Determination of water in NIST reference material for mineral oils

The accuracy of the reference concentrations of moisture in electrical insulating oil RM 8506 and lubricating oil RM 8507 (both of mineral type) and specified by the National Institute of Standards and Technology (NIST) as containing 39.7 and 76.8 ppm (w/w) water, respectively, has recently been the subject of debate in this journal. To shed some further light on this controversy, we report in this correspondence results for these oils obtained by two additional methods, one based on specially designed reagents for diaphragm-free Karl Fischer (KF) coulometry and the other based on the concept of stripping at elevated temperature/continuous KF coulometry. A positive interference effect was shown to take place for RM 8506 when the direct coulometric method was used. If the results are corrected for this, the values including six different procedures varied in the range 13.5-15.6 ppm (w/w). For RM 8507, all values were between 42.5 and 47.2 ppm (w/w), which means that the values recommended by NIST for both reference oils using volumetric titration are about twice as high as those obtained with the other techniques. A possible explanation for this discrepancy is presented.     

Determination of the analytical performance of a headspace capillary gas chromatographic technique and karl Fischer coulometric titration by system calibration using oil samples containing known amounts of moisture

Over the past few years, concerns have been raised in the literature about the accuracy of the Karl Fischer (KF) method for assessing moisture in transformer mineral oils. To better understand this issue, the performance of a static headspace capillary gas chromatographic (HS-CGC) technique was compared to that of KF coulometric titration by analyzing moisture in samples containing known amounts of water and various samples obtained from the National Institute of Standards and Technology (NIST). Two modes of adding samples into the KF vessel were used: direct injection and indirect injection via an azeotropic distillation of the moisture with toluene. Under the conditions used for direct injection, the oil matrix was totally dissolved in the anolyte, which allowed the moisture to be titrated in a single-phase solution rather than in a suspension. The results have shown that when HS-CGC and combined azeotropic distillation/KF titration are calibrated with moisture-in-oil standards, a linear relation is observed over 0-60 ppm H(2)O with a correlation coefficient better than 0.9994 (95% confidence), with the regression line crossing through zero. A similar relation can also be observed when calibration is achieved by direct KF addition of standards prepared with octanol-1, but in this case an intercept of 4-5 ppm is noted. The amount of moisture determined by curve interpolation in NIST reference materials by the three calibrated systems ranges from 13.0 to 14.8 ppm for RM 8506 and 42.5 to 46.4 ppm for RM 8507, and in any case, the results were as high as those reported in the literature with volumetric KF titration. However, titration of various dehydrated oil and solvent samples showed that direct KF titration is affected by a small bias when samples contain very little moisture. The source of error after correction for the large sample volume used for the determination (8 mL) is about 6 ppm for Voltesso naphthenic oil and 4 ppm for toluene, revealing a matrix effect on the measurement. Finally, the results revealed that HS-CGC is a good technique for measuring moisture in oil samples and that the use of azeotropic vapors for introducing moisture into the titrator almost completely eliminates the matrix effect observed with the oil components. Direct KF injection could also be used provided the system is calibrated with moisture-in-oil standards prepared in the same matrix which is to be used for the determination.     

Bias assessment of current technologies used for the determination of low levels of moisture in mineral oil samples

The problem in the current debate on the accuracy of Karl Fischer (KF) titrations lies in the fact that coulometry is being compared to volumetry on mineral oil samples for which the true moisture content is unknown. To clarify this point, dehydrated oil samples equilibrated under known temperature and relative humidity conditions and equilibrated oil samples containing known amounts of added moisture were used to assess the accuracy of the determinations. In addition, the measurements were extended to other techniques given that it is unlikely that they would be affected by the same phenomenon causing the KF systematic errors. The samples sent to different laboratories were analyzed by headspace/capillary gas chromatography, gas-phase H2 sensor, oil-phase or gas-phase RH sensors, KF coulometric titration with direct or indirect injection, and KF volumetric titration using a standard or NIST modified procedure. The laboratory comparison showed that with the exception of 4 techniques out of 10 that were tested, the measurements gave results in the expected concentration range. Considering the exceptions, two techniques based on volumetric titration yielded results tainted with an important positive bias for both sample types. This bias, tentatively associated with the high iodine end point concentration used by these systems, was estimated at approximately 22 ppm under the conditions applied by NIST. On the other hand, the two RH sensors showed a marked tendency to underestimate the value of the samples containing high moisture content. In this case, a loss of analyte through wall adsorption during the time required to achieve steady-state conditions in the measuring chamber seems to be at the origin of the negative biases.     

Source of the Difference between the Measurement of Water in Hydrocarbons As Determined by the Volumetric and Coulometric Karl Fischer Methods

The disparity between the volumetric and coulometric Karl Fischer methods for the measurement of water in hydrocarbons and hydrocarbon mixtures (oils) has been resolved. The amount of water detected by the volumetric method when the titration vessel solution is homogeneous is higher than that measured coulometrically or volumetrically when the titration vessel solution is heterogeneous. Water in oil that is not measured by the coulometric method when the oil is incompletely dissolved has been shown to reside in the oil phase of the heterogeneous (multiphasic) coulometric vessel suspension. Water that is not measured volumetrically under relatively low chloroform concentrations after the point of transition to a heterogeneous titration vessel solution is reached also appears to reside in the nonaqueous phase of the titration vessel solution. It appears that this water is retained in the hydrocarbon phase in a manner such that it is completely inaccessible to the volumetric or coulometric Karl Fischer reagents.     

An evaluation of field total petroleum hydrocarbon (TPH) systems

An evaluation of several field kits and petroleum hydrocarbon measuring systems was conducted. The field kits were the immunoassay based EnviroGard petroleum fuels in soil test kit (EnviroGard, Millipore Canada, Mississauga, Ont., Canada), the turbidimetric based PetroFlag hydrocarbon test kit for soil (Dexsil, Hamden, CT, USA), a DR/2000 field kit (Hach Company, Loveland CO, USA) employing colorimetric test procedures and a total organic carbon (TOC) analysis instrument (Dohrmann Division, Rosemount Analytical Inc., Santa Clara, CA, USA) using oxidation principles. These procedures were compared to the traditional technique of extraction of the petroleum hydrocarbons using trichlorotrifluoroethane (Freon 113) as the solvent and subsequent infrared (IR) analysis using a portable fixed wavelength analyzer (Buck Scientific, East Norwalk, CT, USA).The EnviroGard kit was affected by the sample matrix. The soil type and the presence or lack thereof specific chemical components affected the capability to detect the petroleum hydrocarbon concentration. The PetroFlag soil test kit tended to generate results higher than the accepted concentration. The IR method was better capable of producing results similar to the expected concentration values of the prepared samples.Results indicate that the total organic carbon analysis technique evaluated is best suited for samples containing dissolved hydrocarbons in water and is not a preferred procedure for water samples containing dispersed or floating oil. At low concentrations of 10ppm and less, the TOC method and IR method have concentration values within a few parts-per-million (ppm) of each other, however, an examination of the trends in the results for all samples shows no similarity. This would indicate that the traditional extraction and infrared method and the total organic carbon method are not measuring the same parameter.Finally, the colorimetric field kit was capable of quantifying the concentration of oil in water samples within limits. The results from the oil-in-water method built into the unit at the factory were not comparable with analysis carried out by the infrared technique. With specific methods for each oil incorporated into the spectrophotometer, the comparability of data increased significantly. Results generated by the kit are dependent upon the color and amount of the oil in the sample. The kit is best suited for dark colored oils and the water samples with concentrations in the range of 10 to 85ppm by weight.     

Screening of oil samples on the basis of excitation-emission room-temperature phosphorescence data and multiway chemometric techniques. Introducing the second-order advantage in a classification study

Room-temperature phosphorescence excitation-emission matrices and multiway methods have been analyzed as potential tools for screening oil samples, based on full matrix information for polyaromatic hydrocarbons. Crude oils obtained from different sources of similar geographic origin, as well as light and heavy lubricating oils, were analyzed. The room-temperature phosphorescence matrix signals were processed by applying multilayer perceptron artificial neural networks, parallel factor analysis coupled to linear discriminant analysis, discriminant unfolded partial least-squares, and discriminant multidimensional partial least-squares (DN-PLS). The ability of the latter algorithm to classify the investigated oils into four categories is demonstrated. In addition, the combination of DN-PLS with residual bilinearization allows for a proper classification of oils containing unsuspected compounds not present in the training sample set. This second-order advantage concept is applied to a classification study for the first time. The employed approach is fast, avoids the use of laborious chromatographic analysis, and is relevant for oil characterization, identification, and determination of accidental spill sources.     

Quantitative determination of moisture in lubricants by Fourier transform infrared spectroscopy

This paper describes the development of a practical Fourier transform infrared (FT-IR) method for the determination of moisture in lubricants through the combined use of signal transduction and differential spectroscopy to circumvent matrix effects. The acid-catalyzed stoichiometric reaction of 2,2-dimethoxypropane (DMP) with moisture to produce acetone was used to provide IR signals proportional to the amount of moisture present in oils. Calibration standards were prepared by spiking polyalphaolefin (PAO) gravimetrically with water using dioxane as a carrier. For FT-IR analysis, standards and samples were diluted with acidified isooctane and then split, with one aliquot treated with DMP and the other with a blank reagent. The spectra of the two aliquots were collected, and a differential spectrum was obtained so as to ratio out the invariant spectral contributions from the sample. Quantitation for moisture was based on measurement of the peak height of the nu(C=O) absorption of acetone at 1717 cm(-1), yielding a standard error of calibration of approximately 40 ppm H2O. The method was validated by standard addition of water in dioxane to PAO containing added base as well as to new and used oils. In all cases the method responded quantitatively to standard addition, the average standard error of prediction being approximately 80 ppm, with the results showing only a minor dependence on the oil formulation. From an analytical perspective, the FT-IR method is both more reproducible and more accurate than Karl Fischer methods and has advantages in terms of environmental considerations, sample size, and speed of analysis as well as the variety of oil types that can be handled. Signal transduction/differential spectroscopy may have broader utility as an alternative means for the determination of low levels of moisture in complex matrices.     

A new Fourier transform infrared method for the determination of moisture in edible oils

A rapid, practical, and accurate Fourier transform infrared (FT-IR) method for the determination of moisture content in edible oils has been developed based on the extraction of water from oil samples into dry acetonitrile. A calibration curve covering a moisture content range of 0-2000 ppm was developed by recording the mid-infrared (MIR) spectra of moisture standards, prepared by gravimetric addition of water to acetonitrile that had been dried over molecular sieves, in a 500 microm ZnSe transmission flow cell and ratioing these spectra against that of the dry acetonitrile. Water was measured in the resulting differential spectra using either the OH stretching (3629 cm(-1) or bending (1631 cm(-1)) bands to produce linear standard curves having standard deviations (SDs) of approximately +/-20 ppm. For moisture analysis in oils, the oil sample was mixed with dry acetonitrile in a 1:1 w/v ratio, and after centrifugation to separate the phases, the spectrum of the upper acetonitrile layer was collected and ratioed against the spectrum of the dry acetonitrile used for extraction. The method was validated by standard addition experiments with samples of various oil types, as well as with oil samples deliberately contaminated with alcohols, hydroperoxides, and free fatty acids to investigate possible interferences from minor constituents that may be present in oils and are potentially extractable into acetonitrile. The results of these experiments confirmed that the moisture content of edible oils can be assessed with high accuracy (on the order of +/-10 ppm) by this method, thus providing an alternative to the conventional, but problematic, Karl Fischer method and facilitating the routine analysis of edible oils for moisture content.     

Production and characterization of pyrolytic oils by pyrolysis of waste machinery oil

The main objective of this work is to propose an alternative method for evaluation of the waste machinery oil which is an environmental problem in Turkey. For this purpose, pyrolysis of waste machinery oil was conducted in a tubular reactor. Effect of the experimental conditions (various temperatures, catalyst type) on the formation of pyrolytic oil, gas, and char was investigated. Nickel supported on silica and zeolite (HZSM-5) were used as catalysts. Properties of the pyrolytic oils were characterized by gas chromatograph equipped with a mass selective detector (GC–MS), gas chromatography with flame ionization detector (GC–FID for boiling point range distribution), nuclear magnetic resonance (¹H NMR) spectroscopy, higher heating value measurement, and elemental analysis. The behavior of the metals in the waste machinery oil and the pyrolytic oil samples was also quantitatively detected by inductively coupled plasma (ICP) analysis. As, Cd and Cr contents of the all pyrolytic oils were found as <0.05 ppm, while Cu content of the pyrolytic oils varied between 0.3 ppm and 0.61 ppm. Only Vanadium contents of the pyrolytic oils obtained at 800 °C (0.342 ppm) and in the presence of HZSM5 (0.57 ppm) increased compared to that obtained by waste machinery oil (0.1 ppm). Lower metal contents of the pyrolytic oils reveal that pyrolysis of the waste machinery oils leads to the formation of environmental friendly pyrolytic oils with higher heating values.     

Systematic bias in the measurement of water in oils by tubular oven evaporation and azeotropic distillation.

Water in oil has been measured by tubular oven evaporation and by azeotropic distillation into a coulometric moisture analyzer. The results of these measurements were compared to the results obtained by volumetric titration of water in oil. The volumetric measurements were consistently higher than the measurements made by tubular oven evaporation or azeotropic distillation. A mass balance study was performed by volumetric Karl Fischer titration of the water in the oil that remained in the tubular oven and in the distillation apparatus. This study indicated that measurable amounts of water were not removed after exhaustive evaporation or distillation. The sum of the water removed by distillation from toluene and that remaining in the distillation chamber was equal to the amount of water measured in the oil by the volumetric method. The data are consistent with the existence of an oil-water azeotrope that does not release water upon evaporation at 160 degrees C or upon dissolution in toluene and distillation of the water-toluene azeotrope. These results were obtained for oils varying in viscosity from 8 to 850 m2/s, and the amount of water remaining associated with the oil appears to be dependent upon the composition of the oil and the method of analysis.     

Progress in Karl Fischer coulometry using diaphragm-free cells

Different designs of a semiopen, drainable cathode compartment of a medium-sized coulometric Karl Fischer (KF) cell for the determination of water in the range 0.1-500 microg were evaluated. The main criterion for the design was to keep the resistance between the anolyte and catholyte low enough to permit the generation of currents larger than 20 mA (for an output voltage of 28 V). It was found that a good compromise between the size of this current and a minimal influence from diffusing/migrating oxidizable reduction products from the catholyte was achieved by means of an interface having a channel length and diameter of 8 and 2.1 mm, respectively (catholyte volume, approximately 1 mL). To show the general applicability of the concept, the following different types of coulometric reagents suitable for nonpolar and polar samples, as well as for samples containing active carbonyl compounds, were investigated: Hydranal Coulomat A, AD, AK, AG-H (modified with chloroform, Merck), and two homemade methanolic reagents modified with 40% (v/v) chloroform and 50% (v/v) formamide, respectively. Except for Hydranal Coulomat A, the mean value of five consecutive titrations of 50 microg water did not deviate by more than 0.2% from the expected value for all reagents. Draining after every titration was sufficient to obtain accurate results, even for Coulomat A which, when used in the commercial diaphragm-free system of Metrohm, gave values which were about 10% too high. As compared to earlier reported results for diaphragm-free coulometry, the descibed modified cell represents a significant improvement, mainly because of the high accuracy achieved for all types of reagents.     

Determination of aniline derivatives in oils related to the toxic oil syndrome by atmospheric pressure ionization-tandem mass spectrometry

In 1981, an unknown disease appeared in Spain, the Spanish Toxic Oil Syndrome. Nowadays and despite all efforts, the etiological agent is still unknown. Early studies showed a link between this illness and the consumption of denatured rapeseed oil fraudulently processed and marketed as edible oil. Two families of aniline derivatives present in these oils (fatty acid anilides and acylated phenyl amino propanediol derivatives or PAPs) were found to be good chemical markers of toxic oils. In this work, a new method has been developed to analyze these aniline derivatives in oil samples by HPLC-MS and HPLC-MS/MS with an API source. For their quantification, three different internal standards were used, one for anilides and two for PAPs. Quantification limits were 8 ppm for anilides and 0.2 ppm for PAPs. Anilides and PAPs were found in marker-positive samples at levels up to 50,000 and 330 ppm, respectively. The relative abundance of the different fatty acid anilides and PAPs correlates with the fatty acid composition of the oils. More than 2,600 different samples were analyzed by this method in the most exhaustive screening of suspected toxic oils carried out to date.     

Critical examination of the quantification of aromatic compounds in three standard reference materials

Three standard reference materials from the National Institute of Standards and Technology (NIST), namely, SRM 1597 coal tar, 1582 crude oil, and 1580 shale oil, were investigated in detail to determine the concentration of polycyclic aromatic sulfur heterocycles using gas chromatography with the atomic emission detector in the carbon- and sulfur-selective modes. Coelution problems were found to be common, and the use of two capillary gas chromatographic columns with stationary phases of widely differing polarity was necessary for the separation of the important analytes phenanthrene, anthracene, dibenzothiophene, and the naphthothiophenes. On the commonly used nonpolar stationary phases, phenanthrene and dibenzothiophene coelute with the isomeric naphthothiophenes and this leads to too high concentrations being measured for the two major analytes and must be corrected for. For (sulfur and oxygen) heterocycles, individual response factors must be used if the flame ionization detector is employed. The NIST values were obtained without regard to those factors. This is done here for the three SRMs, and it is shown that the adjusted NIST values agree very well with the GC/AED values. It is suggested that the (noncertified) NIST values for several polycyclic aromatic compounds (PACs) should be reexamined. Very probably many other determinations of PACs might suffer from the same shortcomings.     

Removal of residual pesticides in vegetables using ozone microbubbles

The removal of fenitrothion (FT) pesticide residues from vegetables by immersion in ozone-microbubbled solution was demonstrated. FT-treated lettuce, cherry tomatoes, and strawberries were immersed in ozone-microbubbled, ozone-millibubbled, and dechlorinated water. After that the percentage of residual FT in the vegetables was determined. Residual FT was efficiently removed from lettuce by immersing it in ozone-microbubbled solution containing more than 1.0 ppm dissolved ozone, or continuously generated ozone-microbubbled solution containing 2.0 ppm dissolved ozone. Similarly, for cherry tomatoes and strawberries, the continuously generated ozone-microbubbled solution containing 2.0 ppm dissolved ozone was highly effective. These results showed that ozone microbubbles effectively removed residual pesticides not only from leafy vegetables but also from fruity vegetables.     

Conditions for accurate Karl Fischer coulometry using diaphragm-free cells

Factors influencing the extent of formation of oxidizable reduction products in coulometric cells used for Karl Fischer (KF) determination of water were investigated. For methanolic KF reagents buffered with imidazole (Im) or diethanolamine (DEA) (separately or in combination), three parameters were found to be of outmost importance: the cathodic current density, the pH, and the concentration of protonated base (ImH+ or DEAH+). For reagents buffered with only Im, the relative formation of oxidizable reduction products varied in the range 2-40%; i.e., 51-70 micrograms of water was found for a 50 micrograms water sample, depending on the above-mentioned parameters. The lowest values were observed for reagents having a pH around 10 in combination with cathodic current densities in the range 2000-5000 mA cm-2. For all the Imbuffered reagents investigated, the addition of modifiers such as chloroform, hexanol, and carbon tetrachloride was found to decrease the formation of oxidizable reduction products significantly. For example, a reagent buffered at pH 10 containing 1 M hexanol gave less than 0.3% formation in the current density interval from 200 to 4000 mA cm-2. The best reagents based on the above-mentioned modifiers were tested in the continuous coulometric mode with errors typically in the interval 0-0.5% using optimum conditions. One prerequisite for obtaining such small errors with diaphragm-free continuous coulometry is to use a cathode area no larger than 0.002 cm2. For some of the reagents based on both Im and DEA, the formation of oxidizable reduction products was close to zero at certain current densities, although the analytical performance was not as good as for the reagents buffered solely by Im due to longer conditioning and titration times.     

Water determination in drugs containing ascorbic acid.

A new rapid analytical method was applied for water determination in tablets of vitamin C, Ce De Calcium Veterinary, and C-Tamin-500 containing ascorbic acid and therefore is not amenable for direct Karl Fischer (KF) titration. The method is based on the consecutive titration first of ascorbic acid by a novel reagent and then of water by a conventional KF reagent (KFR) in the same sample and cell with the electrometric "dead-stop" location of the end point in both titrations. The new reagent consists of iodine, potassium iodide, and sodium acetate in nonaqueous medium. Estimated repeatability and accuracy of both water and ascorbic acid determination are satisfactory.     

超疏水石墨烯/甲醛-三聚氰胺-亚硫酸氢钠共聚物海绵的制备及其在油水分离中的应用

采用两步法合成了石墨烯（GE）改性的超疏水超亲油甲醛-三聚氰胺-亚硫酸氢钠（FMS）共聚物海绵,首先在FMS海绵基质上进行GE原位聚合,然后通过聚甲基苯基硅氧烷构筑超疏水结构。采用FTIR、SEM、TGA、光学接触角测量仪对海绵结构进行表征分析。结果表明,GE成功地修饰了FMS海绵,制备出的GE/FMS共聚物海绵的接触角达158.9°。将GE/FMS共聚物海绵用于油水分离,经20次对机油吸附-解吸附测定后仍能保持稳定的超疏水性质。改性后的GE/FMS海绵具有良好的可重复利用性且对油和有机溶剂具有高度选择吸收性,对氯仿和机油的吸收量分别达到自身质量的约125倍和90倍,对油或有机溶剂的回收率达到87%以上。进一步对油或有机溶剂与水的分离进行了应用模拟,结果表明:改性后的GE/FMS海绵可以高效快速地将油或有机溶剂从水中分离出来,对于投入生产及吸附应用具有实际意义。      

Thermal Characterization of Edible Oils by Using Photopyroelectric Technique

Thermal properties of several edible oils such as olive, sesame, and grape seed oils were obtained by using the photopyroelectric technique. The inverse photopyroelectric configuration was used in order to obtain the thermal effusivity of the oil samples. The theoretical equation for the photopyroelectric signal in this configuration, as a function of the incident light modulation frequency, was fitted to the experimental data in order to obtain the thermal effusivity of these samples. Also, the back photopyroelectric configuration was used to obtain the thermal diffusivity of these oils; this thermal parameter was obtained by fitting the theoretical equation for this configuration, as a function of the sample thickness (called the thermal wave resonator cavity), to the experimental data. All measurements were done at room temperature. A complete thermal characterization of these edible oils was achieved by the relationship between the obtained thermal diffusivities and thermal effusivities with their thermal conductivities and volumetric heat capacities. The obtained results are in agreement with the thermal properties reported for the case of the olive oil.     

Effects of surfactant on release characteristics of clonidine hydrochloride from ethylcellulose film

The effects of Tween 80 (polysorbate 80) and Span 80 (sorbitan monooleate) surfactants on release characteristics of clonidine hydrochloride from ethylcellulose 10 and 20 cps matrix films containing castor oil as a plasticizer were investigated. The release rates of drug from these films in water at 37°C were found to increase with the addition of surfactant, which was highest for the film prepared from ethylcellulose 20 cps with Tween 80. The experimental values of the cumulative amount of drug released were found to conform to the solution matrix model. The calculated values of the cumulative amount of clonidine hydrochloride released using the experimentally determined diffusion coefficients were also found to be in good agreement with the observed values.     

Effects of Surfactant on Release Characteristics of Clonidine Hydrochloride from Ethylcellulose Film

The effects of Tween 80 (polysorbate 80) and Span 80 (sorbitan monooleate) surfactants on release characteristics of clonidine hydrochloride from ethylcellulose 10 and 20 cps matrix films containing castor oil as a plasticizer were investigated. The release rates of drug from these films in water at 37°C were found to increase with the addition of surfactant, which was highest for the film prepared from ethylcellulose 20 cps with Tween 80. The experimental values of the cumulative amount of drug released were found to conform to the solution matrix model. The calculated values of the cumulative amount of clonidine hydrochloride released using the experimentally determined diffusion coefficients were also found to be in good agreement with the observed values.