Determination of resin acids in pulp mill EOP bleaching process effluent

Resin acids are tricyclic diterpenoids which are natural constituents of the wood from conifers. They are released from the wood during the manufacture of pulp and paper. These acids are very resistant to chemical degradation and survive the pulping and also the EOP bleaching process (EOP=alkaline extraction, oxygen and peroxide, the chemicals used in the bleaching process). Resin acids were extracted from alkaline medium using liquid–liquid extraction with t-butyl methyl ether and solid phase extraction with RP C18 adsorbent and a highly porous polystyrene-divinylbenzene polymer. After conversion of the acids to their pentafluorobenzyl esters, the extracts were analysed by GC/MS using a 25 m OV17 capillary column. Recovery values for single resin acids were determined by all three extraction methods. The solid phase extraction methods were applied to the analysis of the EOP effluent from a pulp mill bleaching process. 14 different resin acids and one resin acid methyl ester have been identified in the effluent. One of these was an oxo resin acid which might well be a product of the bleaching process.     

Comparison of gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry for the determination of fatty and resin acids in paper mill process waters

A comparative study of the performance of liquid chromatography (LC)-atmospheric pressure chemical ionisation (APCI)-mass spectrometry (MS) and gas chromatography (GC)-mass spectrometry techniques for the determination of resin and fatty acids from paper mill process waters was carried out. These compounds are responsible for the high toxicity of paper mill effluents and little research has been carried out regarding their analysis using mass spectrometric techniques. To prove the usability of GC and LC-MS, 16 treated and untreated water samples of recycle, kraft and pulp paper mills were analysed and good agreement was observed as regards to compounds detected and corresponding concentrations. This paper also reports the limits of detection, recoveries, reproducibility, linearity and precision using the two methods. GC-MS presented better selectivity and lower detection limits (below 0.2 microg/l), but derivatization of the extracts and the short life of derivatives (12-24 h) made the technique tedious and prone to high variations. Although LC-APCI-MS presented coelution of the non-aromatic resin acids, it also showed good sensitivity (limits of detection <3 microg/l) and permitted the detection of resin and fatty acids at microg/l level. In addition, since samples could be directly injected to the chromatographic system, LC-APCI-MS was proven as a powerful technique for quick and unequivocal quality control during papermaking.     

Separation of resin acids from fatty acids in relation to environmental studies.

Kraft mills pulping coniferous wood species discharge to their receiving waters effluents containing mixed resin and fatty acids. To study the fish-toxic properties of these fractions it is desirable to be able to separate them without causing double bond isomerizations in the acid-labile resin acid fraction. A method is described using toluenesulphonic acid as catalyst under very mild conditions and four examples of its application are given. It was not possible to separate tall oil samples without a low degree of resin acid isomerization.     

Resonance electron capture for determining double bond and hydroxy group locations in fatty acids

The nature and location of modifications of fatty acids are determined by resonance electron capture (REC) ionization of free acids and their methyl esters and pyrrolidides. The molecular negative ions (MNI) formed in the high resonance region undergo both charge-remote and charge-driven decomposition. The spectra of fragments arising from dissociation of these high-energy MNI contain decisive information on the original structure of the neutrals. The pyrrolidides of fatty acids result in simpler spectra on the one hand, and on the other hand these spectra give complete structure information.     

四种油料作物中脂肪酸的测定

建立了拟南芥种子中脂肪酸含量的超声萃取-气相色谱检测方法. 研究探讨了超声时间、加热温度、超声功率、静置萃取时间、萃取剂种类等试验条件对拟南芥种子中脂肪酸含量检测的影响,优化了样品前处理条件及气相色谱检测条件. 结果表明,最优的样品处理条件为：甲酯化超声加热温度90 ℃,超声功率400 W,时间30 min,萃取剂为正己烷,加入萃取剂后4 000 r/min离心5 min. 在最优条件下,脂肪酸分离效果和标准曲线线性关系良好,检出限（LOD）为2.9~21.5 mg/kg,定量限（LOQ）为14.5~94.0 mg/kg,精密度为0.5%~7.9%. 方法所需样品量少,操作简单快速,准确性高,对于部分油料作物如油菜籽、花生、大豆中脂肪酸含量的检测同样适用.     

Determination of novel complexing agents in pulp and paper mill effluents and in lake water by liquid chromatography

A simple and sensitive high performance liquid chromatographic (HPLC) method with UV detection was developed for the determination of new diethanolamine derivative complexing agents. The quantitation of three complexing agents was accomplished as their Cu(II) complexes and their separation on a reversed phase C18 column using 0.01 M tetrabutyl ammoniumhydroxide and methanol as isocratic mobile phase. The limit of detection (LOD) ranges from 0.1 to 2.0 mg/l and the method has a wide linear range, from LOD to 150 mg/l. The method was successfully applied for the analysis of lake water and wastewater effluent from pulp and paper mill spiked with studied complexing agents.     

Effect of fatty and resin acids on properties of the surface of kraft lignin

The effect of oleic and abietic acids on the properties of the surface of alkali lignins and the capability of lignins to stabilize water-oil emulsions was examined with kraft spruce and birch lignins as examples. The kinetics of the breakdown of oleic acid-water and abietic acid-water emulsions stabilized by kraft lignins was studied.     

Determination by MS-MS of 1,1-dichlorodimethyl sulfone from pulp mill bleach plant effluents in aquatic organisms

Gas chromatography (GC) with electron capture detection (ECD), GC combined with mass spectrometry (MS), GC with multi-stage mass spectometry (MS-MS), and direct inlet MS-MS have been used to determine 1,1-dichlorodimethyl sulfone (DDS) in aquatic organisms in the receiving waters outside a pulp mill bleach plant. Both GC-MS-MC and direct inlet MS-MS of tissue extracts of fish and mussel appear to be sensitive, selective, and rapid analytical techniques for the determination of DDS.     

Determination of free fatty acids by capillary zone electrophoresis

Capillary zone electrophoresis was investigated for the separation of free fatty acids as an alternative to well established techniques such as GC or HPLC. The analysis was performed with indirect UV detection in a counterelectroosmotic flow mode using a diethylbarbiturate carrier electrolyte at a pH between 10 and 11 in a mixed aqueous-organic solvent. Separation of saturated and unsaturated fatty acids could be achieved after bromination of the double bonds. Problems with wall adsorption of fatty acids could be overcome by increasing the temperature and using a high concentration of a zwitterionic reagent to inactivate the silica surface. Increased sensitivity could be achieved after preconcentration on alumina. The method was applied to the determination of free fatty acids in dairy products. The advantages compared to traditional methods include short analysis times and simple preparation steps.Dedicated to Univ. Prof. Dr. Karl Winsauer on the occasion of his 70th birthday     

Characterisation of pulp and paper mill sludge for beneficiation

Cellulose - In this study, three different pulp and paper mill sludge (PPMS) samples collected from different South African mills were chemically and physically characterised to investigate their...     

Studies related to biological detoxification of kraft pulp mill effluent. V. The synthesis of 12- and 14-chlorodehydroabietic acids and 12,14-dichlorodehydroabietic acid,fish-toxic diterpenes from kraft pulp mill effluent

An improved synthesis of the isomeric 12- and 14-chlorodehydroabietic acids ( 3 and 2 , respectively) and 12,14-dichlorodehydroabietic acid ( 4 ) is described. The monochioro isomers were conveniently separated as the imidazole derivatives, and conversion of the latter to the free acids or their corresponding methyl esters could be achieved in high yield. Studies involving microbial degradation of 2–4 are underway.     

Determination of the position distribution of fatty acids in natural phosphatidylcholines

Summary It has been shown that the snake venom ofVipera lebetina obtusa/ul can be used as a source of phospholipase A.A method is given for the accelerated enzymatic hydrolysis of natural phosphatidylcholines in order to determine the position distribution of the fatty acids by bringing the pH of the medium to 10.15.A technique for calculating the composition of the diglycerides of the phosphatidylcholines is given.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 137–141, March, 1971.     

Determination of fatty acids in atmospheric samples via GC/MS

Summary Atmospheric precipitation and aerosol samples are characterized by a complex mixture of several organic compounds. A simple method for the simultaneous determination of the main compound classes by GC/MS is presented. In detail, seasonal variations of C₈–C₃₂ fatty acids in precipitation in a semirural area have been studied. Total fatty acids concentrations of 7–53 g/l were detected. Summer rain is characterized by high amounts of fatty acids >C₂₀ and lower amounts of C₁₁–C₂₀ species. Two effects may be responsible: larger emission rates of fatty acids during vegetation periods and an increased influence of vapour phase due to higher temperatures during summer. CPI values showed no general trend; lower CPI values for winter rain could not be observed. This would be expected if anthropogenic sources play an important role. Monounsaturated fatty acids (C_16:1, C_18:1) were more abundant during winter than in summer. High concentrations of polyunsaturated fatty acids (C_18:x) could be detected during summer. High relative concentrations of the potential oxidation products of the unsaturated species, nonanedioic acid and w-oxononanoic acid, are associated with relatively low concentrations of their precursors.     

HPLC-APCI-MS法分析测定白刺籽油中游离脂肪酸

利用荧光衍生试剂1,2-苯并-3,4-二氢咔唑-9-乙基对甲苯磺酸酯(BDETS)作为脂肪酸柱前衍生化试剂,采用梯度洗脱在Eclipse XDB-C8色谱柱上对游离脂肪酸(FFA)(油酸、亚油酸、软脂酸和硬脂酸)衍生物进行分离.利用柱后在线的串联质谱以大气压化学电离源(APCI)正离子模式实现了各组分的质谱定性.荧光检测的激发和发射波长分别为λex=333 nm,λem=390 nm.脂肪酸的线性回归系数大于0.9990,检出限为3.38～6.59 nmol/L.建立的方法具有良好的重现性.利用此方法对超临界CO2提取的唐古特白刺籽油中几种游离脂肪酸进行了分析.结果表明白刺籽油中含有大量的游离不饱和脂肪酸.     

Direct injection analysis of fatty and resin acids in papermaking process waters by HPLC/MS

A novel HPLC-atmospheric pressure chemical ionization/MS (HPLC-APCI/MS) method was developed for the rapid analysis of selected fatty and resin acids typically present in papermaking process waters. A mixture of palmitic, stearic, oleic, linolenic, and dehydroabietic acids was separated by a commercial HPLC column (a modified stationary C(18) phase) using gradient elution with methanol/0.15% formic acid (pH 2.5) as a mobile phase. The internal standard (myristic acid) method was used to calculate the correlation coefficients and in the quantitation of the results. In the thorough quality parameters measurement, a mixture of these model acids in aqueous media as well as in six different paper machine process waters was quantitatively determined. The measured quality parameters, such as selectivity, linearity, precision, and accuracy, clearly indicated that, compared with traditional gas chromatographic techniques, the simple method developed provided a faster chromatographic analysis with almost real-time monitoring of these acids.     

Determination of volatile fatty acids in landfill leachates by ion-exclusion chromatography

An ion-exclusion chromatographic method with on-line desalinization for the determination of volatile fatty acids in landfill leachates is described. Highly sensitive conductivity detection of the organic acids was achieved by using dilute p-hydroxybenzoic acid solution as an eluent. Interference with mineral acids was reduced by treatment with barium chloride solution prior to desalinization. A silver-loaded cation-exchange guard column for the desalinization was installed in series with the analytical column to avoid the contamination of organic acids. This method features detection limits of 0.01 mg L(-1) formic acid, 0.02 mg L(-1) acetic acid, 0.05 mg L(-1) propionic acid, and 0.1 mg L(-1) butyric acid, respectively, with an injection of 20 microL sample. Application of the on-line desalinization LC method is illustrated for leachate samples from a Japanese sanitary landfill.     

超高效液相色谱法测定生物柴油中的11种脂肪酸及脂肪酸甲酯

建立了采用超高效液相色谱(UPLC)-蒸发光散射检测器(ELSD)测定生物柴油中11种常见的脂肪酸及脂肪酸甲酯含量的方法。这11种常见的脂肪酸及脂肪酸甲酯为豆蔻酸、亚油酸、棕榈酸、油酸、亚麻酸甲酯、硬脂酸、亚油酸甲酯、棕榈酸甲酯、油酸甲酯、芥酸和硬脂酸甲酯。样品经提取后用甲醇溶解,采用Acquity UPLC BEH Phenyl C18柱(100 mm×2.1 mm,1.7 μm)分离,乙腈-水（体积比为3∶1)混合液为流动相进行等度洗脱,采用的ELSD条件为增益80,漂移管温度为45 ℃,载气压力为172 kPa,雾化器为冷却模式,并用外标法进行定量分析。结果表明,在一定的质量浓度范围内,峰面积的对数和质量浓度的对数线性关系良好。与其他检测生物柴油成分的方法相比,该方法简单,分离效果好,速度快,特别是此方法可以同时实现脂肪酸及脂肪酸甲酯的分离,并进行定量分析,能有效测定反应的进行程度,从而满足生物柴油工艺研究的需要。     

Determination of iodine value fatty acids by a flow-injection method

An automated method for determining the iodine value for various industrial fatty acids is described. The method is based on flow-injection techniques and the chemistry is a modified version of the standard Wij's solution method. The system is fully computerized with an AIM-65 microcomputer. Two detection system, u.v.-visible absorbance and potentiometric sensing, are compared. Results comparable to the conventional method are obtained. Continuous-run sample throughput rates of 12 h^?1 are eralistic.