Biodiesel Production by Enzymatic Catalysis Process Using Two Analytical Ways： Gas Chromatography and Total Glycerol Determination

Currently, biodiesel is presented as one of the best alternatives for gradually replacing the use of fossil fuels, but it has some factors that make it economically impractical if it does not have a government support. For this reason, research efforts focused on this area have been responsible for optimizing the process of biodiesel production by different catalytic routes to achieve greater efficiency at a lower cost. In this case, the biggest problem has been the high cost generated by an investigation, which in many occasions is the main factor to decide if an investigation could be carried out. Trying to reduce these costs, in the current study, we are using a technique of glycerol quantification by volumetric methods and comparing obtained results with the chromatographic method, which is conventionally used and comparatively much more expensive. Biodiesel employee was obtained by an enzymatic catalysis process varying one of three process variables：oil：alcohol molar ratio, temperature and proportion of catalyst. The numerical differences obtained between the two quantification methods generated relative errors lower than 10%, resulting in some occasions lower than 1%. By gas chromatography analysis the best yield was obtained at the same conditions of the volumetric method, a temperature of 45 ℃, an oil：alcohol ratio 1：4 and 8 wt.% of catalyst, but a yield of 95.5% and 97.1%, respectively. Due to the high precision of gas chromatography, this method is used to carry out a surface response analysis obtaining as ideal operating conditions a temperature of 43.5 ℃, 8.9 wt.%. of catalyst and an oil：alcohol ratio 1：4.     

Analysis of Water-Soluble Vitamins in Honey by Isocratic RP-HPLC

An isocratic RP-HPLC method has been developed for the identification and quantification of water-soluble vitamins in honey. The mobile phase tested was an aqueous solution of sulphuric acid and the detection was carried out simultaneously by UV and fluorescence. The separation of vitamins C (l-ascorbic acid), B₁ (thiamine), B₃N (nicotinamide), B₃H (nicotinic acid), B₅ (d-pantothenic acid) and B₆ (pyridoxine) is achieved in these conditions in 15 min. The addition to the mobile phase of methanol 2 %?v/v reduced significantly the analysis time in the separation of these vitamins up to 10 min. Moreover, in presence of a cationic surfactant hexadecyltrimethylammonium bromide (CTAB) in the mobile phase, the separation of vitamin C, B₁, B₃N, B₃H, B₂ (riboflavin) and B₆ is possible in 6 min. The combination of both mobile phases, H₂SO₄/methanol and H₂SO₄/methanol/CTAB, has been applied to the analysis, in isocratic mode, of several monofloral honeys (rosemary, thyme, lavender, chestnut, echium) and a honeydew honey in a short time analysis.     

As, Hg, and Se flue gas sampling in a coal-fired power plant and their fate during coal combustion

As, Hg, and Se are the most volatile elements in the flue gas from a coal-fired power plant. Significant amounts of these elements cause an undesired direct gaseous emission, which leads to a serious environmental health risk. The main focus of this study is to evaluate the possibility of simultaneous sampling of these volatile elements using an accurate official method for Hg (the most volatile element). A study of As, Hg, and Se emissions from a 1400 MW coal-fired power plant equipped with electrostatic precipitators (ESPs) was carried out for the combustion of a mixture of two types of coal. Simultaneous sampling of coal, bottom ash, fly ash, flue gas, and particles associated with the gas phase has been performed. Flue gas has been sampled by the Ontario Hydro Method Sampling Train, an ASTM method for Hg speciation. This sampling method was tested for As and Se sampling. As and Se determinations have been performed by HG-AAS, and Hg has been determined by CV-AAS. The results were used to examine the following: overall mass balances, relative distribution of these elements in the coal-fired power plant; As, Hg, and Se concentrations in coal and combustion residues; and predominant oxidation state for Hg in flue gas. The mass balances obtained for As, Hg, and Se were satisfactory in all cases; nevertheless, relative enrichment values in fly ash for As and Se were low; therefore, we concluded that As sampling in flue gas can be conducted by application of the Ontario Hydro Method; nevertheless Se released in the gas phase is not completely collected by this sampling train. Application of this sampling method allowed for performance of Hg speciation. The results indicated that Hg(II) was the predominant species in flue gas. It has also been proved that 24%, more than 99.8%, and 90% for As, Hg, and Se in the stack emissions, respectively, were in the gaseous phase.     

Downstream environmental effects of dam operations: Changes in habitat quality for native fish species

Hydropeaking dam operation and water extractions for irrigation have been broadly stated as alterations to natural flow regimes, which have also been noticed in the Biobío Watershed, in Central Chile, since 1996. In the Biobío River, most of native fish species are endemic and very little is known about them. Their ecological and social values have never been estimated, and there is lack of information about their habitat preferences. Furthermore, changes on fish habitat availability due to natural and/or man‐made causes have not been evaluated. In this study, eight native fish species, in a representative reach of the Biobío River, were studied and their preferred habitats were surveyed and characterized. A hydrodynamic model was built and linked to the fish habitat simulation model CASiMiR. Fuzzy rules and fuzzy sets were developed for describing habitat preference of the native fish species. CASiMiR was then used to simulate how physical habitat conditions vary due to flow control (i.e. upstream dams). Results show how overall habitat quality, expressed as weighted usable area (WUA) and hydraulic habitat suitability (HHS), changes and fluctuates due to the dam operation and how the daily hydropeaking is influencing quantity, quality and location of different habitats. The study suggests that the analysed fish are highly susceptible to flow control, as dams are currently operated, and fish habitat improvement suggestions are proposed. Copyright © 2010 John Wiley & Sons, Ltd.     

PARTICLE SIZE, SOLVENT, OXYGEN, TEMPERATURE AND PRESSURE EFFECTS ON THE CONTENTS OF INSOLUBLE FRACTIONS FROM SOLID VACUUM RESIDUA

n-Heptane insoluble contents were determined for an extraheavy-oil vacuum residue, one petroleum and one coal pitch as a function of particle size. This variable was found to affect the yields of insoluble material, aspect which was also observed during extractions carried out with aromatic and halogenated solvents. The precision of results was observed to be independent on the operators. A study was carried out to determine the effect of sample drying time on fraction yields. It was found that maltene fractions were strongly dependent on this variable, whereas asphaltene fractions were totally independent

Predissolution in aromatic solvents proved worthless from the repeatability point of view. However, predissolution of the oil residue in CH₂Cl₂ followed by filtration and asphaltene precipitation with simultaneous solvent removal, was deemed to be a suitable technique to remove mineral matter and isolate asphaltenes in a single step

Sample oxidation during asphaltene precipitation and isolation was detected by gravimetric and spectroscopic techniques. This fact is very important since common precipitation techniques do not address this issue

Preliminary accelerated extraction experiments carried out with pitch samples at high temperature and pressure, revealed that this approach can be a very interesting research tool to investigate solubility properties.     

Assessment of the bioavailability of toxic and non-toxic arsenic species in seafood samples

Bioavailability of total arsenic, toxic (arsenite, As(III); and arsenate, As(V)), and non-toxic (monomethylarsonic acid, MA; dimethylarsonic acid, DMA; arsenobetaine, AB; and arsenocholine, AC) arsenic species has been assessed in different raw seafood samples (white fish, cold water fish and molluscs) by using an in vitro model that combines simulated gastric and intestinal digestion/dialysis methods. Correlations between arsenic species bioavailability and seafood nutrient contents (fat and protein) have also been established. Total arsenic content in seafood samples, and dialyzable and non-dialyzable fractions, were analyzed by inductively coupled plasma – mass spectrometry (ICP–MS) after a microwave-assisted acid digestion treatment. The determination of the different arsenic species concentrations in the samples (after an optimised matrix solid phase dispersion (MSPD) approach) and in the dialyzable fraction was done by high performance liquid chromatography (HPLC) coupled to ICP-MS as a selective detector. Accuracy of the procedure (total arsenic determination) was assessed by analyzing DORM-2 and BCR-627 certified reference materials. The accuracy of the in vitro procedure was established through a mass-balance study. After statistical evaluation (95% confidence interval), good accuracy of the whole in vitro process, for total arsenic and for arsenic speciation, was observed. High dialyzability percentages for total arsenic and for arsenic species were found (i.e. from 84.6 ± 1.7% to 106 ± 2.6%). Bioavailability of arsenic exhibits a negative correlation with the fat content of the seafood. However, no correlation was observed between the bioavailable fraction of total arsenic and arsenic species and the protein content of the seafood studied.     

Browning Inhibition in Fresh-cut'Fuji'Apple Slices by Natural Antibrowning Agents

ABSTRACT Response surface methodology was used to study the effect of antibrowning agents (4‐hexylresorci‐nol, glutathione, N‐acetylcysteine, and ascorbic acid) and storage time (14 d) on the color of minimally processed Fuji apples. The selected color parameters were L*,a*, b*, hue angle (h*), and color difference (ΔE*). Storage time had a significant effect on all the studied color parameters (P± 0.05). 4‐hexylresorcinol showed the most effective individual effect on keeping constant a*values (P± 0.0001). Besides, the interaction of N‐acetylcysteine/ glutathione was found to have a significant effect (P± 0.05) on maintaining a* values over time. On the other hand, individual treatment with N‐acetylcysteine in concentrations higher than 0.75% w/v may be used to preserve a*and h*.According to the F‐test, 4‐hexylresorcinol and N‐acetylcysteine (P± 0.05) displayed a significant individual effect on ΔE*, indicating that ΔE* decreased when increasing the concentration of these antibrowning agents. Nevertheless, color difference went down when 4‐hexylresorcinol concentration increased up to 0.5%, but higher concentrations of this agent led to an increase in ΔE* that indicates browning.     

Visual Navigation in Natural Environments: From Range and Color Data to a Landmark-Based Model

This paper concerns the exploration of a natural environment by a mobile robot equipped with both a video color camera and a stereo-vision system. We focus on the interest of such a multi-sensory system to deal with the navigation of a robot in an a priori unknown environment, including (1) the incremental construction of a landmark-based model, and the use of these landmarks for (2) the 3-D localization of the mobile robot and for (3) a sensor-based navigation mode.For robot localization, a slow process and a fast one are simultaneously executed during the robot motions. In the modeling process (currently 0.1 Hz), the global landmark-based model is incrementally built and the robot situation can be estimated from discriminant landmarks selected amongst the detected objects in the range data. In the tracking process (currently 4 Hz), selected landmarks are tracked in the visual data; the tracking results are used to simplify the matching between landmarks in the modeling process.Finally, a sensor-based visual navigation mode, based on the same landmark selection and tracking, is also presented; in order to navigate during a long robot motion, different landmarks (targets) can be selected as a sequence of sub-goals that the robot must successively reach.     

Using Structural Equation Modeling (SEM) for the Study of Impurity Profiles of Drug Substances

The impurity profile is one of the most important quality characteristics of a drug substance. Although it is always desirable to determine the chemical structure of all impurities forming the impurity profile, unfortunately this is not always economically and technically feasible because of the extremely low concentrations at which some impurities may be found in the drug substance. Therefore, alternative approaches to the chemical analysis are needed for trying to determine the origin of the unidentified impurities.

In a previous study conducted by our group, based on exploratory (principal component and hierarchical cluster) analysis, we were able to suggest a hypothesis for explaining the origin of the unidentified impurities of a drug substance. However, there was still a concern that alternative hypotheses might explain the same phenomenon equally well. This article explores the application of recent developments in structural equation modeling for the systematic generation and selection of hypotheses (models) worthy of being confirmed by chemical research.     

Surfactant to dye binding degree-based methodology for the determination of ionic amphiphilic compounds

A new analytical measurement parameter based on the effect of amphiphilic substances on the degree of binding of a surfactant to dye molecules, which induce the formation of surfactant premicellar aggregates, is presented. The theory for dye-surfactant intermolecular interactions in mixed surfactant systems, which assumes a mononuclear model for the formation of dye-induced premicellar aggregates, has been used to derive an expression that provides linear calibrations for the determination of amphiphilic compounds. The dye-surfactant interactions involved have been investigated, and the variables affecting the measurement analytical parameter have been discussed. The analytical applicability of the surfactant-dye binding degree method is demonstrated by quantifying major anionic surfactants at the nanograms-per-milliliter level and determining the total concentration of these amphiphilic substances in sewage samples (average recoveries ranged from 98 to 102%).