Removal of basic dyes from aqueous solutions with a treated spent bleaching earth

A spent bleaching earth from an edible oil refinery was treated by impregnation with a normal sodium hydroxide solution followed by mild thermal treatment (100 degrees C). The obtained material (TSBE) was washed, dried, and characterized by X-ray diffraction, FTIR, SEM, BET, and thermal analysis. The clay structure was not apparently affected by the treatment and the impregnated organic matter was quantitatively removed. We have investigated the comparative sorption of safranine and methylene blue on this material, the spent bleaching earth (SBE), and the virgin bleaching earth (VBE). The kinetic results fit the pseudo-second-order kinetic model and the Weber and Morris intraparticle diffusion model. The pH had no effect on the sorption efficiency. The sorption isotherms followed the Langmuir model for various sorbent concentrations with good values of the determination coefficient. A linear relationship was found between the calculated maximum removal capacity and the solid/solution ratio. A comparison between the results obtained with this material and those of the literature highlighted the low cost and the good removal capacity of treated spent bleaching earth.     

An effective ostrich oil bleaching technique using peroxide value as an indicator

Ostrich oil has been used extensively in the cosmetic and pharmaceutical industries. However, rancidity causes undesirable chemical changes in flavour, colour, odour and nutritional value. Bleaching is an important process in refining ostrich oil. Bleaching refers to the removal of certain minor constituents (colour pigments, free fatty acid, peroxides, odour and non-fatty materials) from crude fats and oils to yield purified glycerides. There is a need to optimize the bleaching process of crude ostrich oil prior to its use for therapeutic purposes. The objective of our study was to establish an effective method to bleach ostrich oil using peroxide value as an indicator of refinement. In our study, we showed that natural earth clay was better than bentonite and acid-activated clay to bleach ostrich oil. It was also found that 1 hour incubation at a 150 °C was suitable to lower peroxide value by 90%. In addition, the nitrogen trap technique in the bleaching process was as effective as the continuous nitrogen flow technique and as such would be the recommended technique due to its cost effectiveness.     

Investigation of the properties of oil at the bleaching unit of an oil refinery

Color removal from neutralized sunflower oil was studied with different kinds of commercial bleaching earths. The effect of changes in time (25 and 35 min), temperature (80-125 degrees C), and bleaching earth dosage (0.1-0.9% by weight) on color, chlorophyll and carotene concentrations, and oxidation degree were investigated. To obtain adsorption curves from coloring compounds adsorbed onto activated bleaching earths, the Langmuir and Freundlich equations was used, the constant parameters and correlation coefficient R were calculated for each type of bleaching earth, and color changes were explained by both adsorption isotherms. It was observed that an increase in bleaching earth dosage decreases color. Its effect on oxidation state, however, is complex and related to both primary and secondary oxidation products. In addition, an increase in temperature seems to decrease chlorophyll and carotene adsorptions. Generally, time beyond equilibrium is considered useless for the removal of unwanted components. This study also confirms this claim and reveals that the peroxide value does not indicate the oxidation state of the oil completely.     

Cholesterol degradation in archaeological pottery mediated by fired clay and fatty acid pro-oxidants

Cholesterol is generally absent in animal fat residues preserved in archaeological ceramic vessels. It is known from edible oil refining that during bleaching with activated clay sterols are degraded, largely via oxidation. Laboratory heating experiments using fired clay from replica pottery vessels promoted rapid degradation of cholesterol via oxidation. Furthermore, heating cholesterol with fatty acids (saturated and unsaturated) revealed additional degradation to occur independently of the ceramic matrix. As both conditions are met in archaeological pottery during animal (and plant) product processing involving heating, the very rare detection of sterols in organic residues can be explained.     

Analysis of Changes in the Amount of Phytosterols after the Bleaching Process of Hemp Oils

Unrefined vegetable oils from niche oilseeds are now sought after by consumers because of their unique nutritional properties and taste qualities. The color and flavor intensity of niche oils is a big problem, and their refining is not industrially feasible due to the small production scale. The study undertaken aimed analyze the effect of changing the amount of phytosterols (PSs) after the bleaching process of hemp oils of the ‘Finola’, ‘Earlina 8FC’ and ‘Secuieni Jubileu’ varieties. Cold-pressed (C) and hot-pressed (H) crude vegetable oils were bleached with selected bleaching earth (BE) at two concentrations. The post-process BE was extracted with methanol. The amount of PSs in the crude oils and the extract after washing the BE with methanol was analyzed by GC (gas chromatography). The study shows that the bleaching process did not significantly affect the depletion of PSs in the oils. Trace amounts of PSs remain on the BE and, due to methanol extraction, can be extracted from the oil. The conclusion of the performed research is that the bleaching of hemp oil does not cause depletion of the oil, and it significantly improves organoleptic properties. The oil bleaching process results in an oil loss of less than 2% by weight of the bleached oil, while the loss depends on the type of BE used. The study shows that the loss of phytosterols after the bleaching process averages 2.69 ± 0.69%, and depends on the type of BE used and the oil extracted from different varieties of hemp seeds.     

Nanoparticle-based assay for the detection of virgin argan oil adulteration and its rapid quality evaluation

A new method, based on the formation of gold nanoparticles (AuNPs) and spectrophotometric analysis, is proposed to determine total phenolic acids in virgin argan oil samples. These compounds have reducibility due to the presence of the phenol group in their molecular structure, and a redox reaction occurs in the presence of HAuCl₄. The formation of AuNPs as a result of the redox reaction leading to colour changes can be visually observed, resulting in strong light signals that show absorption at 555 nm. As ferulic acid represents more than 95% of the total phenolic acid content of virgin argan oil, this compound was used as an adulteration marker to carry out the screening of samples for the evaluation of the authenticity of virgin argan oils. The analytical features of this screening method also allowed a low precision quantization of the quality of the product. Then, a reference HPLC-DAD/FD method was used to confirm the potential adulterated samples, as well as to provide a detailed quantitative analysis of the most representative phenolic compounds in the samples. The overall screening-confirmation strategy was validated by analysing pure virgin argan oil samples and argan oil samples adulterated with other commercial vegetable oils, demonstrating the reliability of the results. This approach is characterised by its simplicity, low cost, rapid information and responded to practical laboratories needs.     

Direct olive oil authentication: detection of adulteration of olive oil with hazelnut oil by direct coupling of headspace and mass spectrometry, and multivariate regression techniques

Control of adulteration of olive oil, together with authentication and contamination, is one of the main aspects in the quality control of olive oil. Adulteration with hazelnut oil is one of the most difficult to detect due to the similar composition of hazelnut and olive oils; both virgin olive oil and olive oil are subjected to that kind of adulteration. The main objective of this work was to develop an analytical method able to detect adulteration of virgin olive oils and olive oils with hazelnut oil by means of its analysis by a headspace autosampler directly coupled to a mass spectrometer used as detector (ChemSensor). As no chromatographic separation of the individual components of the samples exists, a global signal of the sample is obtained and employed for its characterization by means of chemometric techniques. Four different crude hazelnut oils from Turkey were employed for the development of the method. Multivariate regression techniques (partial least squares and principal components analysis) were applied to generate adequate regression models. Good values were obtained in both techniques for the parameters employed (standard errors of prediction (SEP) and prediction residual error sum of squares (PRESS)) to evaluate its goodness. With the proposed method, minimum adulteration levels of 7 and 15% can be detected in refined and virgin olive oils, respectively. Once validated, the method was applied to the detection of such adulteration in commercial olive oil and virgin olive oil samples.     

Classification of edible and lampante virgin olive oil based on synchronous fluorescence and total luminescence spectroscopy

Total luminescence and synchronous fluorescence spectroscopies were tested as regards their ability to differentiate edible from lampante virgin olive oils. Total luminescence spectra were recorded by measuring the emission spectra in the range 350-720 nm at excitation wavelengths from 320 to 535 nm. The synchronous fluorescence spectra of 41 edible and 32 lampante virgin olive oils were acquired by synchronous scanning the excitation and emission monochromator maintained at an offset value of 80 nm. Classification of virgin olive oils based on their synchronous fluorescence spectra was performed by hierarchical cluster analysis and principal component analysis using the spectral range of 429-545 nm. Principal component analysis provided better discrimination between the two classes, without any classification error, while hierarchical cluster analysis allowed 97.3% correct classification. These results indicate the capability of fluorescence techniques to differentiate virgin olive oils according to their quality.     

Synchronous fluorescence spectroscopy for quantitative determination of virgin olive oil adulteration with sunflower oil

Adulteration of extra virgin olive oil with sunflower oil is a major issue for the olive oil industry. In this paper, the potential of total synchronous fluorescence (TSyF) spectra to differentiate virgin olive oil from sunflower oil and synchronous fluorescence (SyF) spectra combined with multivariate analysis to assess the adulteration of virgin olive oil are demonstrated. TSyF spectra were acquired by varying the excitation wavelength in the region 270–720 nm and the wavelength interval (Δλ) in the region from 20 to 120 nm. TSyF contour plots for sunflower, in contrast to virgin olive oil, show a fluorescence region in the excitation wavelength range 325–385 nm. Fifteen different virgin olive oil samples were adulterated with sunflower oil at varying levels (0.5–95%) resulting in one hundred and thirty six mixtures. The partial least-squares regression model was used for quantification of the adulteration using wavelength intervals of 20 and 80 nm. This technique is useful for detection of sunflower oil in virgin olive oil at levels down to 3.4% (w/v) in just two and a half minutes using an 80-nm wavelength interval.     

Quantitative Determination and Variation Trends of Six Alkaloids in Crude and Processed Corydalis Yanhusuo

A convenient, sensitive, and accurate analytical method using reversed-phase high-performance liquid chromatography coupled with ultraviolet-visible detection was investigated for the determination of 6 alkaloids (tetrahydrocoptisine, protopine, tetrahydropalmatine, coptisine, corydaline, and palmatine) in crude and processed samples of corydalis yanhusuo. The results revealed that the content of the alkaloids in crude corydalis yanhusuo samples varied from those of the processed samples. The concentrations of tetrahydrocoptisine, protopine, tetrahydropalmatine, coptisine, and corydaline were reduced after processing; however, the concentration of palmatine increased after processing. This method was established using a C₁₈ column (250 mm × 4.6 mm, 5 µm). The mobile phase, a mixture (19:81) of acetonitrile and a 0.6% solution of acetic acid (pH 3.5, adjusted using triethylamine), was used to elute the target compounds in the isocratic elution mode. The solvent flow rate was 1.0 mL/min, the column temperature was 35°C, and the detection wavelength was 280 nm. All of the calibration curves exhibited good linearity with R >0.9999. The inter- and intra-day precisions for all of the investigated components ranged from 0.10–2.64% RSD, and the recoveries were in the range of 97.3–102.5%. The validated method provides a new solution for analyzing the contents of crude and processed samples of corydalis yanhusuo.     

Carbon-mineral adsorbents prepared by pyrolysis of waste materials in the presence of tetrachloromethane

Natural bentonite spent in the process of plant oil bleaching was used as an initial material for preparation of carbon-mineral adsorbents. The spent bleaching earth was treated using four procedures: T (thermal treatment); H (hydrothermal treatment); C (thermal treatment with addition of CCl4 vapor); M (modification of porous structure). Raw bentonite, RB (raw bleaching earth), and carbon materials prepared using plant oil were compared. The physicochemical characteristics of the adsorbents were determined using different methods: nitrogen adsorption/desorption, XRD, TEM, and MS-TPD. Carbon-mineral adsorbents contain from 5.23 to 19.92% C (w/w) and carbon adsorbents include from 84.2 to 91.18% C (w/w). Parallel processes of organic substance carbonization, porous structure modification, sublimation or evaporation of metal chlorides, and removal of hydrogen chloride take place during pyrolysis of waste mineral materials in the CCl4 atmosphere.     

Pyrolysis of residual palm oil in spent bleaching clay by modified tubular furnace and analysis of the products by GC–MS

In this study, spent bleaching clay containing 26.6 wt.% of residual palm oil was pyrolyzed using a tubular furnace. Carboxylic acids ranging from C₉-C₁₈ and alkanes ranging from C₁₆-C₄₄ were the major classes of compounds found in the pyrolytic products analyzed using GC-MS. Significant amounts of monoaromatic compounds, alkenes, alcohols, ketones, aldehydes, esters, nitrogenated compounds, and polycyclic aromatic hydrocarbons (PAHs) were found in the bio-oil produced in this study. The bio-oil resulting from the pyrolysis process gave n-hexadecanoic acid as the major compound. Decomposition temperature of the adsorbed oil determined using TGA was found to be in the range of 573-683 K. Topographical and elemental analyses of the clay was done using SEM-EDX. The functional groups were determined using FTIR.     

Bleacing of olive mill wastewater by clay in the presence of hydrogen peroxide

Treatment of olive mill wastewater (OMW) with clayey soils in the presence of hydrogen peroxide (H₂O₂) allows the elimination of phenolic compounds responsible for the black-brownish color of this industrial effluent. The aim of this research was to define optimal physicochemical parameters for the bleaching of OMW with clay in the presence of hydrogen peroxide. Two clayey soil powders were tested (A and B) and the results obtained indicate that high bleaching could be reached after 24 hours exposure of OMW to 7 % (W/V) clay material A in the presence of 0.5 % (V/V) hydrogen peroxide. Under these conditions, the bleaching led to about 87 % decrease of polyphenols (PF) and a 66 % decrease of the Chemical Oxygen Demand (COD). The structure of clay and its concentration in iron salts have an effective adsorbent and catalytic effect on the removal of the majority of polyphenols.     

Incorporation of clay nano-particles in aqueous foams

During the process of crude oil/gasoline loading and storage, significant amounts of volatile organic compounds (VOCs) can be emitted to the environment. Stable aqueous foams can be spread as a flexible blanket on the top of the oil to control the VOC emission by providing a mass transfer barrier during the loading process. In this work, novel aqueous foams have been formulated by incorporating clay nano-particles in an aqueous solution of surfactants and polymers. The stability and mass transfer resistance of these foams were investigated at temperatures up to 125 F. In the presence of VOC, clay decreases the rate at which the liquid is drained out of the foam lamellae and increases the foam drainage half-life. These foams were found to be very stable in the presence of gasoline and crude oil and can last much longer than one day at the room temperature. The use of clay in the foam formulation reduces vapor diffusion through the lamellae and vapor emission through the foam column significantly for the first 10 h. Increase in temperature increases the rate of foam breakage due to higher water evaporation and lower liquid viscosity. In spite of this increase, the 0.5% polymer and 0.5% clay foam suppresses vapor emission from a gasoline longer than 3600, 1500 and 1100 min at 75 F, 105 F and 125 F, respectively. This foam also suppresses vapor emission from a crude oil longer than 4200, 2000 and 700 min at 75 F, 105 F and 125 F, respectively.     

Fluorescence spectra measurement of olive oil and other vegetable oils

Fluorescence spectra of some common vegetable oils, including olive oil, olive residue oil, refined olive oil, corn oil, soybean oil, sunflower oil, and cotton oil, were examined in their natural state, with a wavelength of 360 nm used as excitation radiation. All oils studied, except extra virgin olive oil, exhibited a strong fluorescence band at 430-450 nm. Extra virgin olive oil gave a different by interesting fluorescence spectrum, composed of 3 bands: one low intensity doublet at 440 and 455 nm, one strong at 525 nm, and one of medium intensity at 681 nm. The band at 681 nm was identified as the chlorophyll band. The band at 525 nm was at least partly derived from vitamin E. The low intensity doublet at 440 and 455 nm correlated with the absorption intensity at 232 and 270 nm of olive oil. The measurements of these fluorescence spectra were quick (about 5 min) and easy and could possibly be used for authentification of virgin olive oil.     

On testing quality and traceability of virgin olive oil by calorimetry

Extra Virgin olive oils (7 samples) originating from different areas of Tuscany, defective olive oils (5 samples), commercial edible seed oils (4 samples) and two commercial samples of olive oil (one declared ‘extra virgin olive oil’ and one ‘olive oil’) were studied by different calorimetric techniques: high sensitivity isothermal, differential scanning, and modulated scanning calorimetry. The temperature interval (–60) – (+30)°C was explored for monitoring: i) the main features of the liquid↔solid phase transitions, ii) the nucleation and growth rate of the polymorphous crystalline phases of the triacylglicerols, and iii) the melting process. This investigation was planned for verifying the utility and effectiveness of calorimetry for screening quality and origin of olive oil. To this end, the main calorimetric operation modes have been applied, the experimental results reported and their utility for developing an effective and reliable screening protocol discussed.     

Separation and continuous determination of the light rare earth elements and thorium in Baotou Iron Ore by a micro-column

A method for continuous determination of the light rare earth elements (LREEs) and thorium in Baotou Iron Ore was established. The light rare earths and thorium were adsorbed on a micro-column packed with HD-8 cation exchange resins. The light rare earth elements were eluted with 4 mol L⁻¹ HCl–2 mol L⁻¹ NH₄Cl solution and determined with tribromo-arsenzao by a 721-E spectrophotometry at 630 nm; thorium was eluted with 5% potassium oxalate solution and determined with Arsenazo III by a 721-E spectrophotometry at 660 nm. The measured values by the proposed method were in close agreement with the certified values (Baotou main ore standard sample, Baotou ore R-715 standard sample and GSD-2 standard sample). The RSD of the light rare earths and thorium in Baotou Iron Ore were of <1.70% and <1.99%, respectively.     

三酰甘油氧化聚合物的制备型快速柱层析-体积排阻色谱测定法

建立了一种简便、灵敏、无需内标的检测油脂中三酰甘油氧化聚合物(TGP)的分析方法。以制备型快速层析柱(PFC)(flash硅胶柱,20 g,40～60μm,6 nm)分离1 g油脂样品中极性组分(PC),经高效体积排阻色谱(HPSEC)(GPC柱,Ф7.8 mm×300 mm,粒径5μm,孔径10 nm)将PC细分为氧化三酰甘油寡聚物(TGO)、氧化三酰甘油二聚物(TGD)、氧化三酰甘油单体(ox-TGM)、二酰甘油(DG)、游离脂肪酸(FFA)。结合重量法测定油脂中PC、面积归一法测定PC中TGP,可准确定量油脂中的TGP含量。结果表明,TGO、TGD分别在28～1 800、11～2 800 mg/L范围内线性关系良好,相关系数(r2)分别为0.998 2、0.998 7,TGO及TGD的检出限(LOD)分别为28、11 mg/L,定量下限(LOQ)分别为113、44 mg/L;相当于油脂中TGP的LOD为0.01%。PFC-HPSEC法检测油脂TGP的相对标准偏差(RSD)均小于10%。PFC对3个PC加标水平(2.27%、8.47%、30.94%)的平均回收率为95%～98%,相对标准偏差(RSD)均低于4%。PFC-HPSEC方法与经典的硅胶柱-HPSEC方法定量油脂TGP的结果吻合度高,相对误差为0～8.9%。该方法能够在2 h内实现各种油脂中TGP含量的定量检测,包括使用过的废弃油脂与未使用的食用油脂,尤其适用于低含量TGP的初榨油和精炼油脂。     

The origin of virgin argan oil's high oxidative stability unraveled

To prepare either virgin edible or beauty argan oil, roasted or unroasted argan kernels are cold-pressed, respectively. Comparing the physicochemical parameters of edible and beauty argan oil immediately after preparation and after a two-year delay has led to the suggestion that phospholipids are a new and essential type of oil component participating in the excellent oxidative stability of edible argan oil, in addition to the already suggested Maillard-reaction products, phenols, and tocopherols.     

Thermal properties of polystyrene nanocomposites formed from rigid intercalation agent‐treated montmorillonite

Polystyrene (PS)/clay nanocomposites were prepared with two different new intercalation organophilic clays, the phosphonium salt (APP) and the ammonium 4‐(4‐adamantylphenoxy)‐1‐butanamine (APB) salts, by emulsion polymerization technique. X‐ray diffraction and transmission electron microscopy were performed to characterize the layered structures of APB‐ and APP‐treated polymer–clay nanocomposites, and both resulted in exfoliated structures. Molecular weights of PS obtained from these nanocomposites are slightly lower than the virgin PS formed under similar polymerization conditions. Coefficient of thermal expansion showed approximately a 44–55% decrease for APB‐ and APP‐intercalated clay nanocomposites relative to the pure PS. Both T_g and thermal decomposition temperature of the PS component in the nanocomposite are higher than the virgin PS, implying that the presence of clay is able to enhance thermal stabilities of the PS. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1781–1787, 2007