led to limited analyte/particle interaction, poor renewal of the particle surface, swelling effects, establishment of preferential pathways, and increased backpressure. These hindrances are circumvented by fluidizing the solid particles. Fluidization is a worldwide-accepted industrial process, which can be successfully implemented in flow analysis. This review emphasizes historical and conceptual aspects, as well as advantages, limitations, applications, and perspectives for future development of flow analysis relying on fluidized particles.

Temporal Changes in Cadmium Speciation in Brazilian Soils Evaluated Using Cd LIII-Edge XANES and Chemical Fractionation.

Chemical speciation of soil cadmium (Cd) dictates its mobility and potential toxicity in the environment. Our objective was to compare temporal changes in speciation of Cd(II) reacted with samples from six Brazilian soils having varying Cd(II) sorption capacities. Cadmium L-edge X-ray absorption near edge structure (XANES) analysis showed there were short-term changes in speciation after reaction with 4.45 mmol Cd kg for 0.5 and 6 h. Chemical fractionation evaluated changes in Cd extractability after reaction with 89 µmol Cd kg for up to 4 mo. The XANES spectral fits suggested that Cd(II) bound with organic matter was a dominant species in all samples, along with Cd(II) bound with iron and aluminum oxides or montmorillonite. In several samples, CdCl apparently precipitated from aqueous Cd(II) during drying. The XANES spectral fits typically showed <25% change in speciation between 0.5 and 6 h of reaction, and chemical fractionation showed significant ( < 0.05) temporal changes in Cd extractability over time in two samples. Our results suggest that Cd(II) discharged into these soils, such as that occurring as a release into the environment, would bind with soil organic matter and oxide minerals or remain dissolved, with little change in speciation in the months following release.

Sulphate radical generation through interaction of peroxymonosulphate with Co(II) for in-line sample preparation aiming at spectrophotometric flow-based determination of phosphate and phosphite in fertilizers.

An advanced oxidative process relying on the interaction of peroxymonosulphate and cobalt(II) was implemented for generating the sulphate radicals in flow analysis, in order to accomplish in-line sample preparation thus improving the spectrophotometric determination of phosphate and phosphite in liquid foliar fertilizers. To this end, a flow-batch system with a heated chamber was designed. The sample was handled twice, with and without the step of phosphite oxidation to phosphate, and the formed orthophosphate was quantified after interaction with the vanadate-molybdate reagent. Phosphite was determined as the difference in analytical signals corresponding to sample handling with and without the oxidation step. Influence of Co(II) on the peroxymonosulphate activation, reagent concentrations and added volumes, acidity, temperature and heating time were investigated like aiming at to improve analytical recovery and measurement repeatability, as well as the and system ruggedness. The 6.6-20.0mgL(-1) P2O5 standards were in-line prepared from a single stock solution. Detection limits were estimated as 0.8 and 0.1mgL(-1) for P2O5 and P-PO4. Twenty-four samples are were run per hour, and results are were in agreement with those obtained by the official procedure.

A critical review on photochemical conversions in flow analysis.

Photochemical conversions are cost-effective and environmental friendly processes that require mild experimental conditions and avoid generation of highly acidic wastes. Treated samples are then compatible with most of the analytical techniques. These characteristics become more relevant when the photoconversions are accomplished to flow analysis, thus allowing exploitation of incomplete reactions, the effective use of the photogenerated unstable radicals and in-line sample treatment. Decreasing of reagent consumption and waste generation, sample processing in a closed environment, and improvement of efficiency of the photochemical processes are other inherent advantages. These aspects are critically reviewed in this article, which emphasizes applications to fractionation and speciation analysis, photo-induced luminescence, miniaturization, and in-line waste treatment. Design of flow-through photochemical cells, use of auxiliary reagents in homogeneous and heterogeneous media, and configurations of flow manifolds are also discussed.

Multivariate classification of cigarettes according to their elemental content determined by inductively coupled plasma optical emission spectrometry.

In this paper we describe our study on the characterization of cigarette samples according to their mineral content. Acid digestion assisted by microwaves was employed, and inductively coupled plasma optical emission spectrometry was the analytical technique used for the determination of Al, Ba, Ca, Cu, Fe, K, Mg, Mn, Na, P and Sr in conventional, light, and flavorized cigarettes. Multivariate techniques, such as hierarchical clusters analysis (HCA) and principal-component analysis (PCA), were applied to discriminate among different types of cigarettes. Cluster analysis and principal-component analysis showed differences in cigarettes according to the type and mineral composition. The cigarette samples were divided within the 3 groups according to their mineral composition. Ca, Sr, Cu, K and Na were the most important elements for cigarette classification, and only these 5 variables were sufficient for the classification and discrimination of the evaluated types of cigarettes.