Analysis of the polyethylene glycol glucosides and FA esters thereof by atmospheric-pressure ionization MS

Polyethylene glycol (PEG) glucosides (PEGG) and the PEGG esters of lauric acid were analyzed by atmospheric-pressure ionization MS (API-MS) with electrospray ionization. Straightforward mass characterization of the complex mixtures could be achieved without prior chromatographic separation. The constituents were identified on the basis of quasi-molecular ions. Individual components could be observed as protonated molecular ions [M+H]⁺ and/or as their NH₄ ⁺, Na⁺, or K⁺ adducts in positive ion mode. The mass spectrometric investigation showed that mixtures of PEGG consisted of monoglucoside, diglucoside, polyglucoside, and free PEG. The esterification product is a mixture of two types of nonionic surfactants: PEG-laurates and PEGG-laurates. The reasons for distortion of the quasi-molecular ion intensities and the stabilization of adduct ions were discussed. The rapid and highly sensitive API-MS analysis technique proposed here is well suited for direct characterization of complex mixtures and suitable for development as a routine analytical method.     

Exhaust Emissions from an Engine Fueled with Biodiesel from High-Oleic Soybeans

Biodiesel is a fuel comprising mono-alkyl esters of medium to long-chain fatty acids derived from vegetable oils or animal fats. Typically, engines operated on soybean-based biodiesel exhibit higher emissions of oxides of nitrogen (NOx) compared with petroleum diesel. The increase in NOx emissions might be an inherent characteristic of soybean oil’s polyunsaturation, because the level of saturation is known to affect the biodiesel’s cetane number, which can affect NOx. A feedstock that is mostly monounsaturated (i.e. oleate) helps to balance the tradeoff between cold flow and oxidative stability. Genetic modification has produced a soybean event, designated 335-13, with a fatty acid profile high in oleic acid (>85%) and with reduced palmitic acid (<4%). This high-oleic soybean oil was converted to biodiesel and run in a John Deere 4045T 4.5-L four-stroke, four-cylinder, turbocharged direct-injection diesel engine. The exhaust emissions were compared with those from conventional soybean oil biodiesel and commercial No. 2 diesel fuel. There was a significant reduction in NOx emissions (α = 0.05) using the high-oleic soybean biodiesel compared with regular soybean oil biodiesel. No significant differences were found between the regular and high-oleic biodiesel for unburned hydrocarbon and smoke emissions.     

Nitrate leaching from loamy soils as affected by crop rotation and nitrogen fertilizer application

Nitrate leaching as affected by cropping system/crop rotation, history of farmyard manure application or fertilizer nitrogen application (0 N, 0.5 N and 1 N) was studied at nine sites on loamy soils during 1986/87, 1987/88 and 1988/89. Soil solution from 80 to 90 cm soil depth was sampled every second week in the period November to May by the use of porous ceramic cups and analysed for NO₃-N and Cl. Climatical conditions were obtained from standard meteorological observations in the region. Drainage from soil profiles was calculated from measured and simulated values of precipitation and actual evapotranspiration, respectively.The results show that type of crop is of the utmost importance for the leaching magnitude of nitrate as 40% of the total variance in nitrate concentrations in the soil solution could be explained by the type of crop.The second factor of importance was the history of farmyard manure (FYM) application, which was able to explain 28% of the total variation in nitrate concentration in the soil solution. Nitrate concentration/leaching from arable land without FYM ever being applied was considerably lower than from arable land which received periodical FYM applications until the early 70's or from arable land which besides periodical FYM applications in the past presently still receives regular applications of FYM. Only about 1% of the total variation in nitrate concentration in the soil solution was explainable by the level of fertilizer nitrogen application.Differences between years explained 14% of the total variation in nitrate concentration in the soil solution due to differences between the years in soil temperatures and water run-off. The run-off during the autumn and winter of 1986/87, 1987/88 and 1988/89 was 95, 275 and 55 mm, respectively. As expected nitrate leaching increased with increasing run off. However, nitrate leaching at the 275 mm run off was considerably lower than expected, which seems explainable by a substantial denitrification. The soil at the sites in question seems thus partly to purify the soil solution for nitrate before it leaves the root zone at the observed high run off conditions.     

An easy pot incubation method for measuring nitrogen mineralization from easily decomposable organic material under well defined conditions

A pot incubation method for measuring mineralization dynamics from fresh plant material was tested. The aim was to develop a method which under well-defined conditions could produce mineralization data suited for estimating model input parameters for nitrogen prediction models. The results showed that the water tension of the soil could be controlled easily and precisely by diffusion through porous ceramic cups, and that nitrogen mineralization or immobilization could be measured already after 15 days at 15°C. The results showed that for the incubated catch crop residues carbon, nitrogen and nitrate-N contents were the most important factors determining mineralization. No significant effects ould be ascribed to other parameters measured.     

棉籽油间歇式酯交换反应动力学的研究

生物柴油(棉籽油甲酯)可以由棉籽油与甲醇在催化剂KOH存在下通过酯交换反应制得。故对棉籽油间歇式酯交换反应动力学进行了研究,并考察了反应温度和催化剂浓度对产物棉籽油甲酯浓度的影响。用液相色谱法分析棉籽油的组成;用气相色谱法分析产物中棉籽油甲酯的含量。由实验数据绘制的动力学曲线得到酯交换反应在开始阶段为准二级反应,以后紧接转为一级反应和零级反应,与文献报导的棕榈油酯交换反应动力学结果一致。由实验数据求出酯交换反应在开始阶段的动力学参数,35℃、45℃时的反应速率常数分别为0.9179Lmol-1min-1和1.049Lmol-1min-1,酯交换反应的活化能为10.88kJmol-1。根据实验结果得到棉籽油酯交换反应的最佳反应温度为45℃,最佳催化剂为1.1%KOH。     

Electrodeposition of silver from nitrate solution: Part II. Mechanism of the effect of phosphate ions

The mechanism of compact Ag-film formation by electrolysis from nitrate solution with addition of small amounts of phosphate ions is elucidated. It is shown that the phosphate ions exert their effect by lowering the exchange current density. Consequently, the radii of nucleation exclusion zones also diminishes, thus producing conditions stimulating electrodeposition of continuous thin Ag-film.     

含氯离子废水化学需氧量分析方法比较

含氯离子废水化学需氧量的分析方法的研究是当前环境监测研究的热点之一，各种文献报道也较多，但各自使用的效果不一。采用试验的方法对含氯离子废水中CODCr的分析进行了初步研究，比较了硫酸汞加入法、稀释法、硝酸银滴定法、氯气校正法、氯离子校正法等方法在不同化学需氧量不同氯离子浓度下的分析结果，利用分析结果与配置的标准溶液浓度相比较，分析了各种方法的优缺点，结果表明硝酸银滴定法是比较理想的适应范围较广的方法。     

Lipase-catalyzed esterification of lactic acid with straight-chain alcohols

Enzymatic synthesis of esters of lactic acid and straight-chain alcohols with different chain lengths (C₆–C₁₈) were investigated in batch reactions with hexadecanol (C₁₆) as the model alcohol. Cyclohexane was the best solvent for higher ester yields, and the best biocatalyst was the immobilized Candida antarctica lipase B (Novozym 435) as well as the textile-immobilized Candida sp. lipase. A method was established to obtain ester yields in the range of 71 to 82% for the different alcohols, and the most favorable conditions for the esterification reaction using Novozym 435 were an equimolar ratio of lactic acid to alcohol, each at a concentration of 120 mM each; a 50°C reaction temperature; 190 rpm shaking speed; and the addition of 100 mg molecular sieves (4 Å) for drying. The ester yield increased with increasing lipase load, and a yield of 79.2% could be obtained after 24 h of reaction at 20 wt% of Novozym 435. The immobilized Candida sp. lipase prepared in the laboratory also could be used to produce esters of lactic acid and straight-chain alcohols, but it had a much lower activity than Novozym 435 with a temperature optimum of 40°C.     

Dependence of oil stability index of fatty compounds on their structure and concentration and presence of metals

During storage and use, vegetable oil-derived industrial products such as biodiesel and biodegradable lubricants can be subjected to conditions that promote oxidation of their unsaturated components. The materials arising during oxidation and subsequent degradation can seriously impair the quality and performance of such products. Therefore, oxidative stability is a significant issue facing these vegetable oil-derived products, and enhanced understanding of the influence of various components of vegetable oils and storage parameters is necessary. In this work, the oil stability index (OSI) was used for assessing oxidation of monoalkyl esters of FA by varying several parameters. Neat fatty compounds and prepared mixtures thereof were studied for assessing the influence of compound structure and concentration. Small amounts of more highly unsaturated compounds had a disproportionately strong effect on oxidative stability. The recently developed concept of bis-allylic equivalents correlated more closely than the iodine value with the OSI times of mixtures of fatty esters. The OSI times of free acids were shorter than those of the corresponding alkyl esters. The presence of copper, iron, and nickel also reduced oxidative stability, but their effect was less than the presence of more highly unsaturated fatty compounds. Of these metals, copper had the strongest catalytic effect on OSI time. OSI may be an alternative to long-term storage tests for determining the influence of extraneous materials such as metals on oxidative stability.     

磷矿中氧化钙,氧化镁测定方法的研究

用硝酸铋分离磷酸根离子，在滤液中用ＥＧＴＡ－ＥＤＴＡ分别测定氧化钙，氧化镁较之传统方法简便效果好。