Characterization and Authentication of Significant Chinese Edible Oilseed Oils by Stable Carbon Isotope Analysis

The ratios of stable carbon isotopes (δ¹³C) of 12 oils extracted from Chinese edible oilseed samples and their individual fatty acids were determined by elemental analysis-isotope ratio mass spectrometry (EA-IRMS) and gas chromatography-isotope ratio mass spectrometry (GC-IRMS). The results have demonstrated that the δ¹³C ratios of the oils from C3-plant seeds range from ?26.8 to ?30.7‰, while the δ¹³C ratios of C4-plant maize oil are in the interval of ?14.1 to ?16.2‰. Eighteen fatty acids were identified and their abundances were measured by gas chromatography–mass spectrometry (GC–MS) in these oils with C_16:0, C_18:0, C_18:1 and C_18:2 as the major constituents. From the data on fatty acids and stable carbon isotopes, several sensitive markers were developed to detect the adulteration of Chinese edible oilseed oils. Examples are provided with pre-blended samples to illustrate the discrimination procedures and corresponding sensitive markers with emphasis on camellia seed oil, flax seed oil and perilla seed oil.     

Natural Abundance Carbon Isotopic Analysis Indicates the Equal Contribution of Local Synthesis and Plasma Uptake to Palmitate Levels in the Mouse Brain

Saturated fatty acids are the most abundant fatty acids in the brain, however, there has been some debate regarding the ability of intact dietary saturated fatty acids to be incorporated into the brain. In the present study, we use compound specific isotope analysis to measure the natural abundance carbon isotopic signature of brain, liver, and blood palmitic acid (PAM) and compare it to the dietary PAM and sugar isotopic signatures to calculate the relative contribution of both the incorporation of intact and endogenously synthesized PAM to these pools. Mice were equilibrated to the study diet, and extracted fatty acids were analyzed with gas chromatography isotope ratio mass spectrometry to determine the carbon isotopic signature of PAM (δ¹³C_PAM). Liver, serum total, and serum unesterified fatty acid δ¹³C_PAM ranged between ?20.6 and ?21.1 mUr and were approximately 8.5 mUr more enriched in ¹³C when compared to the dietary PAM signature. Brain δ¹³C_PAM was found to be more enriched than liver or blood pools (?16.7 ± 0.2 mUr, mean ± SD). Two end‐member‐mixed modeling using the carbon isotopic signature of dietary PAM and dietary sugars determined the contribution of synthesis to the total tissue PAM pool to range between 44% and 48%. This suggests that endogenous synthesis and dietary PAM are near equal contributors to brain, liver, and blood PAM pools. In conclusion, our data provide evidence that brain PAM levels are maintained by both local endogenous synthesis and through the uptake of intact PAM from the blood.     

Identification of Turkish extra virgin olive oils produced in different regions by using NMR (1H and 13C) and IRMS (13C/12C)

Isotope ratio mass spectroscopy (IRMS) and nuclear magnetic resonance (NMR) spectroscopy techniques are two of the analytical methods that are used to characterize food products. The aim of this study is to classify extra virgin olive oil (EVOO) samples collected from different regions of Turkey based on ¹H and ¹³C NMR spectra along with IRMS δ¹³C carbon isotope ratio data by using chemometrics multivariate data analysis methods. A total of 175 EVOO samples were analyzed in 2014/15 and 2015/16 harvest seasons. Multivariate classification and clustering models were used to identify geographical and botanical origins of the EVOOs. IRMS results showed that there was no significant difference in terms of δ¹³C values between the years in terms of harvest year (p > 0.05), only extraction phase and variety were statistically significant factors (p < 0.05). The interactions of the factors showed that the harvest year × variety interaction is important. The outcomes of this research clearly indicated that considering the partial least squares discriminant analysis result with NMR spectra, the percent success of the model in the South Marmara, North Aegean, and South Aegean region samples were 95%, 95.7%, and 96.4% in the model set, respectively. The results showed that by using classification and clustering models, geographic marking and labeling of these oils can be carried out regardless of differences in year and production systems (2 and 3 phase extraction system) according the NMR analysis.     

Application of a multidisciplinary approach for the evaluation of traceability of extra virgin olive oil

In this work, a multidisciplinary approach for the evaluation of extra virgin olive oil traceability (geographical provenience and botanical differentiation) is presented. Conventional techniques such as major chemical component determination (triacylglycerols, TAG and fatty acids) and other novel approaches as stable isotopic ratio (¹³C/¹²C in combination with ¹⁸O/¹⁶O) and thermal properties obtained from cooling curves and their deconvoluted peaks by means of differential scanning calorimetry were compared. Fifty‐three samples from different Italian regions, diverse cultivars, and two Mediterranean areas (Italy and Croatia) were analyzed with all the three techniques. The oils exhibited different values especially for δ¹⁸O and thermal properties of the deconvoluted peaks of crystallization according to Italian regions and/or cultivars. Data were treated by means of linear discriminant analysis inserting all parameters as predictors in models where the potentiality to discriminate oils was tested. All models revealed a good resolution among categories with selected TAG, δ¹⁸O values, and thermal properties of the deconvoluted peak set at the highest temperature exhibiting the highest weight for the discriminant functions. These findings could give strength to the utilization of new analytical techniques supporting those traditionally employed, also sustained by proper chemometric procedures, as suitable for the resolution of extra virgin olive traceability. Practical applications: Consumers' awareness of extra virgin olive oil traceability has recently increased the interest for new methods that can assess its geographical and botanical origins and new findings in this sector represent a key factor affecting the purchases in non‐producer countries. Multidisciplinary approaches supported by chemometric procedures enable the building of large databases and classification models for the determination of the provenience of extra virgin olive oil.     

Determination of iodine value of palm and palmkernel oil by carbon‐13 nuclear magnetic resonance spectroscopy

High resolution carbon‐13 nuclear magnetic resonance ( ¹³ CNMR) can be used for characterization of palm oil and palmkernel oil in determining the iodine value (IV) of the oil. It is only necessary to obtain the quantitative ¹³ CNMR spectrum of the oil in dilute CDCl₃ solution in the region of δ30.0‐δ24.7 ppm, which pertains to the methylene carbons along the acyl chain from the β‐carbonyl to the ω‐4. From the peak areas in the spectrum the average number of double bonds per triacylglycerol molecule and the average molecular weight can be calculated and hence the IV. The IVs of 18 samples of palm and palmkernel oil have been determined by ¹³ CNMR and by the Official Method of the American Oil Chemists Society. There is good agreement between the two sets of IVs. Conditions for obtaining reliable IVs by this ¹³ CNMR method are given.     

Chloramine T with iodine: A new reagent to determine the iodine value of edible oils

Chloramine T (N-chloro-p-toluenesulfonamide sodium salt) and iodine (2:1, w/w) in carbon tetrachloride and acetic acid (1:1, vol/vol), referred to as reagent (I) was found to be effective for the determination of Iodine value of edible oils. Reagent (I) reacted quantitatively with the double bonds of oils of known weight. The reagent left unreacted after 20–25 min was titrated against standard sodium thiosulfate solution (0.04 M) in presence of potassium iodide (10%, 5 mL). The difference in volume of sodium thiosulfate solution consumed by reagent (I) without and with oil was a basis to calculate the iodine value of oils used. The iodine values of different oils were also determined separately following the standard procedure of Wijs, and calculated iodine value was obtained from the gas chromatographic profile of fatty acids. The iodine value obtained by the new method was in agreement with the results of the standard methods. The results obtained indicate that the method could be a complementary or an alternative to the Wijs method.     

Chloramine T with iodine: A new reagent to determine the iodine value fo edible oils

Chloramine T (N-chloro-p-toluenesulfonamide sodium salt) and iodine (2:1, w/w) in carbon tetrachloride and acetic acid (1:1, vol/vol), referred to as reagent (I) was found to be effective for the determination of Iodine value of edible oils. Reagent (I) reacted quantitatively with the double bonds of oils of known weight. The reagent left unreacted after 20–25 min was titrated against standard sodium thiosulfate solution (0.04 M) in presence of potassium iodide (10%, 5 mL). The difference in volume of sodium thiosulfate solution consumed by reagent (I) without and with oil was a basis to calculate the iodine value of oils used. The iodine values of different oils were also determined separately following the standard procedure of Wijs, and calculated iodine value was obtained from the gas chromatographic profile of fatty acids. The iodine value obtained by the new method was in agreement with the results of the standard methods. The results obtained indicate that the method could be a complementary or an alternative to the Wijs method.     

Determination of selenium,arsenic, iodine and bromine in fish,plant and mammalian oils by cyclic instrumental neutron activation analysis

The concentrations of arsenic, selenium, iodine and bromine in a series of fish, plant and mammalian oils have been determined by cyclic instrumental neutron activation analysis (CINAA). Crude fish oils contain between 0.047 and 0.151 μg Se g⁻¹, 2.36–14.5 μg As g⁻¹, 2.36–9.63 μg Br g⁻¹ and 0.97–4.76 μgI g⁻¹. Seal oil contains the same four elements, but at levels below the lower end of the fish oil ranges. Iodine, bromine and arsenic were not detected in rape-seed or soybean oils and the concentration of selenium varied from < 0.010 to 0.042 μg g⁻¹. The levels of selenium, iodine and bromine are reduced markedly by hydrogenation of the menhaden oils. The CINAA method yielded results which were in agreement with pub-lished values obtained by other methods. The technique was rapid, requiring minimal sample manipulation, and was essentially free from interferences.     

Characterization of farmed and wild salmon (Salmo salar) by a combined use of compositional and isotopic analyses

Gas chromatography, isotope ratio mass spectrometry, and high-resolution ²H site-specific natural isotope fractionation/nuclear magnetic resonance spectroscopy have been used to study the different kinds of fish oils and lipids extracted from muscle of wild and farmed salmon (Norway, Scotland). A statistical analysis of the fatty acid compositions, overall ²H and ¹³C isotope ratios, and molar fractions of the isotopomeric deuterium clusters was carried out to select the most efficient variables for distinguishing the different groups of salmons and fishes studied. A classification analysis based on four fatty acid compositions, three deuterium molar fractions, and the overall (D/H)_tot isotope ratio of fish oils completely assings the oils to the right group.     

Authentication of Edible Vegetable Oil and Refined Recycled Cooking Oil Using a Micro-UV Spectrophotometer Based on Chemometrics

We have developed a new method to make a clear distinction between edible oil and refined recycled cooking oil by using a micro-ultraviolet spectrophotometer and analysis of spectra full data combined with principal component analysis (PCA) and cluster discriminant analysis (CDA). This method shows an excellent capability of distinguishing edible oil from refined recycled cooking oil, which is difficult to accomplish by previous methods using physical and chemical properties. Edible oils and refined recycled cooking oils have the different positions on the resulting plot of PCA and CDA. The oil samples are respectively concentrated relatively distribution and distinct from other kinds, with a certain amount of edge intersection between samples. But the edible oil and refined recycled cooking oil samples have a clear divisional interface. By the increase in sampling and the improvement of modeling, the edge intersection or overlap of commonality between samples can be reduced. Using this method, it is possible to determine qualitatively the identity of unknown samples.     

Purity assessments of major vegetable oils based on δ13C values of individual fatty acids

The fatty acid compositions and δ¹³C values of the major fatty acids of more than 150 vegetable oils were determined to provide a database of isotopic information for use in the authentication of commercial maize oil. After extraction of oils from seeds, nuts or kernels, and methylation, fatty acid compositions were determined by capillary gas chromatography. All compositions were within the ranges specified by the Codex Alimentarius. Gas chromatography combustion-isotope ratio mass spectrometry was employed to determine the δ¹³C values of the major fatty acids of the oils. A large number of pure maize oils and potential adulterant oils from various parts of the world were studied to assess the sources of variability in δ¹³C values. Such information is vital to establishing the compound specific isotope technique as a reliable means of assessing vegetable oil purity. Variability in δ¹³C values was related to the geographical origin of the oil, year of harvest, and the particular variety of oil. This suggests that the ultimate δ¹³C values of fatty acids are determined by a combination of environmental and genetic factors.     

13C NMR as a primary method for determining saturates,cis‐ and trans‐monounsaturates and polyunsaturates in fats and oils for nutritional labeling purposes

The suitability of ¹³C NMR as a primary method for the analysis of lipids to obtain nutritional labeling compositional data (NLCD), i.e. the percentages of saturated, cis‐monounsaturated, trans‐monounsaturated, and cis‐polyunsaturated fat, was assessed. The ¹³C NMR methodology was developed by using mixtures of pure triglycerides as model lipids to optimize and standardize scan conditions and spectral pre‐processing procedures, establish fixed integration limits for measurement of the ¹³C resonances used in the determination of NLCD, and evaluate the quantitative accuracy of the ¹³C NMR analysis. The standardized ¹³C NMR methodology allowed the NLCD of the model triacylglycerol mixtures to be determined within ?±1%. To further evaluate the methodology, two sets of validation samples, consisting of ten unhydrogenated oils from the American Oil Chemists' Society Laboratory Proficiency Program (AOCS‐LPP) and two trans‐containing AOCS‐LPP samples combined with three samples from a hydrogenation process, were analyzed. Good overall agreement between the NMR‐determined NLCD (in units of mol‐%) and the mol‐% NLCD calculated for these samples from fatty acid compositional data obtained by gas chromatography was found, including good tracking of the trans content in the second validation set. Given that the NLCD must be expressed on a wt‐% basis to be of practical utility, a means of mol‐% to wt‐% conversion was developed assuming all unsaturates to be C₁₈ and obtaining the weight‐average molecular weight of the saturated fatty acid contributions from the NMR data. This conversion was shown to be especially effective for oil blends, where errors become significant if unit conversion is not done. This work indicates that ¹³C NMR can provide excellent primary NLCD data, even in wt‐% terms, which can be used for calibrating simpler and automatable instrumental methods such as FTIR spectrometers to determine or screen for NLCD for fats and oils or lipids extracted from food on a routine basis.     

Comparison of catabolic rates of fatty acids using stable isotope and isotope‐ratio mass spectrometry

The catabolic rates of individual fatty acids in mice were compared using stable isotope (¹³C)‐labeled fatty acids and isotope‐ratio mass spectrometry (IRMS). The catabolic rates were evaluated from the ratio of ¹³C and ¹²C in carbon dioxide expired by mice. The results showed that the catabolic rate of octanoic acid is three times faster than that of palmitic acid. This result is consistent with previous reports using radioisotope ¹⁴C showing that medium‐chain fatty acids are more easily beta‐oxidized than long‐chain fatty acids. The catabolic rates of odd‐numbered fatty acids such as pentadecanoic acid and heptadecanoic acid were significantly lower compared to those of even‐numbered fatty acids such as palmitic acid. These findings support previous reports that show odd‐numbered fatty acids easily accumulating in body fat. The high accumulation of odd‐numbered fatty acids in body fat thus directly reflects a low degree of beta‐oxidization. The combination of stable isotope‐labeled compounds and IRMS serves as a powerful tool in lipid analysis.     

Changes in Tissue Lipid and Fatty Acid Composition of Farmed Rainbow Trout in Response to Dietary Camelina Oil as a Replacement of Fish Oil

Camelina oil (CO) replaced 50 and 100 % of fish oil (FO) in diets for farmed rainbow trout (initial weight 44 ± 3 g fish^?1). The oilseed is particularly unique due to its high lipid content (40 %) and high amount of 18:3n‐3 (α‐linolenic acid, ALA) (30 %). Replacing 100 % of fish oil with camelina oil did not negatively affect growth of rainbow trout after a 12‐week feeding trial (FO = 168 ± 32 g fish^?1; CO = 184 ± 35 g fish^?1). Lipid and fatty acid profiles of muscle, viscera and skin were significantly affected by the addition of CO after 12 weeks of feeding. However, final 22:6n‐3 [docosahexaenoic acid (DHA)] and 20:5n‐3 [eicosapentaenoic acid (EPA)] amounts (563 mg) in a 75 g fillet (1 serving) were enough to satisfy daily DHA and EPA requirements (250 mg) set by the World Health Organization. Other health benefits include lower SFA and higher MUFA in filets fed CO versus FO. Compound‐specific stable isotope analysis (CSIA) confirmed that the δ¹³C isotopic signature of DHA in CO fed trout shifted significantly compared to DHA in FO fed trout. The shift in DHA δ¹³C indicates mixing of a terrestrial isotopic signature compared to the isotopic signature of DHA in fish oil‐fed tissue. These results suggest that ~27 % of DHA was synthesized from the terrestrial and isotopically lighter ALA in the CO diet rather than incorporation of DHA from fish meal in the CO diet. This was the first study to use CSIA in a feeding experiment to demonstrate synthesis of DHA in fish.     

Comparative analysis of different properties of polyhydroxyalkanoates isolated from two different bacterial strains: Alkaliphilus oremlandii OhILAs and recombinant Escherichia coli XL1B

We synthesized poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [P(3‐HB‐co‐3‐HV)] copolymer having different contents of 3‐hydroxyvalerate (3‐HV) units (16.04, 16.3, 24.95, 25.62, and 16.52 mol % 3‐HV) with different yields of polyhydroxyalkanoates (PHAs) by feeding with different cooking oils and with Alkaliphilus oremlandii OhILAs strain. The PHA production efficiency of the Alkaiphilus strain was compared with that of the control strain, Bacillus cereus. The synthesis of each PHA biopolymer was performed with different toxic spent oils as the sole carbon source in an oil‐in‐water‐based microemulsion medium. We observed that the productivity of the poly(3‐hydroxybutyrate) [P(3‐HB)] copolymer from the Alkaliphilus strain was higher than those of the PHAs isolated from B. cereus and the Escherichia coli XL1B strain. The synthesized PHA copolymers were characterized by ¹H‐NMR and Fourier transform infrared (FTIR) spectroscopy. In the ¹H‐NMR spectra, a doublet resonance peak at 1.253 ppm of the/ methyl protons of the 3‐hydroxybutyrate (3‐HB) side group and one at 0.894 ppm due to the methyl protons of the 3‐HV side group indicated the presence of 3‐HB and 3‐HV units in the copolymer. The chemical shift values at 1.25 and 2.2 ppm, due to the resonance absorption peaks of the methyl protons and methylene protons, confirmed the synthesis of the P(3‐HB) homopolymer. From the FTIR spectra, a strong C?O stretching frequency in the range of 1745–1727 cm^?1, together with strong C? O stretching bands near 1200 cm^?1 and a strong band near 3400 cm^?1, confirmed the synthesis of P(3‐HB‐co‐3‐HV) and P(3‐HB). Thus, waste cooking oil as a substrate provided an alternate route for the formation of P(3‐HB‐co‐3‐HV) and P(3‐HB) by Alkaliphilus and E. coli strains, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41080.     

Extraction and Identification of Phytosterols in Manketti (Schinziophyton rautanenii) Nut Oil

Phytosterols of manketti (Schinziophyton rautanenii) nut oil extracted by Soxhlet, mechanical shaking using hexane, screw press and supercritical carbon dioxide, were analyzed by gas chromatography with flame ionization detection and identified by gas chromatography–mass spectrometry. The presence of several phytosterols (campesterol, stigmasterol, β‐sitosterol, Δ⁵‐avenasterol, 22‐dihydrospinasterol and Δ⁷‐avenasterol) previously reported in manketti oil, was confirmed. In addition, another fourteen phytosterols (lanosterol, Δ^5,23‐stigmastadienol, Δ⁷‐campesterol, clerosterol, obtusifoliol, Δ^5,24(25)‐stigmastadienol, α‐amyrin, gramisterol, cycloeucalenol, cycloartenol, stigmasta‐8,24‐dienol‐3‐β‐ol, 28‐methylobtusifoliol, 24‐methylenecycloartenol and citrostadienol) were identified. The phytosterols, β‐sitosterol, Δ⁵‐avenasterol and campesterol, had the highest concentrations in oils extracted by all the methods, whereas stigmasterol and cycloartenol were abundant in oils extracted by mechanical shaking and supercritical carbon dioxide. Total phytosterols and the quantities of individual phytosterols differed significantly (p ≤ 0.05) in oils from the four extraction methods. Mechanical shaking extracted the highest levels of total sterols (22,100 mg/100 g oil), followed by supercritical fluid extraction (9,550 mg/100 g oil). Screw press and Soxhlet extracted oils contained the lowest levels of total sterols, 3,810 mg/100 g oil and 3,350 mg/100 g oil, respectively.     

Heat and Mass Transfer During Fry-Drying of Sewage Sludge

Deep-frying, which consists of immersing a wet material in a large volume of hot oil, presents a process easily adaptable to dry rather than cook materials. A suitable material for drying is sewage sludge, which may be dried using recycled cooking oils (RCO) as frying oil. One advantage is that this prepares both materials for convenient disposal by incineration.

This study examines fry-drying of municipal sewage sludge using recycled cooking oil. The transport processes occurring during fry-drying were monitored through sample weight, temperature, and image analysis. Due to the thicker and wetter samples than the common fried foods, high residual moisture is observed in the sludge when the boiling front has reached the geometric center of the sample, suggesting that the operation is heat transfer controlled only during the first half of the process followed by the addition of other mechanisms that allow complete drying of the sample. A series of mechanisms comprising four stages (i.e., initial heating accompanied by a surface boiling onset, film vapor regime, transitional nucleate boiling, and bound water removal) is proposed. In order to study the effect of the operating conditions on the fry-drying kinetics, different oil temperatures (from 120 to 180°C), diameter (D = 15 to 25 mm), and initial moisture content of the sample (4.8 and 5.6 kg water·kg^?1 total dry solids) were investigated.     

Dietary trans α‐linolenic acid does not inhibit Δ5‐ and Δ6‐desaturation of linoleic acid in man

Dietary trans monoenes have been associated with an increased risk of heart disease in some studies and this has caused much concern. Trans polyenes are also present in the diet, for example, trans α‐linolenic acid is formed during the deodorisation of α‐linolenic acid‐rich oils such as rapeseed oil. One would expect the intake of trans α‐linolenic acid to be on the increase since the consumption of rapeseed oil in the western diet is increasing. There are no data on trans α‐linolenic acid consumption and its effects. We therefore carried out a comprehensive study to examine whether trans isomers of this polyunsaturated fatty acid increased the risk of coronary heart disease. Since inhibition of Δ6‐desaturase had also been linked to heart disease, the effect of trans α‐linolenic acid on the conversion of [U‐¹³C]‐labelled linoleic acid to dihomo‐γ‐linolenic and arachidonic acid was studied in 7 healthy men recruited from the staff and students of the University of Edinburgh. Thirty percent of the habitual fat was replaced using a trans ‘free’‐ or ‘high’ trans α‐linolenic acid fat. After at least 6 weeks on the experimental diets, the men received 3‐oleyl, 1,2‐[U‐¹³C]‐linoleyl glycerol (15 mg twice daily for ten days). The fatty acid composition of plasma phospholipids and the incorporation of ¹³C‐label into n‐6 fatty acids were determined at day 8, 9 and 10 and after a 6‐week washout period by gas chromatography‐combustion‐isotope ratio mass spectrometry. Trans α‐linolenic acid of plasma phospholipids increased from 0.04 ? 0.01 to 0.17 ? 0.02 and cis ? ‐linolenic acid decreased from 0.42 ? 0.07 to 0.29 ? 0.08 g/100 g of fatty acids on the high trans diet. The composition of the other plasma phospholipid fatty acids did not change. The enrichment of phosphatidyl ¹³C‐linoleic acid reached a plateau at day 10 and the average of the last 3 days did not differ between the low and high trans period. Both dihomo‐γ‐linolenic and arachidonic acid in phospholipids were enriched in ¹³C, both in absolute and relative terms (with respect to ¹³C‐linoleic acid). The enrichment was slightly and significantly higher during the high trans period (P<0.05). Our data suggest that a diet rich in trans α‐linolenic acid (0.6% of energy) does not inhibit the conversion of linoleic acid to dihomo‐γ‐linolenic and arachidonic acid in healthy middle‐aged men consuming a diet rich in linoleic acid.     

Estimation of Glycerides and Free Fatty Acid in Oils Extracted From Various Seeds from the Indian Region by NMR Spectroscopy

The present study is focused on the quantification of glycerides and free fatty acid in oils extracted from various seeds for biodiesel production from Indian territory. A new method based on ¹H- and ¹³C-NMR spectroscopic techniques was developed in order to estimate triglycerides (TG), diglycerides, monoglycerides, free fatty acids (FFA) and various other components such as para-substituted phenols, silylated methyl esters, aromatic acids, naphthalenes, etc. Iodine values of the extracted oils were estimated using the developed ¹H-NMR spectroscopic method, which was correlated with the TG content present in the sample. Results by the NMR method were validated by the blend preparation, fatty acid composition determined by the GC and from the iodine value of the samples. The developed method is direct, rapid and no sample treatment is required. The results from these comprehensive studies indicated that NMR spectroscopic technique is useful for the quantification of extracted oils and can be used effectively for the development and monitoring of biodiesel production and determining the fuel quality.     

N.m.r. study of US Eastern and Western shale oils produced by pyrolysis and hydropyrolysis

Shale oils produced from US Eastern and Western oil shales by pyrolysis and hydropyrolysis processes have been investigated by both ¹H and ¹³C high-resolution n.m.r. techniques. Eastern shale oils produced by hydropyrolysis, and subsequently hydrotreated, were also included. From the n.m.r. data of the shale oils, the average molecular structure parameters were calculated. These parameters quantitatively represent the differences observed in the n.m.r. spectra of the various shale oils because of changes in the chemical composition. Mol percentages of aromatics, olefins, and alkanes were also determined for the shale oils, and show that the composition of the shale oil is dependent upon the geographic origin of the oil shale, the pyrolysis method, and the hydrogenation process. In addition to the study of shale oils, solid-state ¹³C n.m.r. spectra of Eastern and Western oil shales before and after pyrolysis and hydropyrolysis were obtained. The spectral data show that the carbon aromaticities for the Eastern oil shales and shale oils are higher than for the Western oil shale and shale oils. The data also show that hydropyrolysis relative to pyrolysis reduces the amount of residual organic carbon remaining on the spent shales. Carbon aromaticity data for both oil shale and shale oil suggest that the organic moieties present in kerogen may be retained in the shale oils to a greater extent after hydropyrolysis than after pyrolysis.