Humic acid fouling in the membrane distillation process

This work investigates the extent of humic acid fouling during the membrane distillation process for water treatment. The effects of pH, ionic strength, and divalent ion on fouling were studied. The experiments were performed with a 0.22-μm PVDF flat-sheet membrane in a direct contact membrane distillation unit. Flux declines were negligible (less than 6%) for the ranges of humic acid concentration, ionic strength, and pH studied. The examination of the membrane surface by SEM revealed a thin deposit layer. The addition of divalent cations (Ca²⁺) into the solution considerably reduced flux when Ca²⁺ concentration exceeded the critical coagulation concentration. Ca²⁺ affected flux by forming complexes with humic acids and resulted in coagulation on the membrane surface. The normalized flux, J/J₀, was 0.57 after 18 h of operation when the CaCl₂ concentration was 3.775 mM. However, the deposit of humic acid coagulate on the membrane surface was loosely packed, and was rather easily removed. Rinsing of the fouled membrane with clean water and a 0.1 M NaOH solution gave 100% of flux recovery.     

Enhancement of Palmarumycins C12 and C13 Production in Liquid Culture of Endophytic Fungus Berkleasmium sp. Dzf12 after Treatments with Metal Ions

The influences of eight metal ions (i.e., Na⁺, Ca²⁺, Ag⁺, Co²⁺, Cu²⁺, Al³⁺, Zn²⁺, and Mn⁴⁺) on mycelia growth and palmarumycins C₁₂ and C₁₃ production in liquid culture of the endophytic fungus Berkleasmium sp. Dzf12 were investigated. Three metal ions, Ca²⁺, Cu²⁺ and Al³⁺ were exhibited as the most effective to enhance mycelia growth and palmarumycin production. When calcium ion (Ca²⁺) was applied to the medium at 10.0 mmol/L on day 3, copper ion (Cu²⁺) to the medium at 1.0 mmol/L on day 3, aluminum ion (Al³⁺) to the medium at 2.0 mmol/L on day 6, the maximal yields of palmarumycins C₁₂ plus C₁₃ were obtained as 137.57 mg/L, 146.28 mg/L and 156.77 mg/L, which were 3.94-fold, 4.19-fold and 4.49-fold in comparison with that (34.91 mg/L) of the control, respectively. Al³⁺ favored palmarumycin C₁₂ production when its concentration was higher than 4 mmol/L. Ca²⁺ had an improving effect on mycelia growth of Berkleasmium sp. Dzf12. The combination effects of Ca²⁺, Cu²⁺ and Al³⁺ on palmarumycin C₁₃ production were further studied by employing a statistical method based on the central composite design (CCD) and response surface methodology (RSM). By solving the quadratic regression equation between palmarumycin C₁₃ and three metal ions, the optimal concentrations of Ca²⁺, Cu²⁺ and Al³⁺ in medium for palmarumycin C₁₃ production were determined as 7.58, 1.36 and 2.05 mmol/L, respectively. Under the optimum conditions, the predicted maximum palmarumycin C₁₃ yield reached 208.49 mg/L. By optimizing the combination of Ca²⁺, Cu²⁺ and Al³⁺ in medium, palmarumycin C₁₃ yield was increased to 203.85 mg/L, which was 6.00-fold in comparison with that (33.98 mg/L) in the original basal medium. The results indicate that appropriate metal ions (i.e., Ca²⁺, Cu²⁺ and Al³⁺) could enhance palmarumycin production. Application of the metal ions should be an effective strategy for palmarumycin production in liquid culture of the endophytic fungus Berkleasmium sp. Dzf12.     

Effects of co-ion initial concentration ratio on removal of Pb<Superscript>2+</Superscript> from aqueous solution by modified sugarcane bagasse

A modified sugarcane bagasse (SCB) fixed bed column was used to remove Pb²⁺ from aqueous solution. To determine the optimal condition for Pb²⁺ separation, Ca²⁺ was chosen as the model interfering ion, and effects of Ca²⁺ and Pb²⁺ initial concentration ratio (C ₀ ^Ca : C ₀ ^Pb ) on the adsorption of Pb²⁺ were investigated. Results showed that adsorption amount ratio of Ca²⁺ and Pb²⁺ (q _e ^Ca : q _e ^Pb ) had a good linear relationship with C ₀ ^Ca : C ₀ ^Pb . Mass ratio of Pb²⁺ absorbed on the modified SCB was higher than 95% at C ₀ ^Ca : C ₀ ^Pb <1.95, illustrating that Pb²⁺ could be selectively removed from aqueous solution. To verify that, simulated waste water containing co-ions of K⁺, Na⁺, Cd²⁺ and Ca²⁺ was treated, and results showed that the equilibrium amount of Pb²⁺, K⁺, Na⁺, Cd²⁺ and Ca²⁺ adsorbed was 134.14, 0.083, 0.058, 1.28, and 1.28mg g^?1, respectively, demonstrating that the modified SCB could be used to remove Pb²⁺ from aqueous solution in the investigated range.     

Isolation and characterization of the monounsaturated long chain fatty acids ofMycobacterium tuberculosis

The positions of double bond in the monounsaturated C₁₅−C₃₂ fatty acids ofMycobacterium tuberculosis H37Ra were established by gas chromatography/mass spectrometry of the ozonized esters and their pyrrolidide derivatives. The monounsaturated C₁₅−C₂₁ fatty acids had the double bond primarily at the Δ⁹ position while the monounsaturated longer chain fatty acids (C₂₂−C₃₂) had the double bond in several positions. Many of the latter acids, especially the odd-numbered series, were very complex isomeric mixtures. Quantitation showed the most abundant even-numbered long chain fatty acid isomers to be as follow: C₂₂, Δ⁴; C₂₄, Δ⁵; C₂₆, Δ⁷ and Δ⁹; C₂₈, Δ⁹; C₃₀, Δ¹¹ and Δ¹³; C₃₂, Δ¹³ and Δ¹⁵.     

Mass spectrometric analysis of the fatty acids and nonsaponifiable lipids ofEimeria tenella oocysts

The fatty acids and nonsaponifiable lipids ofEimeria tenella oocysts were analyzed by gas liquid chromatography and combined gas liquid chromatographymass spectrometry. The fatty acids detected were identified as C_14∶0, C_16∶0, C_16∶1, C_18∶0, C_18∶1, and C_18∶2. Though the wt of the fatty acid fraction decreased during sporulation from 91 μg per 10⁶ oocysts to 47 μg per 10⁶ oocysts, the relative amounts of these fatty acids did not change appreciably. The nonsaponifiable lipids ofE. tenella consisted of cholesterol and unbranched primary alcohols of 22, 24, 26, 28, 30, and 32 carbons. Mass fragmentography demonstrated that each species of alcohol consisted of saturated and monounsaturated derivatives. Trimethylsilyl ethers of fatty alcohols were found to offer several important advantages over free alcohols for mass spectrometric characterization. Before sporulation, most fatty alcohols were in the oocyst wall. During sporulation, the wt of the nonsaponifiable lipids increased from 16 μg per 10⁶ oocysts of 44 μg per 10⁶ oocysts due largely to synthesis of C₂₄ and C₂₆ alcohols. The newly synthesized fatty alcohols were not deposited in the oocyst wall.     

Characterization of chilean hazelnut (Gevuina avellana mol) seed oil

The fatty acid composition, tocopherol and tocotrienol content, and oxidative stability of petroleum benzene-extracted Gevuina avellana Mol (Proteaceae) seed oil were determined. Positional isomers of monounsaturated fatty acids were elucidated by gas chromatography-electron impact mass spectrometry after 2-alkenyl-4,4-dimethyloxazoline derivatization. This stable oil (Rancimat induction period at 110°C: 20 h) is composed of more than 85% monounsaturated fatty acids and about equal amounts (6%) of saturated and polyunsaturated (principally linoleic) fatty acids. Unusual positional isomers of monounsaturated fatty acids, i.e., C_16:1 Δ¹¹, C_18:1 Δ¹², C_20:1 Δ¹¹, C_20:1 Δ¹⁵, C_22:1 Δ¹⁷, and presumably C_22:1 Δ¹⁹ were identified. The C_18:1 Δ¹² and C_22:1 Δ¹⁹ fatty acids are described for the first time in G. avellana seed oil. While only minute quantities of α-, γ-tocopherols and β-, γ- and δ-tocotrienols were found, the oil contained a substantial amount of α-tocotrienol (130 mg/kg). The potential nutritional value of G. avellana seed oil is discussed on the basis of its composition.     

Synthesis and Surface Active Properties of Sulfonated Acrylate Esters Based on Al‐Cedre Oil

Sulfonated acrylate esters have been synthesized by using renewable raw materials such as fatty alcohols of Al‐Ceder oil. Mixed fatty acids were isolated from Al‐Ceder oil by hydrolysis; both saturated and unsaturated fatty acids were isolated from the mixed fatty acids. The methyl esters of mixed fatty acid, saturated and unsaturated acids of Al‐Cedre oil were subjected to reduction with (LiAlH4) to give the corresponding fatty alcohols. The products of the reduction process were saponified and the hydroxyl values were estimated to further confirm the reduction occurrence. The acrylate esters were synthesized by esterification of acrylic acid with fatty alcohols of C_16:0, C_18:0, C_18:1, and C_18:2 mixed saturated, mixed unsaturated and mixed fatty acids of Al‐Cedre oil, respectively. This esterification was followed by addition of NaHSO₃ to form bisulfite adducts. The structures of the prepared surfactants were characterized by IR and ¹HNMR spectroscopy. A series of useful surface parameters, stability towards acids and base hydrolysis and calcium stability have been determined.     

Stable isotope characterization of olive oils: II-deuterium distribution in fatty acids studied by nuclear magnetic resonance (SNIF-NMR)

Site-specific isotope fractionation of hydrogen was investigated, at natural abundance, by deuterium nuclear magnetic resonance (SNIF-NMR) on nearly two hundred olive oil samples. Owing to the complexity of the ²H-NMR spectra of the mixtures of fatty acids obtained after hydrolysis of the oils, the different signals were gathered into six clusters. Knowing the contribution to the clusters of each of the four fatty acids considered (C_16:0, C_18:0, C_18:1, and C_18:2) and the composition of the fatty acids in the mixture, it is possible to compute the site-specific isotope ratios of the clusters from the molar fractions obtained from the ²H-NMR-spectra and from the total isotope ratio of the mixture, determined by isotope ratio mass spectrometry (IRMS). The results are discussed in terms of geographical (country, region and elevation) and temporal (year) parameters and they are tentatively explained on a climatic basis.     

Fatty Acid Composition in Ergosteryl Esters and Triglycerides from the Fungus Ganoderma lucidum

Free and esterified ergosterols are detected almost solely in fungi and are often employed as a biomarker of living fungi. In this work, the fatty acid composition and δ¹³C values of major fatty acids in triglycerides and ergosteryl esters from the fungus Ganoderma lucidum were analyzed by gas chromatography–mass spectrometer and gas chromatography–isotopic ratio mass spectrometer, respectively. The results showed that the fatty acid profiles varied in triglycerides and ergosteryl esters. The percentage of saturated fatty acids in ergosteryl esters was remarkably higher than that in triglycerides, where C_18:1^Δ9c was the predominant fatty acid and constituted 61.26 % of the total fatty acids. In contrast, C_16:0 was the predominant fatty acid and constituted 71.88 % of the total fatty acids in ergosteryl esters. The study suggests that, after fungal death, free ergosterols in the cell membrane of the dead fungus were esterified with preferentially saturated fatty acids, mainly C_16:0, from triglycerides and then stored in lipid particles for a longer period while free ergosterol markedly decreased. The δ¹³C values of C_16:0, C_18:0, C_18:1 and C_18:2 in ergosteryl esters exhibit a pronounced depletion in ¹³C compared with that in triglycerides within the range of ?1.3 to ?0.9 ‰, supporting the above inference. It is again suggested that free ergosterol in the cell membrane should be used as an indicator of living fungi, and ergosteryl esters in the lipid particles should not be included in the measurement of living fungal biomass.     

Fast atom bombardment and tandem mass spectrometry of phosphatidylserine and phosphatidylcholine

Fast atom bombardment (FAB) desorption of phosphatidylserine and various phosphatidylcholines produces a limited number of very informative negative ions. Especially significant is the formation of (M-H)⁻ ions for phosphatidylserine, a compound which does not yield informative high mass ions by other ionization methods. Phosphatidylcholines of not yield (M-H)⁻ ions but instead produce three characteristic high mass ions, (M-CH ₃ ⁺ _⁻, [M-HN(CH₃) ₃ ⁺ ]⁻ and [M-HN(CH_{3 3} ⁺ -C₂H₂]⁻. Both classes of lipids also yield anions attributed to the carboxylate components of these complex lipids. FAB desorption in combination with collisional activation allows for characterization of fragmentation and determination of structural features. Collisional activation of the carboxylate anion fragments from the complex lipids is especially informative. Structural characterization of the fatty acid chain can be achieved as the released saturated carboxylate anions undergo a highly specific 1,4-elimination of H₂, which results in the losses of the elements of CH₄, C₂H₆, C₃H₈...in a fashion entirely consistent with the chemistry of carboxylate anions desorbed from free fatty acids. These C_nH_2n+2 losses begin at the alkyl terminus and progress along the entire alkyl chain. Modified fatty acids undergo a similar fragmentation; however, the modification affects the series of C_nH_2n+2 losses in a manner which permits determining the type of modification and its location on the fatty acid chain.     

Peroxidative formation of C3-hydrocarbons from an ω-4 polyunsaturated fatty acid(16∶3ω4) in the algaBumilleriopsis

Under peroxidative conditions (i.e., illumination in the presence of Cu²⁺ or ap-nitro diphenylether herbicide), the xanthophycean microalga,Bumilleriopsis filiformis, evolves C₂ and C₅ hydrocarbons besides substantial amounts of propane and propene. Fatty acids were separated as methyl esters by argentation and reversed-phase thin layer chromatography and the fractions subsequently peroxidized by illuminated and copper-supplementedAnacystis thylakoids. These membranes do not contain polyunsaturated fatty acids and are, therefore, unable to evolve volatile hydrocarbons by itself. The C₂ and C₅ hydrocarbons formed by the fractions added match with their content of ω-3 and ω-6 fattyacid species having 2–4 double bonds. The fractions yielding C₃ hydrocarbons contain a fatty acid hitherto unknown forBumilleriopsis, which was isolated and identified as 16∶3ω4.     

Isovaleric acid as a precursor of odd numbered iso fatty acids in Tetrahymena

Tris isovalerate-supplementedTetrahymena pyriformis W showed no qualitative change in fatty acid composition; however, an increase in polar lipids that contain odd numbered iso acids (C₁₃, C₁₅, C₁₇, C₁₉) occurred. This change was accompanied by a decrease in the proportional amount of even numbered normal acids (C₁₄, C₁₆, C₁₈). The neutral and polar lipids from cells incubated with [1-¹⁴C] isovaleric acid were found to contain radioactivity. The methyl esters of the saturated fatty acids obtained from the polar lipids by alkaline methanolysis were separated by reversed phase chromatography, the identities confirmed by gas chromatography-mass spectrometry, and the specific activities determined. Iso acids were found to be the most heavily labeled materials. In addition to ceramide, two sphingolipid components were detected. One yielded saturated fatty acids after acidic methanolysis, while the other contained >93% α-hydroxy fatty acids. Radioactivity was noted in the long chain base fraction derived from the sphingolipids. Progressive growth inhibition occurred as the isovalerate concentration was increased in the culture medium; however, the ciliates were morphologically indistinguishable from unsupplemented cells.     

Studies on characterization and variation in triglyceride fatty acids from punt/us sarana body lipids

Body lipids of P. sarana of four different sizes were fractionated into phospholipids, neutral lipids, nonsaponifiables, total fatty acids, polyunsaturated, monounsaturated and saturated fatty acid fractions. Percentage composition of each fraction was determined. The triglyceride fatty acids were identified by thin layer and gas liquid chromatography. C₈ to C₂₃ fatty acids including both odd numbered and branched chain acids were detected. The major constituents were C₁₄, C₁₅, C₁₆, C_16:1, C₁₈ C_18:1, C_18:2, C_18:3; forty-three other acids were detected in lower proportions. Composition of each fatty acids and their variation with size have been discussed.tP. sarana body lipids in general showed a behavior typical of fresh water fish by having a higher percentage of saturated C₁₆ and unsaturated C₁₈ acids and a lower percentage of unsaturated C₂₀ acid.     

Mechanochemical solid-phase reactions of humic acids with metal ions

The mechanochemical solid-phase reactions of humic acid with Cu²⁺, Ni²⁺, and Cd²⁺ metal ions were studied. The analysis of the mineral composition of humic acids by atomic emission spectrometry showed an increase in the concentrations of Cu²⁺, Ni²⁺, and Cd²⁺ ions after mechanical treatment.     

Swelling behaviour of poly(α‐hydroxyacrylic acid) gel

Poly(α‐hydroxy acrylic acid) (PHA) and poly(acrylicacid) (PAA) gels were prepared by irradiating the respective 15 wt% aqueous solutions with γ‐rays. Swelling ratios for PHA gel were measured as a function of pH and divalent cation (Mg²⁺, Ca²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺) concentration C₂ in the external solution to provide a comparison with the results for PAA gels. It was found that the swelling ratio of PHA gel steeply increases between pH 2 and 4, followed by a gradual swelling in the higher pH region. The corresponding steep swelling of PAA gel was observed at pH 3–6. Cation specificity in the equilibrium swelling ratio at a lower C₂ value (1.0 × 10⁻³ M) was approximately consistent with the binding selectivity in the solution system. Typically, the swelling ratio of PHA gel in the presence of Ca²⁺ was significantly lower than in the Mg²⁺ system, while the difference was slight for PAA gel. The response of the swelling ratio to changes in pH and C₂ was analysed as a first order relaxation to estimate the time constants. The (de)swelling kinetics measured by both the pH and C₂ jump were qualitatively interpreted in terms of main‐chain stiffness and intermolecular hydrogen bonding in the respective polymers. © 2000 Society of Chemical Industry     

Gas chromatographic identification of fatty acids,fatty alcohols,and hydrocarbons ofConvolvulus pluricaulis (chois)

Convolvulus pluricaulis (Chois) (Family: Convolvulaceae) (Hindi: Shankhapushpi), widely grown in the northern part of India, was analyzed for its fatty acids and waxy constituents. Straight chain hydrocarbons (C₂₂–C₃₃), fatty acids (C₁₄–C₂₈), and fatty alcohols (C₂₄–C₃₂) were found in the whole plant 95% aqueous ethanol extract. Hydrocarbons (C₂₇, C₃₁, and C₃₃), fatty acids (C₁₄, C₁₆, and C_18:2), and alcohols (C₂₆, iso-C₂₈, iso-C₃₀, and C₃₂) were the major components.     

Characterization of 2:1 type layered aluminosilicate via intercalation reaction

The stable intercalation compounds were synthesized by ion exchange reaction of the cations (Ca²⁺, Mg²⁺, etc.) existing in the interlayer of the 2:1 type layered natural aluminosilicate with n-decylammonium ion and by successive molecular intercalation reaction of the primary n-alcanol (ROH, R = C₁₀H₂₁, C₁₂ H₂₅, C₁₄H₂₉). The charge densities were calculated from the basal spacings of n-decylammonium derivatives under primary n-alcanol. As the result, the aluminosilicates used in this study have the charge density of 0.25, 0.34 per formula unit and interlayer cation exchange capacity of 69.3, 92.4 meg./l00g, respectively.     

Stable isotope characterization of olive oils. I—Compositional and carbon-13 profiles of fatty acids

Nearly 200 olive oils produced in the Mediterranean basin, mainly in Greece, during 4 yr from 1993 to 1996, were studied by gas chromatography (GC) and on-line GC-isotope ratio mass spectrometry (GC-C-IRMS). The composition of the oils in the more abundant fatty acids (C_16:0, C_16:1, C_18:0, C_18:1, C_18:2, and C_18:3) was obtained by GC after transesterification of the triglycerides into methyl esters. Using the hyphenated GC-C-IRMS technique, the ¹³C contents of the three most abundant acids, C_16:0, C_18:1, and C_18:2, were measured with satisfactory accuracy. The results, analyzed in terms of geographical, temporal, and botanical factors, provide new criteria for the authentication of olive oils.     

Molecular compounds generated by ruthenium tetroxide oxidation and preparative off line thermochemolysis of lignite humic acids from South Moravia: Implications for molecular structure

The composition of humic acids (HAs) isolated from a South Moravian lignite deposit was examined via thermochemolysis and RuO₄ oxidation. The combination of thermochemolysis with TMAH and TEAAc shows that fatty acids were mostly in a “free” form, tightly trapped within the humic acid organic network. Humic acids contain also trapped hydrocarbons. The relative distributions of these compounds confirm their higher plant origin. RuO₄ oxidation resulted in a lipophilic fraction containing mainly fatty acids. The hydrophilic fractions released upon RuO₄ oxidation comprised mostly aliphatic C₂-C₉ dicarboxylic acids and hydroxy acids related to short methylene bridges, to bridges between aromatic and/or oxygenated moieties such as aliphatic chains of ligneous units.     

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.