A green sample preparation strategy for Cl and S determination in crude oil by ion chromatography.

Determination of Cl and S in crude oil by ICP-OES after sample digestion by microwave-induced combustion in disposable vessels

Research has been carried out to determine the feasibility of chemometric modeling of infrared (IR) and near-infrared (NIR) spectra of crude oils to predict the long residue (LR) and short residue (SR) properties of these samples. A novel method is described to predict short residue properties at different flashing temperatures based on the IR spectrum of a crude oil measured at room temperature. The resulting method is the subject of European patent application number 07251853.3 filed by Shell Internationale Research Maatschappij B.V. The study has been carried out on 47 crude oils and 4 blends, representing a large variety of physical and chemical properties. From this set, 28 representative samples were selected by principle component analysis (PCA) and used for calibration. The remaining 23 samples were used as a test set to validate the obtained partial least squares (PLS) regression models. The results demonstrate that this integrated approach offers a fast and viable alternative for the currently applied elaborate ASTM (American Society for Testing and Materials) and IP (Institute of Petroleum) methods. IR spectra, in particular, were found to be a useful input for the prediction of different LR properties. Root mean square error of prediction values of the same order of magnitude as the reproducibility values of the ASTM methods were obtained for yield long on crude (YLC), density (D(LR)), viscosity (V(LR)), and pour point (PP), while the ability to predict the sulfur contents (S) and the carbon residue (CR) was found to be useful for indicative purposes. The prediction of SR properties is also promising. Modeling of the IR spectra, and to a lesser extent, the NIR spectra as a function of the average flash temperature (AFT) was particularly successful for the prediction of the short residue properties density (D(SR)) and viscosity (V(SR)). Similar results were obtained from the models to predict SR properties as a function of the yield short on crude (YSC) values. Finally, it was concluded that the applied protocol including sample pretreatment and instrumental measurement is highly reproducible and instrument and accessory independent.

Chlorine and sulfur determination in extra-heavy crude oil by inductively coupled plasma optical emission spectrometry after microwave-induced combustion

Portions of the sulfur in coal frequently are transformed from one form into another when coal undergoes chemical changes through weathering, pyrolysis, or chemical cleaning. Only three forms of sulfur (sulfatic, pyritic, and organic) are distinguished by the widely-used analytical procedure to determine forms of sulfur in coal, American Society for Testing and Materials (ASTM) Method D-2492. Although the ASTM method is adequate for most fresh untreated coals, two other sulfur forms, elemental and sulfidic, may be present as a result of weathering effects or coal desulfuriza-tion treatments. Results concerning the proportions of organic and pyritic sulfur removed from coal by chemical or thermal desulfurization treatments can sometimes be misleading when using the standard ASTM methods on treated or altered coals. Quantitative tracking of the major forms of sulfur (organic and pyritic) in a coal to the products of different coal treatments is now possible by using carefully selected coals with distinctive sulfur isotope characteristics and analytical methods discussed in this chapter.

<div class="htmlview paragraph">During the last 10 years many researchers and technical groups have studied and performed tests in the area of diesel fuel lubricity [<span class="xref">1</span>]<span class="xref"><sup>1</sup></span>. Protection of diesel engine fuel delivery system components from excessive wear has been the major mission of these efforts. Understanding of the issue, developing laboratory test methods, specifying appropriate fuel properties, and creating mechanical modifications to the equipment, as well as adding lubricity additives to the fuels, describes the bulk of the work which has been performed in this area.</div> <div class="htmlview paragraph">Technical groups from several organizations such as the Society of Automotive Engineers (SAE), the Coordinating European Council (CEC), and the International Organization for Standardization (ISO) have made substantial progress and some have come up with test methods and fuel specifications [<span class="xref">2</span>]. The working group at the American Society for Testing and Materials (ASTM) has been very active in recent years, but has not been able to define a diesel fuel lubricity specification that is acceptable to its members. This group is searching for an appropriate test method and the proper correlation to actual equipment before reaching a consensus on fuel specifications. Other organizations such as the National Conference on Weights and Measures (NCWM) are not involved in the development of test methods. However, they are waiting for the outcome of the work done by ASTM to be able to apply a workable test method in their definition of a premium diesel fuel.</div> <div class="htmlview paragraph">This paper will summarize the efforts of some of these groups and will attempt to spell out the steps necessary to reach consensus on an ASTM fuel lubricity specification. It also presents some encouraging work that has been done with a new Ball on Three Disks (BOTD) test method for measuring lubricity and compares the results to those obtained using the two ASTM methods, SLB-OCLE and HFRR. The results are of interest, specifically, for additized fuels.</div>

Occupational exposures to endotoxin-contaminated, water-based metalworking fluids (MWFs) are thought to contribute to cases of respiratory illness. Before occupational exposure limits for endotoxin can be proposed, accuracy and reproducibility of laboratory measurements must be established. The method most commonly used to quantify endotoxin is the Limulus amebocyte lysate (LAL) assay and this is the basis for the American Society for Testing and Materials (ASTM) method E2144-01. This study was conducted to generate multiple samples with similar mass and endotoxin loading in order to compare four alternative extraction methods with the ASTM method. Using an exposure chamber system that provides a uniform distribution of MWF mist, aerosols with three concentrations of endotoxins (4.5, 350 and 1141 EU/m(3)) were collected simultaneously on multiple filter samples. The filters were examined for endotoxin concentration using five different extraction protocols: extraction with 1 h shaking at 25 degrees C in 30 ml pyrogen-free water (PFW) (protocol 1) or in PFW with 0.05% Tween-20 (protocol 2); or shaking at 68 degrees C in 30 ml PFW (protocol 3) or PFW with Tween-20 (protocol 4); or extraction into 20 ml PFW with sonication at 25 degrees C and pH adjustment to 7.5 (ASTM protocol). The uniformity of the aerosol mass yielded coefficients of variation of 12.7, 7.7 and 1.4% for the low, medium and high exposure groups, respectively. The variance in the endotoxin extraction protocols was highest for the ASTM method for the low, medium and high concentration trials. Low, medium and high endotoxin groups were statistically different (P < 0.001), but there were no statistical differences between extraction protocols within these exposure levels. ASTM method E2144-01 yielded comparable estimations of MWF endotoxin aerosol concentrations but with higher variability than the four other extraction methods. This study shows that extraction into PFW at 25 degrees C with or without Tween-20 was an improvement over the ASTM method in that the estimation was more precise and the method is simpler.

The chemical composition of 23 wood chip samples and 132 wood pellet samples manufactured in the United States and Canada were analyzed for their energy and chemical properties and compared to German standards for pellet quality. The pellet samples obtained from various locations across northern New York and New England included 100 different manufacturers and duplicate samples of some brands. The calorific value, moisture content, and ash content of the samples were determined according to the American Society for Testing and Materials (ASTM) methods. Sulfate and chloride samples were prepared using ASTM methods and analyzed by ion chromatography (IC). The elemental compositions of the ashed wood samples were determined using inductively coupled plasma mass spectrometry (ICP–MS). Mercury was measured by direct analysis of wood samples. The distributions of the sample characteristics, such as heating value, ash content, moisture content, ions, and heavy elements, are presented. Major ash-forming elements were Ca, K, Al, Mg, and Fe. Although heavy elements are found naturally in wood and bark, some pellet samples had unusually high concentrations of heavy elements. This contamination was likely because of inclusion of extraneous materials, such as scrap or painted wood, bark or leaves, and other possible contaminants, during pellet manufacturing processes. Most of the commercially available wood pellets of this study would meet German and European industrial standards. However, standards for elemental compositions of commercial wood pellets and chips need to be established in the United States to exclude extraneous materials. The promulgation of such standards would reduce environmental problems related to air emissions and ash used as fertilizers for agriculture soils, where there are limits on the allowable concentrations for many elements.

Water analysis is an excellent interdisciplinary topic for project-based learning. An undergraduate course was designed to engage the senior undergraduate chemistry students in a real-life experience. In this course, students developed methodologies based on published American Society for Testing and Materials (ASTM) methods for the measurement of fluoride, phenols, and metals in real water samples. The procedures were utilized to analyze target analytes in real water samples from various sources, such as seawater, sewage water, swimming pool water, tap water, and drinking water in the eastern province of the Kingdom of Saudi Arabia (KSA). These areas are profoundly affected by urbanization. The students analyzed the samples by employing a portable total dissolved solids (TDS) meter, a pH/ion-selective electrode (ISE) benchtop meter, an inductively coupled plasma–optical emission spectrometry (ICP-OES), and a gas chromatography–flame ionization detector (GC-FID). The ASTM methods allowed the students to gather research-level data and study regional environmental issues. The students prepared and presented their results at the departmental conference. Through the water analysis project, students acquired field and laboratory research skills, performed a quantitative analysis of data sets, developed collaborative interactions, as well as utilized their writing and communication skills. The exposure of students to these research tools provided them with experience in dealing with the limitations of trace level analysis in real samples. The outcome of this study provided the students with an overview of how their theoretical knowledge was connected to the country’s limited water sources and pollution problems.

Chloride determination by ion chromatography in petroleum coke after digestion by microwave-induced combustion

Western Research Institute (WRI) has developed a new commercial product ready for technology transfer, the Diesel Dog{reg_sign} Portable Soil Test Kit, for performing analysis of fuel-contaminated soils in the field. The technology consists of a method developed by WRI (U.S. Patents 5,561,065 and 5,976,883) and hardware developed by WRI that allows the method to be performed in the field (patent pending). The method is very simple and does not require the use of highly toxic reagents. The aromatic components in a soil extract are measured by absorption at 254 nm with a field-portable photometer. WRI added significant value to the technology by taking the method through the American Society for Testing and Materials (ASTM) approval and validation processes. The method is designated as ASTM Method D 5831-96, Standard Test Method for Screening Fuels in Soils. This ASTM designation allows the method to be used for federal compliance activities. In June 2001, the Diesel Dog technology won an American Chemical Society Regional Industrial Innovations Award. To gain field experience with the new technology, Diesel Dog kits have been used for a variety of site evaluation and cleanup activities. Information gained from these activities has led to improvements in hardware configurations and additional insight into correlating Diesel Dog results with results from laboratory methods. The Wyoming Department of Environmental Quality (DEQ) used Diesel Dog Soil Test Kits to guide cleanups at a variety of sites throughout the state. ENSR, of Acton, Massachusetts, used a Diesel Dog Portable Soil Test Kit to evaluate sites in the Virgin Islands and Georgia. ChemTrack and the U.S. Army Corps of Engineers successfully used a test kit to guide excavation at an abandoned FAA fuel-contaminated site near Fairbanks, Alaska. Barenco, Inc. is using a Diesel Dog Portable Soil Test Kit for site evaluations in Canada. A small spill of diesel fuel was cleaned up in Laramie, Wyoming using a Diesel Dog Soil Test Kit.

The American Society for Testing and Materials (ASTM) has proposed a standard method for testing the performance characteristics of a wind vane. This paper presents the procedures used to test and evaluate the ASTM method, and the results of that evaluation. Twelve wind vanes were borrowed from manufacturers and tested using the ASTM procedures. The starting threshold, starting accuracy, delay distance, overshoot ratio and damped wavelength were measured. Damping ratio and natural wavelength were computed from the measurements. Based on the results of these tests, it is concluded that the ASTM method provides a reasonable and reliable technique for determining performance characteristics for many types of wind vanes.

Psychometric functions are predominately used for estimating detection thresholds in vision and audition. However, the requirement of large data quantities for fitting psychometric functions (>30 replications) reduces their suitability in olfactory studies because olfactory response data are often limited (<4 replications) due to the susceptibility of human olfactory receptors to fatigue and adaptation. This article introduces a new method for fitting individual-judge psychometric functions to olfactory data obtained using the current standard protocol-American Society for Testing and Materials (ASTM) E679. The slope parameter of the individual-judge psychometric function is fixed to be the same as that of the group function; the same-shaped symmetrical sigmoid function is fitted only using the intercept. This study evaluated the proposed method by comparing it with 2 available methods. Comparison to conventional psychometric functions (fitted slope and intercept) indicated that the assumption of a fixed slope did not compromise precision of the threshold estimates. No systematic difference was obtained between the proposed method and the ASTM method in terms of group threshold estimates or threshold distributions, but there were changes in the rank, by threshold, of judges in the group. Overall, the fixed-slope psychometric function is recommended for obtaining relatively reliable individual threshold estimates when the quantity of data is limited.

The JIc testing procedures proposed by the American Society for Testing and Materials (ASTM) and the Japan Society of Mechanical Engineers (JSME) were evaluated using medium-strength heat-treated steels. Among the three multiple-specimen methods investigated, the ASTM R-curve method generally gave the largest JIc-values, while the JSME R-curve method provided the smallest values. The JSME stretched zone width (SZW) method, which was developed with emphasis on accurate identification of the initiation of ductile tearing, yielded relatively high toughness values that were rather close to those by the ASTM method. The ASTM method provided a relatively stable procedure for toughness determination and yielded values higher than that at the onset of ductile tearing for these materials. The JSME R-curve method seemed to give the values closest to the onset of ductile tearing among the three methods investigated. The JSME SZW method showed sensitivity to interpretation and definition of the critical values of SZW. Development of a stable procedure for determining the critical SZW values may be of primary importance for improving reliability of the JSME SZW method.

Determination of halogens and sulfur in high-purity polyimide by IC after digestion by MIC

Determination of metals and metalloids in light and heavy crude oil by ICP-MS after digestion by microwave-induced combustion