Biomedical subjects

E T Zellers

Publications and source records attributed to E T Zellers.

At least 19 recordsLinked to original sources

PubMed2001

A portable, high-speed, vacuum-outlet GC vapor analyzer employing air as carrier gas and surface acoustic wave detection.

Vacuum-outlet GC with atmospheric-pressure air as the carrier gas is implemented at outlet pressures up to 0.8 atm using a low-dead-volume polymer-coated surface acoustic wave (SAW) detector. Increases in the system outlet pressure from 0.1 to 0.8 atm lead to proportional increases in detector sensitivity and significant increases in column efficiency. The latter effect arises from the fact that optimal carrier gas velocities are lower in air than in more conventional carrier gases such as helium or hydrogen due to the smaller binary diffusion coefficients of vapors in air. A 12-m-long, 0.25-mm-i.d. tandem column ensemble consisting of 4.5-m dimethyl polysiloxane and 7.5-m trifluoropropylmethyl polysiloxane operated at an outlet pressure of 0.5 atm provides up to 4 x 10(4) theoretical plates and a peak capacity of 65 (resolution, 1.5) for a 3-min isothermal analysis. At 30 degrees C, mixtures of vapors ranging in vapor pressure from 8.6 to 76 Torr are separated in this time frame. The SAW detector cell has an internal volume of < 2 microL, which allows the use of higher column outlet pressures with minimal dead time. The sensor response is linear with solute mass over at least 2-3 decades and provides detection limits of 20-50 ng for the vapors tested. The combination of atmospheric-pressure air as carrier gas, modest operating pressures, and SAW sensor detection is well-suited for field instrumentation since it eliminates the need for support gases, permits smaller, low-power pumps to be used, and provides sensitivity to a wide range of vapor analytes.

Acoustics↗

PubMed2001

A dual-adsorbent preconcentrator for a portable indoor-VOC microsensor system.

The development and testing of a miniature dual-adsorbent preconcentrator for a microsensor-based analytical system designed to determine complex volatile organic chemical (VOC) mixtures encountered in indoor working environments at low part-per-billion levels is described. Candidate adsorbents were screened for thermal-desorption bandwidth and breakthrough volume against 20 volatile organic vapors and subsets thereof as a function of several relevant variables. A glass capillary (1.1 mm i.d.) packed with 3.4 mg of Carbopack X and 1.2 mg of Carboxen 1000 provides sufficient capacity for a 1-L dry-air sample containing all 20 vapors at concentrations of 100 ppb as well as providing a composite half-height peak width of <3 s at a desorption temperature of 300 degrees C and a flow rate of 4 mL/min. Required adsorbent masses increase to 7.0 and 1.5 mg, respectively, for the same mixture at component concentrations of 1 ppm. Vapor breakthrough volumes for the Carbopack X are unaffected by humidity from 0 to 100%RH, but those for the Carboxen 1000 are significantly reduced, requiring an additional 0.9 mg of the latter to avoid premature breakthrough at the 100 ppb level. Good peak shapes, efficient chromatographic separation of preconcentrated sample mixture components, and detection limits in the low-parts-per-billion range using an integrated surface-acoustic-wave (SAW) sensor are achieved. Preconcentrator design and operating parameters are considered in terms of the vapor bed-residence times and breakthrough volumes in the context of the modified Wheeler equation.

Adsorption↗

PubMed2001

Use of linear solvation energy relationships for modeling responses from polymer-coated acoustic-wave vapor sensors.

The applicability and performance of linear solvation energy relationships (LSERs) as models of responses from polymer-coated acoustic-wave vapor sensors are critically examined. Criteria for the use of these thermodynamic models with thickness-shear-mode resonator (TSMR) and surface-acoustic-wave (SAW) vapor sensors are clarified. Published partition coefficient values derived from gas-liquid chromatography (GLC) are found to be consistently lower than those obtained gravimetrically, in accordance with previous reports, suggesting that LSERs based on GLC-derived partition coefficients will not provide accurate estimates of acoustic-wave sensor responses. The development of LSER models directly from polymer-coated TSMR vapor sensor response data is demonstrated and a revised model developed from SAW vapor sensor response data, which takes account of viscoelastic changes in polymeric coating films, is presented and compared to those developed by other methods.

Chromatography, Gas↗

PubMed2001

High-speed analysis of complex indoor VOC mixtures by vacuum-outlet GC with air carrier gas and programmable retention.

A pressure-tunable, series-coupled column ensemble was used with atmospheric pressure air as carrier gas for the vacuum-outlet GC analysis of 42 volatile and semivolatile organic compounds commonly encountered as indoor air pollutants. Separation strategies applicable to a field-portable instrument that will employ a dual-stage preconcentrator and a microsensor array as the detector were developed, where coelution of certain analytes can be tolerated. The capillary column ensemble consists of a 4.5-m segment of nonpolar dimethyl polysiloxane followed by a 7.5-m segment of polar trifluoropropylmethyl polysiloxane. Good long-term thermal stability of the column ensemble was observed for continuous operation in air at temperatures up to 210 degrees C. A computer-driven pressure controller at the column junction point is used to adjust vapor retention for specified sets of target compounds. The compounds were divided into two groups according to retention order, and high-speed analysis conditions were determined for the two groups individually as well as for the entire mixture. The earlier eluting group of 21 compounds was analyzed isothermally at 30 degrees C in about 160 s using a single, on-the-fly junction-point pressure change during the separation. The later eluting group of 21 compounds was analyzed in about 200 s with temperature programming and a constant (tuned) junction-point pressure. The entire mixture was analyzed in about 400 s using a two-step temperature program and a three-step pressure program, with minimal overlap in eluting peaks. Separations are adequate for analysis by a sensor array capable of discriminating among small groups of coeluting vapors on the basis of their response patterns.

Air Pollutants↗

PubMed2001

Analysis of solvent vapors in breath and ambient air with a surface acoustic wave sensor array.

This article describes the development and evaluation of a small prototype instrument employing an array of four polymer-coated surface acoustic wave (SAW) sensors for rapid analysis of organic solvent vapors in exhaled breath and ambient air. A thermally desorbed adsorbent preconcentrator within the instrument is used to increase sensitivity and compensate for background water vapor. Calibrations were performed for breath and dry nitrogen samples in Tedlar bags spiked with 16 individual solvents and selected binary mixtures. Responses were linear over the 50- to 400-fold concentration ranges examined and mixture responses were additive. The resulting library of vapor calibration response patterns was used with extended disjoint principal components regression and a probabilistic artificial neural network to develop vapor-recognition algorithms. In a subsequent analysis of an independent data set all individual vapors and most binary mixture components were correctly identified and were quantified to within 25% of their actual concentrations. Limits of detection for a 0.25 l. sample collected over a 2.5-min period were <0.3xTLV for 14 of the 16 vapors based on the criterion that all four sensors show a detectable response. Results demonstrate the feasibility of this technology for workplace analysis of breath and ambient air.

Acoustics↗

PubMed2000

The fractional free volume of the sorbed vapor in modeling the viscoelastic contribution to polymer-coated surface acoustic wave vapor sensor responses.

Surface acoustic wave (SAW) vapor sensors with polymeric sorbent layers can respond to vapors on the basis of mass loading and modulus decreases of the polymer film. The modulus changes are associated with volume changes that occur as vapor is sorbed by the film. A factor based on the fractional free volume of the vapor as a liquid has been incorporated into a model for the contribution of swelling-induced modulus changes to observed SAW vapor sensor responses. In this model, it is not the entire volume added to the film by the vapor that contributes to the modulus effect; it is the fractional free volume associated with the vapor molecules that causes the modulus to decrease in a manner that is equivalent to free volume changes from thermal expansion. The amplification of the SAW vapor sensor response due to modulus effects that are predicted by this model has been compared to amplification factors determined by comparing the responses of polymer-coated SAW vapor sensors with the responses of similarly coated thickness shear mode (TSM) vapor sensors, the latter being gravimetric. Results for six to eight vapors on each of two polymers, poly(isobutylene) and poly(epichlorohydrin), were examined. The model predicts amplification factors of the order of about 1.5-3, and vapor-dependent variations in the amplification factors are related to the specific volume of the vapor as a liquid. The fractional free volume factor provides a physically meaningful addition to the model and is consistent with conventional polymer physics treatments of the effects of temperature and plasticization on polymer modulus.

Elasticity↗

PubMed2000

Determination of solvents permeating through chemical protective clothing with a microsensor array.

The performance of a novel prototype instrument in determining solvents and solvent mixtures permeating through samples of chemical protective clothing (CPC) materials was evaluated. The instrument contains a mini-preconcentrator and an array of three polymer-coated surface-acoustic-wave (SAW) microsensors whose collective response patterns are used to discriminate among multiple permeants. Permeation tests were performed with a 2.54 cm diameter test cell in an open-loop configuration on samples of common glove materials challenged with four individual solvents, three binary mixtures, and two ternary mixtures. Breakthrough times, defined as the times required for the permeation rate to reach a value of 1 microg cm(-2) min(-1), determined by the instrument were within 3 min of those determined in parallel by manual sampling and gas chromatographic analysis. Permeating solvents were recognized (identified) from their response patterns in 59 out of 64 measurements (92%) and their vapor concentrations were quantified to an accuracy of +/- 31% (typically +/- 10%). These results demonstrate the potential for such instrumentation to provide semi-automated field or bench-top screening of CPC permeation resistance.

Humans↗

PubMed2000

Temperature and humidity compensation in the determination of solvent vapors with a microsensor system.

Accounting for changes in temperature and ambient humidity is critical to the development of practical field vapor-monitoring instrumentation employing microfabricated sensor arrays. In this study, responses to six organic vapors were collected from two prototype field instruments over a range of ambient temperatures and relative humidities (RH). Each instrument contains an array of three unthermostated polymer-coated surface acoustic wave (SAW) resonators, a thermally desorbed adsorbent preconcentrator bed, a reversible pump and a small scrubber cartridge. Negligible changes in the vapor sensitivities with atmospheric RH were observed owing, in large part, to the temporal separation of co-adsorbed water from the organic vapor analytes upon thermal desorption of preconcentrated air samples. As a result, calibrations performed at one RH level could be used to determine vapors at any other RH without corrections using standard pattern recognition methods. Negative exponential temperature dependences that agreed reasonably well with those predicted from theory were observed for many of the vapor-sensor combinations. It was possible to select a subset of sensors with structurally diverse polymer coatings whose sensitivities to all six test vapors and selected binary vapor mixtures had similar temperature dependences. Thus, vapor recognition could be rendered independent of temperature and vapor quantification could be corrected for temperature with sufficient accuracy for most applications. The results indicate that active temperature control is not necessary and that temperature and RH compensation is achievable with a relatively simple microsensor system.

Environmental Monitoring↗

PubMed1999

Vapor recognition with small arrays of polymer-coated microsensors. A comprehensive analysis.

A comprehensive analysis of vapor recognition as a function of the number of sensors in a vapor-sensor array is presented. Responses to 16 organic vapors collected from six polymer-coated surface acoustic wave (SAW) sensors were used in Monte Carlo simulations coupled with pattern recognition analyses to derive statistical estimates of vapor recognition rates as a function of the number of sensors in the array (< or = 6), the polymer sensor coatings employed, and the number and concentration of vapors being analyzed. Results indicate that as few as two sensors can recognize individual vapors from a set of 16 possibilities with < 6% average recognition error, as long as the vapor concentrations are > 5 x LOD for the array. At lower concentrations, a minimum of three sensors is required, but arrays of 3-6 sensors provide comparable results. Analyses also revealed that individual-vapor recognition hinges more on the similarity of the vapor response patterns than on the total number of possible vapors considered. Vapor mixtures were also analyzed for specific 2-, 3-, 4-, 5-, and 6-vapor subsets where all possible combinations of vapors within each subset were considered simultaneously. Excellent recognition rates were obtainable for mixtures of up to four vapors using the same number of sensors as vapors in the subset. Lower recognition rates were generally observed for mixtures that included structurally homologous vapors. Acceptable recognition rates could not be obtained for the 5- and 6-vapor subsets examined, due, apparently, to the large number of vapor combinations considered (i.e., 31 and 63, respectively). Importantly, increasing the number of sensors in the array did not improve performance significantly for any of the mixture analyses, suggesting that for SAW sensors and other sensors whose responses rely on equilibrium vapor-polymer partitioning, large arrays are not necessary for accurate vapor recognition and quantification.

Chemistry Techniques, Analytical↗

PubMed1998

Establishing a limit of recognition for a vapor sensor array.

Organic vapor analysis with microsensor arrays relies principally on two output parameters: the response pattern, which provides qualitative information, and the response sensitivity, which determines the limit of detection (LOD). The latter is used to define the operating limit in the low-concentration range, under the implicit assumption that, if a vapor can be detected, it can be identified and differentiated from other vapors on the basis of its response pattern. In this study, the performance of an array of four polymer-coated surface acoustic wave vapor sensors was explored using calibrated response data from 16 solvent vapors in Monte Carlo simulations coupled with pattern recognition analysis. The statistical modeling revealed that the ability to recognize a vapor from its response pattern decreases with decreasing vapor concentration, as expected, but also that the concentration at which errors in vapor recognition become excessive is well above the calculated LOD in most cases, despite the LOD being based on the least sensitive sensor in the array. These results suggest the adoption of a limit of recognition (LOR), defined as the concentration below which a vapor can no longer be reliably recognized from its response pattern, as an additional criterion for evaluating the performance of multisensor arrays. A generalized method for estimating the LOR is presented, as well as a means for improving the LOR via residual error analysis.

Calibration↗

PubMed1998

ASTM F739 method for testing the permeation resistance of protective clothing materials: critical analysis with proposed changes in procedure and test-cell design.

ASTM (American Society for Testing and Materials) Method F739-96 specifies a test-cell design and procedures for measuring the permeation resistance of chemical protective clothing. Among the specifications are open-loop collection stream flow rates of 0.050 to 0.150 L/min for a gaseous medium. At elevated temperatures the test must be maintained within 1 degree C of the set point. This article presents a critical analysis of the effect of the collection stream flow rate on the measured permeation rate and on the temperature uniformity within the test cell. Permeation tests were conducted on four polymeric glove materials with 44 solvents at 25 degrees C. Flow rates > 0.5 L/min were necessary to obtain accurate steady-state permeation rate (SSPR) values in 25 percent of the tests. At the lower flow rates the true SSPR typically was underestimated by a factor of two or less, but errors of up to 33-fold were observed. No clear relationship could be established between the need for a higher collection stream flow rate and either the vapor pressure or the permeation rate of the solvent, but test results suggest that poor mixing within the collection chamber was a contributing factor. Temperature gradients between the challenge and collection chambers and between the bottom and the top of the collection chamber increased with the water-bath temperature and the collection stream flow rate. Use of a test cell modified to permit deeper submersion reduced the gradients to < or = 0.5 degrees C. It is recommended that all SSPR measurements include verification of the adequacy of the collection stream flow rate. For testing at nonambient temperatures, the modified test cell described here could be used to ensure temperature uniformity throughout the cell.

Gloves, Protective↗

PubMed1996

Effects of temperature and humidity on the performance of polymer-coated surface acoustic wave vapor sensor arrays.

The influences of temperature and atmospheric humidity on the performance of an array of eight polymer-coated 158-MHz surface acoustic wave vapor sensors were investigated. Sensitivities to the seven organic vapors examined all exhibited negative Arrhenius temperature dependencies, with responses increasing by factors of 1.5-4.4 on going from 38 to 18 degrees C. The magnitudes of the temperature effects, while generally similar, differed sufficiently among certain sensor-vapor combinations to cause marked changes in vapor response patterns. In addition, it was found that operating identically coated sensors at different temperatures could provide a means for discriminating certain vapors. The changes in sensor responses with temperature agreed reasonably well with those expected assuming ideal vapor sorption behavior and indicated that changes in the moduli of the sensor coatings were not important mediating factors. Responses to relative humidity (RH) from 0 to 85% RH were important even for the nonpolar sensor coatings. Significant changes in the sensitivities to the organic vapors were observed as a function of atmospheric humidity for several sensor-vapor combinations, which, in turn, affected the patterns of responses obtained from the sensor array. Results indicate that small changes in temperature or humidity have a larger effect on baseline stabilities than on the responses to the vapors. Monte Carlo simulations of sensor responses show that the ability to discriminate vapors in binary and ternary mixtures using a four-sensor array remains high regardless of the operating temperature and ambient humidity, provided that temperature-or humidity-induced changes in the response patterns are taken into account.

Acoustics↗

PubMed1996

Respiratory health in asbestos-exposed ironworkers.

This study aimed to determine the prevalence of respiratory morbidity among asbestos-exposed ironworkers and to determine the relationship between respiratory morbidity indices and length of exposure. A medical screening provided information on chest radiographic abnormalities, pulmonary function, rales, finger clubbing, and respiratory symptoms for 547 asbestos-exposed ironworkers. Union pension records furnished data on length of exposure. The study group exhibited on increased prevalence of small irregular opacities, pleural plaques, and pleural thickening on chest x-ray; reduced FEF 25-75; rales; and respiratory symptoms. After controlling for the effect of cigarette smoking and age, years since joining the ironworkers union were significantly associated with profusion, pleural thickening, pleural plaques, rales, percent predicted FVC, reduced FVC, reduced FEV1, reduced FEV1/FVC, and dyspnea grades I, II, III, and IV.

Female↗

PubMed1996

Prototype instrument employing a microsensor array for the analysis of organic vapors in exhaled breath.

A prototype portable instrument capable of selectively measuring organic vapors in breath at low- and sub-ppm concentrations was tested. The instrument employs an array of four polymer-coated surface-acoustic-wave (SAW) resonators and microprocessor-controlled pumps, valves, and heating elements for preconcentration and thermal desorption of breath samples. Response data are passed to an external personal computer for processing. Sensor responses are based on the reversible changes in the mass and viscoelasticity of the polymeric coatings accompanying vapor sorption. Calibrations were performed for perchloroethylene, trichloroethylene, and methoxyflurane at 100% relative humidity using 15 mg of TenaxTA as the preconcentrator adsorbent. Analyses were then conducted of 250-mL breath samples prepared in Tedlar bags spiked with one of the three solvents within the range of 2 to 18 ppm. Differences between concentrations measured using the prototype instrument and those measured by gas chromatography ranged from -6 to 17% for perchloroethylene. Similar results were obtained for trichloroethylene and methoxyflurane with larger differences occurring at lower concentrations. Estimated limits of detection of 0.7, 0.6, and 4 ppm were achieved for perchloroethylene, trichloroethylene, and methoxyflurane, respectively. These preliminary results demonstrate the feasibility of using SAW sensor technology for field breath analysis.

Breath Tests↗

PubMed1996

Investigation of organic vapor losses to condensed water vapor in Tedlar bags used for exhaled-breath sampling.

This study evaluated the potential loss of organic vapors to condensed water in bags used for breath sampling. "Wet" test atmospheres were prepared by transferring nitrogen into 1-L Tedlar bags and spiking with water and each of several organic solvents (methanol, acetone, 2-butanone,m-xylene, 1,1,1 trichloroethane, and perchloroethylene) to yield atmospheres representative of a 500-mL breath sample collected at 37 degrees C and cooled to 25 degrees C. Vapor concentrations were compared with those in bags prepared without water. Differences between mean concentrations in wet and dry bags were significant only for methanol, which yielded a mean wet-bag concentration approximately 10% lower than for dry bags. In a second series of experiments the same initial concentration of solvent vapor was generated in 1 dry bag and 5 bags containing 1 to 20 times the amount of water expected to condense in a 500-mL breath sample. Significant differences between wet and dry bag concentrations were seen for methanol, acetone, and 2-butanone; however, the quantity of water required to produce this difference in the acetone and 2-butanone bags exceeded three times that expected to condense in a breath sample. Results were in good agreement with predictions based on Henry's law. In both experiments permeation of water vapor out of the bags led to a decrease in the quantity of condensed water, thereby reducing the extent of organic vapor partitioning. These results indicate that solvent vapor loss to condensed water is not likely to be significant under typical conditions.

Body Water↗

PubMed1995

Optimal coating selection for the analysis of organic vapor mixtures with polymer-coated surface acoustic wave sensor arrays.

A method for determining the optimal set of polymer sensor coatings to include in a surface acoustic wave (SAW) sensor array for the analysis of organic vapors is described. The method combines an extended disjoint principal components regression (EDPCR) pattern recognition analysis with Monte Carlo simulations of sensor responses to rank the various possible coating selections and to estimate the ability of the sensor array to identify any set of vapor analytes. A data base consisting of the calibrated responses of 10 polymer-coated SAW sensors to each of six organic solvent vapors from three chemical classes was generated to demonstrate the method. Responses to the individual vapors were linear over the concentration ranges examined, and coatings were stable over several months of operation. Responses to binary mixtures were additive functions of the individual component responses, even for vapors capable of strong hydrogen bonding. The EDPCR-Monte Carlo method was used to select the four-sensor array that provided the least error in identifying the six vapors, whether present individually or in binary mixtures. The predicted rate of vapor identification (87%) was experimentally verified, and the vapor concentrations were estimated within 10% of experimental values in most cases. The majority of errors in identification occurred when an individual vapor could not be differentiated from a mixture of the same vapor with a much lower concentration of a second component. The selection of optimal coating sets for several ternary vapor mixtures is also examined. Results demonstrate the capabilities of polymer-coated SAW sensor arrays for analyzing of solvent vapor mixtures and the advantages of the EDPCR-Monte Carlo method for predicting and optimizing performance.

Acoustics↗

PubMed1993

Characterization of polymeric surface acoustic wave sensor coatings and semiempirical models of sensor responses to organic vapors.

Responses from an array of four polymer-coated surface acoustic wave sensors exposed to a series of 39 organic vapors were used to investigate sensor response models based on vapor boiling point, solubility parameters, and solvation parameters in conjunction with linear solvation energy relationships. As part of this effort, sensor response data were used to estimate the solubility parameters and solvation parameters of the sensor coatings by adaptation of methods originally developed for use with gas-liquid chromatographic retention data. Values of these parameters were found to be consistent with the structures of the coatings though in some cases different from those determined by other methods. Discrepancies were attributed to differences in the conditions used for the determinations. Sensor responses were linear over the concentration ranges examined and could be summarized using the empirically determined partition coefficient, Ke, for each vapor-coating pair. Linear correlations were found between log Ke and vapor boiling point, and the slopes of the regressions lines were similar to those expected for ideal behavior. The strength of the correlations decreased with increasing coating polarity, and it was necessary to divide the vapors into two or three broad chemical classes in order to obtain satisfactory results. Improved correlations were found by use of Hildebrand solubility parameters in a model based on regular solution theory which attempts to account for nonideal vapor-coating interactions. The use of solvation parameters in linear solvation energy relationships, however, provided the strongest correlations, with modeled K values falling within a factor of 2 of experimental values in all cases and within +/- 25% of experimental values in 83% of the cases. Application of these models to the prediction of sensor array response patterns appears promising.

Gases↗

PubMed1993

Coated surface acoustic wave sensor employing a reversible mass-amplifying ligand substitution reaction for real-time measurement of 1,3-butadiene at low- and sub-ppm concentrations.

Real-time measurement of 1,3-butadiene gas using a surface acoustic wave (SAW) sensor coated with the square-planar Pt(II)-olefin pi-complex PtCl2-(1-hexene) (pyridine) and related complexes is described. Amplification of the sensor response results from displacement of two 1-hexene molecules by each butadiene molecule and formation of the bridged complex [PtCl2(pyridine)]2(1,3-butadiene). Using a 30-MHz SAW oscillator, the rate of frequency change is linearly related to the butadiene air concentration from 150 ppb to > or = 13 ppm and a calculated detection limit of 101 ppb is obtained. Using a 60-MHz oscillator, the detection limit is reduced to 24 ppb. No effect on the sensor response is observed with changes in relative humidity from 5 to 80% or changes in temperature from 25 to 35 degrees C. No interference is observed from several industrially relevant non-olefin organic gases and vapors. Responses are obtained for several olefins, but they interfere with the response to butadiene only at higher relative concentrations. The reagent can be regenerated repeatedly by brief exposure to 1-hexene vapor with retention of the original response characteristics upon subsequent exposure. The potential for using this sensor to monitor occupational 1,3-butadiene exposures is discussed in light of the recently proposed occupational exposure limit of 2 ppm.

Air Pollutants, Occupational↗