Simultaneous determination of dissolved gases and moisture in mineral insulating oils by static headspace gas chromatography with helium photoionization pulsed discharge detection.

This paper presents the development of a static headspace capillary gas chromatographic method (HS-GC) for simultaneously determining dissolved gases (H2, O2, N2, CO, CO2, CH4, C2H6, C2H4, C2H2, C3H8) and moisture from a unique 15-mL mineral oil sample. A headspace sampler device is used to equilibrate the sample species in a two-phase system under controlled temperature and agitation conditions. A portion of the equilibrated species is then automatically split-injected into two chromatographic channels mounted on the same GC for their separation. The hydrocarbons and the lighter gases are separated on the first channel by a GS-Q column coupled with a MolSieve 5-A column via a bypass valve, while the moisture is separated on the second channel using a Stabilwax column. The analytes are detected by using two universal pulsed-discharge helium ionization detectors (PDHID). The performance of the method was established using equilibrated vials containing known amounts of gas mixture, water, and blank oil. The signal is linear over the concentration ranges normally found for samples collected from open-breathing power transformers. Determination sensitivity varies with the nature of the species considered with values as high as 21 500 A x 10(-9) s (microg/ g)(-1) for H2O, 46-216 A x 10(-9) s (microL/L)(-1) for the hydrocarbons and carbon oxides, and as low as 8-21 A x 10(-9) s (microL/L)(-1) for the O2 and N2 permanent gases. The detection limit of the method is between 0.08 and 6 microL/L for the dissolved gases, except for O2, N2, and CO2, where higher values are observed due to air intrusion during sampler operations, and 0.1 microg/g for the dissolved water. Ten consecutive measurements in the low and high levels of the calibration curves have shown a precision better than 12% and 6%, respectively, in all cases. A comparison study between the HS-GC method and the ASTM standard procedures on 31 field samples showed a very good agreement of the results. The advantages of configuring the arrangement with two PDHID over the conventional flame ionization and thermal conductivity detectors were clearly demonstrated.

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.

A multi-institutional study of factors associated with fetal death in injured pregnant patients.

HYPOTHESIS: Factors associated with fetal death in injured pregnant patients are related to increasing injury severity and abnormal maternal physiologic profile. DESIGN: A multi-institutional retrospective study of 13 level I and level II trauma centers from 1992 to 1996. MAIN OUTCOME MEASURE: Fetal survival. RESULTS: Of 27,715 female admissions, there were 372 injured pregnant patients (1.3%); 84% had blunt injuries and 16% had penetrating injuries. There were 14 maternal deaths (3.8%) and 35 fetal deaths (9.4%). The population suffering fetal death had higher injury severity scores (P<.001), lower Glascow Coma Scale scores (P<.001), and lower admitting maternal pH (P = .002). Most women who lost their fetus arrived in shock (P = .005) or had a fetal heart rate of less than 110 beats/min at some time during their hospitalization (P<.001). An Injury Severity Score greater than 25 was associated with a 50% incidence of fetal death. Placental abruption was the most frequent complication, occurring in 3.5% of patients and associated with 54% mortality. Cardiotrophic monitoring to detect potentially threatening fetal heart rates was performed on only 61% of pregnant women in their third trimester. Of these patients, 7 had abnormalities on cardiotrophic monitoring and underwent successful cesarean delivery. CONCLUSIONS: Fetal death was more likely with greater severity of injury. Cardiotrophic monitoring is underused in injured pregnant patients in their third trimester even after admission to major trauma centers. Increased use of cardiotrophic monitoring may decrease the mortality caused by placental abruption.

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.

Atomic spectroscopy with surface wave plasmas.

The use of microwave induced plasmas, particularly of surface wave plasmas, as detectors in atomic emission spectrometry for elemental analysis is reviewed. Surface wave plasmas have been produced at low HF power and used as gas chromatographic detectors. The analytical performances for the detection of non-metals with a Fourier transform spectrometer and a two-channel filter unit are reported. The excitation behavior of non-metals in helium-based mixed gas-plasmas has also be studied. In particular, the effect of power and of nitrogen concentration on the bromine emission has been systematically investigated. A nine-fold improvement of the detection limits for bromine can be obtained in a high power (900 W) helium-nitrogen (0.1-0.2%) plasma.