A micro passive preconcentrator for micro gas chromatography.

We describe a microfabricated passive preconcentrator (µPP) intended for integration into gas chromatographic microsystems (µGC) for analyzing volatile/semi-volatile organic compounds (S/VOC). Devices (8 × 8 mm) were made from a silicon-on-insulator top layer and a glass bottom layer. The top layer has 237 apertures (47 × 47 µm) distributed around the periphery of a circular region (5.2 mm o.d.) through which ambient vapors diffuse at predictable rates. Two internal annular cavities offset from the apertures are packed with ∼800 µg each of commercial carbon adsorbents. Thin-film heaters thermally desorb captured vapors, which are drawn by a pump through a central exit port to a micro injector for analysis with a bench scale GC. The 15 test compounds spanned a vapor pressure range of 0.033 to 1.1 kPa. Effective (diffusional) µPP sampling rates ranged from 0.16 to 0.78 mL min-1 for short-duration exposures to ∼mg m-3 vapor concentrations. Observed and modeled sampling rates generally agreed within 15%. Sampling rates for two representative compounds declined by ≤30% between 0.25 and 24 h of continuous exposure. For one of these, the sampling rate declined by only 8% over a ∼2300-fold concentration range (0.25 h samples). Desorption (transfer) efficiencies were >95% for most compounds (250-275 °C, 60 s, 5 mL min-1). Sampling rates for mixtures matched those for the individual compounds. Dissipating no energy while sampling, additional advantages of this novel device include short- or long-term sampling, high capacity and transfer efficiency for a diverse set of S/VOCs, low transfer flow rate, and a robust fabrication process.

Room-temperature-ionic-liquid coated graphitized carbons for selective preconcentration of polar vapors.

Most adsorbent materials used for preconcentrating and thermally desorbing volatile and semi-volatile organic compounds (S/VOCs) in portable or "micro" gas chromatographic (GC/µGC) instruments preferentially capture non-polar or moderately polar compounds relative to more polar compounds. Here, we explore the use of a known trigonal-tripyramidal room-temperature ionic liquid (RTIL) as a surface modifier for the graphitized carbons, Carbopack B (C-B) and Carbopack X (C-X), with the goal of enhancing their capacity and selectivity for polar S/VOCs. Breakthrough tests were performed by challenging tubes packed with ∼2.5 mg of C-B or RTIL-coated C-B (RTIL/C-B) with 13 individual S/VOCs, including several organophosphorus compounds and reference alkyl and aromatic hydrocarbons of comparable vapor pressures, at concentrations ranging from 14 to 130 mg/m3. The 10% breakthrough volume, Vb10, was used as the measure of capacity. For the RTIL/C-B, the Vb10 values of the five organophosphorus vapors tested were consistently ∼2.5 times larger than those for the untreated C-B, and Vb10 values of the four non-polar reference vapors were 11-26 times smaller for the RTIL/C-B than for the untreated C-B. For compounds of similar vapor pressure the capacity ratios for polar vs. non-polar compounds with the RTIL/C-B ranged from 1.8 to 34. Similar results were obtained with C-X and RTIL/C-X on a smaller set of compounds. Tests at 70% relative humidity or with a binary mixture of a polar and non-polar compound had no effect on the capacity of the RTIL/C-B, and there were no changes in Vb10 values after several months of testing that included cycling from 25 to 250 °C. Capacity was strongly correlated with vapor pressure. Attempts to reconcile the selectivity using models based on linear-solvation-energy relationships were only partially successful. Nonetheless, these results indicate that RTIL coating of carbon adsorbents affords a simple, reliable means of rendering them selective for polar S/VOCs.

Belt-Mounted Micro-Gas-Chromatograph Prototype for Determining Personal Exposures to Volatile-Organic-Compound Mixture Components.

We describe a belt-mountable prototype instrument containing a gas chromatographic microsystem (µGC) and demonstrate its capability for near-real-time recognition and quantification of volatile organic compounds (VOCs) in moderately complex mixtures at concentrations encountered in industrial workplace environments. The µGC comprises three discrete, Si/Pyrex microfabricated chips: a dual-adsorbent micropreconcentrator-focuser for VOC capture and injection; a wall-coated microcolumn with thin-metal heaters and temperature sensors for temperature-programmed separations; and an array of four microchemiresistors with thiolate-monolayer-protected-Au-nanoparticle interface films for detection and recognition-discrimination. The battery-powered µGC prototype (20 × 15 × 9 cm, ∼2.1 kg sans battery) has on-board microcontrollers and can autonomously analyze the components of a given VOC mixture several times per hour. Calibration curves bracketing the Threshold Limit Value (TLV) of each VOC yielded detection limits of 16-600 parts-per-billion for air samples of 5-10 mL, well below respective TLVs. A 2:1 injection split improved the resolution of early eluting compounds by up to 63%. Responses and response patterns were stable for 5 days. Use of retention-time windows facilitated the chemometric recognition and discrimination of the components of a 21-VOC mixture sampled and analyzed in 3.5 min. Results from a "mock" field test, in which personal exposures to time-varying concentrations of a mixture of five VOCs were measured autonomously, agreed closely with those from a reference GC. Thus, reliable, near-real-time determinations of worker exposures to multiple VOCs with this wearable µGC prototype appear feasible.

Comprehensive two-dimensional gas chromatographic separations with a temperature programmed microfabricated thermal modulator.

Comprehensive two-dimensional gas chromatography (GC×GC) with a temperature-programmed microfabricated thermal modulator (µTM) is demonstrated. The 0.78 cm(2), 2-stage µTM chip with integrated heaters and a PDMS coated microchannel was placed in thermal contact with a solid-state thermoelectric cooler and mounted on top of a bench scale GC. It was fluidically coupled through heated interconnects to an upstream first-dimension ((1)D) PDMS-coated capillary column and a downstream uncoated capillary or second-dimension ((2)D) PEG-coated capillary. A mixture of n-alkanes C6-C10 was separated isothermally and the full-width-at-half-maximum (fwhm) values of the modulated peaks were assessed as a function of the computer-controlled minimum and maximum stage temperatures of µTM, Tmin and Tmax, respectively. With Tmin and Tmax fixed at -25 and 100°C, respectively, modulated peaks of C6 and C7 had fwhm values<53 ms while the modulated peaks of C10 had a fwhm value of 1.3s, due to inefficient re-mobilization. With Tmin and Tmax fixed at 0 and 210°C, respectively, the fwhm value for the modulated C10 peaks decreased to 67 ms, but C6 and C7 exhibited massive breakthrough. By programming Tmin from -25 to 0°C and Tmax from 100 to 220°C, the C6 and C7 peaks had fwhm values≤50 ms, and the fwhm for C10 peaks remained<95 ms. Using the latter conditions for the GC×GC separation of a sample of unleaded gasoline yielded resolution similar to that reported with a commercial thermal modulator. Replacing the PDMS phase in the µTM with a trigonal-tricationic room temperature ionic liquid eliminated the bleed observed with the PDMS, but also reduced the capacity for several test compounds. Regardless, the demonstrated capability to independently temperature program this low resource µTM enhances its versatility and its promise for use in bench-scale GC×GC systems.

Polymer-coated micro-optofluidic ring resonator detector for a comprehensive two-dimensional gas chromatographic microsystem: µGC ×µGC-µOFRR.

We describe first results from a micro-analytical subsystem that integrates a detector comprising a polymer-coated micro-optofluidic ring resonator (µOFRR) chip with a microfabricated separation module capable of performing thermally modulated comprehensive two-dimensional gas chromatographic separations (µGC ×µGC) of volatile organic compound (VOC) mixtures. The 2 × 2 cm µOFRR chip consists of a hollow, contoured SiO(x) cylinder (250 µm i.d.; 1.2 µm wall thickness) grown from a Si substrate, and integrated optical and fluidic interconnection features. By coupling to a 1550 nm tunable laser and photodetector via an optical fiber taper, whispering gallery mode (WGM) resonances were generated within the µOFRR wall, and shifts in the WGM wavelength caused by transient sorption of eluting vapors into the PDMS film lining the µOFRR cylinder were monitored. Isothermal separations of a simple alkane mixture using a PDMS coated 1st-dimension ((1)D) µcolumn and an OV-215-coated 2nd-dimension ((2)D) µcolumn confirmed that efficient µGC ×µGC-µOFRR analyses could be performed and that responses were dominated by film-swelling. Subsequent tests with more diverse VOC mixtures demonstrated that the modulated peak width and the VOC sensitivity were inversely proportional to the vapor pressure of the analyte. Modulated peaks as narrow as 120 ms and limits of detection in the low-ng range were achieved. Structured contour plots generated with the µOFRR and a reference FID were comparable.

Toward a microfabricated preconcentrator-focuser for a wearable micro-scale gas chromatograph.

This article describes work leading to a microfabricated preconcentrator-focuser (µPCF) designed for integration into a wearable microfabricated gas chromatograph (µGC) for monitoring workplace exposures to volatile organic compounds (VOCs) ranging in vapor pressure from ∼0.03 to 13kPa at concentrations near their respective Threshold Limit Values. Testing was performed on both single- and dual-cavity, etched-Si µPCF devices with Pyrex caps and integrated resistive heaters, packed with the graphitized carbons Carbopack X (C-X) and/or Carbopack B (C-B). Performance was assessed by measuring the 10% breakthrough volumes and injection bandwidths of a series of VOCs, individually and in mixtures, as a function of the VOC air concentrations, mixture complexity, sampling and desorption flow rates, adsorbent masses, temperature, and the injection split ratio. A dual-cavity device containing 1.4mg of C-X and 2.0mg of C-B was capable of selectively and quantitatively capturing a mixture of 14 VOCs at low-ppm concentrations in a few minutes from sample volumes sufficiently large to permit detection at relevant concentrations for workplace applications with the µGC detector that we ultimately plan to use. Thermal desorption at 225°C for 40s yielded ≥99% desorption of all analytes, and injected bandwidths as narrow as 0.6s facilitated efficient separation on a downstream 6-m GC column in <3min. A preconcentration factor of 620 was achieved for benzene from a sample of just 31mL. Increasing the mass of C-X to 2.3mg would be required for exhaustive capture of the more volatile target VOCs at high-ppm concentrations.

µGC × µGC: comprehensive two-dimensional gas chromatographic separations with microfabricated components.

The development and characterization of a microanalytical subsystem comprising silicon-micromachined first- and second-dimension separation columns and a silicon-micromachined thermal modulator (µTM) for comprehensive two-dimensional (i.e., µGC × µGC) separations are described. The first dimension consists of two series-coupled 3.1 cm × 3.1 cm µcolumn chips with etched channels 3 m long and 250 µm × 140 µm in cross section, wall-coated with a poly(dimethylsiloxane) (PDMS) stationary phase. The second dimension consists of a 1.2 cm × 1.2 cm µcolumn chip with an etched channel 0.5 m long and 46 µm × 150 µm in cross section wall-coated with either a trigonal tricationic room-temperature ionic liquid (RTIL) or a commercial poly(trifluoropropylmethyl siloxane) (OV-215) stationary phase. The two-stage, cryogen-free µTM consists of a Si chip containing two series-coupled, square spiral channels 4.2 cm and 2.8 cm long and 250 µm × 140 µm in cross section wall-coated with PDMS. Conventional injection methods and flame ionization detection were used. Temperature-ramped separations of a simple alkane mixture using the RTIL-coated second-dimension ((2)D) µcolumn produced reasonably good peak shapes and modulation numbers; however, strong retention of polar compounds on the RTIL-coated (2)D µcolumn led to excessively broad peaks with low (2)D resolution. Substituting OV-215 as the (2)D µcolumn stationary phase markedly improved the performance, and a structured 22 min chromatogram of a 36-component mixture spanning a vapor pressure range of 0.027 to 13 kPa was generated with modulated peak fwhm (full width at half-maximum) values ranging from 90 to 643 ms and modulation numbers of 1-6.

A microfabricated optofluidic ring resonator for sensitive, high-speed detection of volatile organic compounds.

Advances in microanalytical systems for multi-vapor determinations to date have been impeded by limitations associated with the microsensor technologies employed. Here we introduce a microfabricated optofluidic ring resonator (µOFRR) sensor that addresses many of these limitations. The µOFRR combines vapor sensing and fluidic transport functions in a monolithic microstructure comprising a hollow, vertical SiOx cylinder (250 µm i.d., 1.2 µm wall thickness; 85 µm height) with a central quasi-toroidal mode-confinement section, grown and partially released from a Si substrate. The device also integrates on-chip fluidic-interconnection and fiber-optic probe alignment features. High-Q whispering gallery modes generated with a tunable 1550 nm laser exhibit rapid, reversible shifts in resonant wavelength arising from polymer swelling and refractive index changes as vapors partition into the ~300 nm PDMS film lining the cylinder. Steady-state sensor responses varied in proportion to concentration over a 50-fold range for the five organic vapors tested, providing calculated detection limits as low as 0.5 ppm (v/v) (for m-xylene and ethylbenzene). In dynamic exposure tests, responses to 5 µL injected m-xylene vapor pulses were 710 ms wide and were only 18% broader than those from a reference flame-ionization detector and also varied linearly with injected mass; 180 pg was measured and the calculated detection limit was 49 pg without use of preconcentration or split injection, at a flow rate compatible with efficient chromatographic separations. Coupling of this µOFRR with a micromachined gas chromatographic separation column is demonstrated.

Microfabricated gas chromatograph for rapid, trace-level determinations of gas-phase explosive marker compounds.

A prototype microfabricated gas chromatograph (µGC) adapted specifically for the rapid determination of selected gas-phase marker compounds of the explosive 2,4,6-trinitrotoluene (TNT) at sub-parts-per-billion (

Hybrid preconcentrator/focuser module for determinations of explosive marker compounds with a micro-scale gas chromatograph.

This article describes the development and characterization of a partially selective preconcentrator/focuser (PCF) module for a field-portable micro-scale gas chromatograph (µGC) designed to rapidly determine trace levels of two vapor-phase markers of the explosive trinitrotoluene (TNT): 2,3-dimethyl-2,3-dinitrobutane (DMNB) and 2,4-dinitrotoluene (2,4-DNT). The PCF module has three primary components. The first is a high-volume sampler, comprising a resistively-heated 6-cm long stainless steel tube packed with tandem beds of the graphitized carbons Carbopack B (C-B, 30 mg) and Carbopack Y (C-Y, 15 mg), which traps the markers but permits more volatile interferences to pass through largely unretained. The second component is a microfocuser (µF), comprising a 4.2×9.8 mm Si chip containing a deep-reactive-ion-etched (DRIE) cavity packed with 2mg of C-B, a Pyrex cap, integrated heaters, and etched fluidic channels. The third component is a commercial polymer-membrane filter used as a pre-trap to remove particles and adsorbed low volatility interferences. Markers captured in the sampler are thermally desorbed and transferred to the µF, and then thermally desorbed/injected from the µF into a downstream separation (micro)column and detected. Scrubbed ambient air is used as carrier gas. The adsorbent capacities, baseline temperatures, sampling and desorption flow rates, and heating profiles were optimized for each PCF module component while minimizing the analysis time. An overall transfer efficiency of 86% was achieved at marker concentrations of ~0.2-2.6 ppb. In the final configuration the PCF module requires just 60s to collect a 1-L sample (3 L/min), focus (40 mL/min), and inject the markers (3 mL/min), producing half-maximum injection peak widths of ~2 and 5 s, and preconcentration factors of 4500 and 1800, for DMNB and 2,4-DNT, respectively.

Comprehensive two-dimensional gas chromatographic separations with a microfabricated thermal modulator.

Rapid, comprehensive two-dimensional gas chromatographic (GC × GC) separations by use of a microfabricated midpoint thermal modulator (µTM) are demonstrated, and the effects of various µTM design and operating parameters on performance are characterized. The two-stage µTM chip consists of two interconnected spiral etched-Si microchannels (4.2 and 2.8 cm long) with a cross section of 250 × 140 µm(2), an anodically bonded Pyrex cap, and a cross-linked wall coating of poly(dimethylsiloxane) (PDMS). Integrated heaters provide rapid, sequential heating of each µTM stage, while a proximate, underlying thermoelectric cooler provides continual cooling. The first-dimension column used for GC × GC separations was a 6 m long, 250 µm i.d. capillary with a PDMS stationary phase, and the second-dimension column was a 0.5 m long, 100 µm i.d. capillary with a poly(ethylene glycol) phase. Using sets of five to seven volatile test compounds (boiling point ≤174 °C), the effects of the minimum (T(min)) and maximum (T(max)) modulation temperature, stage heating lag/offset (O(s)), modulation period (P(M)), and volumetric flow rate (F) on the quality of the separations were evaluated with respect to several performance metrics. Best results were obtained with a T(min) = -20 °C, T(max) = 210 °C, O(s) = 600 ms, P(M) = 6 s, and F = 0.9 mL/min. Replicate modulated peak areas and retention times were reproducible to <5%. A structured nine-component GC × GC chromatogram was produced, and a 21 component separation was achieved in <3 min. The potential for creating portable µGC × µGC systems is discussed.

Microfabricated gas chromatograph for on-site determination of trichloroethylene in indoor air arising from vapor intrusion. 1. Field evaluation.

Results are presented of inaugural field tests of two identical prototype microfabricated gas chromatographs (µGC) adapted for the in situ determination of trichloroethylene (TCE) in indoor air in support of vapor intrusion (VI) investigations. Each µGC prototype has a pretrap and partially selective high-volume sampler of conventional design, a micromachined-Si focuser for injection, dual micromachined-Si columns for separation, and an integrated array of four microscale chemiresistors with functionalized gold nanoparticle interface films for multichannel detection. Scrubbed ambient air is used as the carrier gas. Field-generated calibration curves were linear for injected TCE masses of 26-414 ng (4.8-77 ppb·L; r(2) > 0.98) and the projected single-sensor detection limit was 0.052 ppb for an 8-L air sample collected and analyzed in 20 min. Consistent performance between the prototypes and good medium-term stability were shown. Above the mitigation action level (MAL) of 2.3 ppb for the field-test site, µGC TCE determinations fell within ±25% of those from the reference method for 21 of 26 measurements, in the presence of up to 37 documented background VOCs. Below the MAL, positive biases were consistently observed, which are attributable to background VOCs that were unresolvable chromatographically or by analysis of the sensor-array response patterns. Results demonstrate that this type of µGC instrument could serve the need for routine TCE determinations in VI-related assessment and mitigation efforts.

Microfabricated gas chromatograph for on-site determinations of TCE in indoor air arising from vapor intrusion. 2. Spatial/temporal monitoring.

We demonstrate the use of two prototype Si-microfabricated gas chromatographs (µGC) for continuous, short-term measurements of indoor trichloroethylene (TCE) vapor concentrations related to the investigation of TCE vapor intrusion (VI) in two houses. In the first house, with documented TCE VI, temporal variations in TCE air concentrations were monitored continuously for up to 48 h near the primary VI entry location under different levels of induced differential pressure (relative to the subslab). Concentrations ranged from 0.23 to 27 ppb by volume (1.2-150 µg/m(3)), and concentration trends agreed closely with those determined from concurrent reference samples. The sensitivity and temporal resolution of the measurements were sufficiently high to detect transient fluctuations in concentration resulting from short-term changes in variables affecting the extent of VI. Spatial monitoring showed a decreasing TCE concentration gradient with increasing distance from the primary VI entry location. In the second house, with no TCE VI, spatial profiles derived from the µGC prototype data revealed an intentionally hidden source of TCE within a closet, demonstrating the capability for locating non-VI sources. Concentrations measured in this house ranged from 0.51 to 56 ppb (2.7-300 µg/m(3)), in good agreement with reference method values. This first field demonstration of µGC technology for automated, near-real-time, selective VOC monitoring at low- or subppb levels augurs well for its use in short- and long-term on-site analysis of indoor air in support of VI assessments.

Microfabricated passive vapor preconcentrator/injector designed for microscale gas chromatography.

The design, fabrication, and preliminary testing of a micromachined-Si passive vapor preconcentrator/injector (µPPI) are described. Intended for incorporation in a gas chromatographic microsystem (µGC) for analyzing organic vapor mixtures, the µPPI captures vapors from the air at a known rate by means of passive diffusion (i.e., without pumping) and then desorbs the vapor sample thermally by means of an integrated heater and injects it downstream (with pumping). The µPPI chip comprises a 1.8 µL deep reactive-ion-etched (DRIE) Si cavity with a resistively heated membrane floor and a DRIE-Si cap containing >1500 parallel diffusion channels, each 54 × 54 × 200 µm. The cavity is packed with 750 µg of a commercial graphitized carbon adsorbent. Fluidic and heat-transfer modeling was used to guide the design process to ensure power-efficient sample transfer during thermal desorption. Experiments performed with toluene at concentrations of ~1 ppm gave a constant sampling rate of 9.1 mL min(-1) for up to 30 min, which is within 2% of theoretical predictions and corresponds to a linear dynamic mass uptake range of ~1 µg. The cavity membrane could be heated to 250 °C in 0.23 s with 1 W of applied power and, with 50 mL min(-1) of suction flow provided by a downstream pump, yielded >95% desorption/injection efficiency of toluene samples over an 8-fold range of captured mass.

Microfabricated optofluidic ring resonator structures.

We describe the fabrication and preliminary optical characterization of rugged, Si-micromachined optofluidic ring resonator (µOFRR) structures consisting of thin-walled SiO(x) cylinders with expanded midsections designed to enhance the three-dimensional confinement of whispering gallery modes (WGMs). These µOFRR structures were grown thermally at wafer scale on the interior of Si molds defined by deep-reactive-ion etching and pre-treated to reduce surface roughness. Devices 85-µm tall with 2-µm thick walls and inner diameters ranging from 50 to 200 µm supported pure-mode WGMs with Q-factors >10(4) near 985 nm. Advantages for eventual vapor detection in gas chromatographic microsystems are highlighted.

Microfabricated gas chromatograph for the selective determination of trichloroethylene vapor at sub-parts-per-billion concentrations in complex mixtures.

A complete field-deployable microfabricated gas chromatograph (µGC) is described, and its adaptation to the analysis of low- and subparts-per-billion (ppb) concentrations of trichloroethylene (TCE) vapors in complex mixtures is demonstrated through laboratory testing. The specific application being addressed concerns the problem of indoor air contamination by TCE vapor intrusion. The µGC prototype employs a microfabricated focuser, dual microfabricated separation columns, and a microsensor array. These are interfaced to a nonmicrofabricated front-end pretrap and high-volume sampler module to reduce analysis time and limits of detection (LOD). Selective preconcentration and focusing are coupled with rapid chromatographic separation and multisensor detection for the determination of TCE in the presence of up to 45 interferences. Autonomous operation is possible via a laptop computer. Preconcentration factors as high as 500 000 are achieved. Sensitivities are constant over the range of captured TCE masses tested (i.e., 9-390 ng), and TCE is measured in a test atmosphere at 120 parts-per-trillion (ppt), with a projected LOD of 40 ppt (4.2 ng captured, 20 L sample) and a maximum sampling + analytical cycle time of 36 min. Short- and medium-term (1 month) variations in retention time, absolute responses, and response patterns are within acceptable limits.

Evaluation of a microfabricated thermal modulator for comprehensive two-dimensional microscale gas chromatography.

A microfabricated thermal modulator (µTM) designed for ultimate use in a comprehensive two-dimensional microscale gas chromatography (µGC × µGC) system is evaluated. The 2-stage device measures 13 mm (l) × 6 mm (w) × 0.5 mm (h) and consists of two interconnected serpentine etched-Si microchannels suspended from a thin Pyrex cap and wall-coated with PDMS (polydimethylsiloxane). The chip is mounted within a few tens of micrometers of a thermoelectric cooler that maintains both stages at a baseline temperature between -35 and -20 °C in order to focus analytes eluting from an upstream separation column. Each stage is heated to 210 °C sequentially at a rate as high as 2400 °C/s by independent thin-film resistors to inject the analytes in consecutive fractions to a downstream column, and then cooled at a rate as high as -168 °C/s. The average power dissipation is only ∼10 W for heating and 21 W for cooling without using consumable materials. In this study, the outlet of the µTM is connected directly to a flame ionization detector to assess its performance. Following a demonstration of basic operation, the modulated peak amplitude enhancement (PAE) and full-width-at-half-maximum (fwhm) are evaluated for members of a series of n-alkanes (C(6)-C(10)) as a function of the rim and stage temperatures; modulation period, phase, and offset; analyte concentration; and carrier-gas flow rate. A PAE as high as 50 and a fwhm as narrow as 90 ms are achieved for n-octane under optimized conditions.

Characterization of dense arrays of chemiresistor vapor sensors with submicrometer features and patterned nanoparticle interface layers.

The performance of arrays of small, densely integrated chemiresistor (CR) vapor sensors with electron-beam patterned interface layers of thiolate-monolayer-protected gold nanoparticles (MPNs) is explored. Each CR in the array consists of a 100-µm(2) interdigital electrode separated from adjacent devices by 4 µm. Initial studies involved four separate arrays, each containing four CRs coated with one of four different MPNs, which were calibrated with five vapors before and after MPN-film patterning. MPNs derived from n-octanethiol (C8), 4-(phenylethynyl)-benzenethiol (DPA), 6-phenoxyhexane-1-thiol (OPH), and methyl-6-mercaptohexanoate (HME) were tested. Parallel calibrations of MPN-coated thickness-shear-mode resonators (TSMR) were used to derive partition coefficients of unpatterned films and to assess transducer-dependent factors affecting responses. A 600-µm(2) 4-CR array with four different patterned MPN interface layers, in which the MPN derived from 7-hydroxy-7,7-bis(trifluoro-methyl)heptane-1-thiol (HFA) was substituted for HME, was then characterized. This is the smallest multi-MPN array yet reported. Reductions in the diversity of the collective response patterns are observed with the patterned films, but projected vapor discrimination rates remain high. The use of such arrays as ultralow-dead-volume detectors in microscale gas chromatographic analyzers is discussed.

Multi-stage preconcentrator/focuser module designed to enable trace level determinations of trichloroethylene in indoor air with a microfabricated gas chromatograph.

This article describes the development and characterization of a multi-stage preconcentrator/focuser (PCF) module designed to be integrated with a microfabricated gas chromatograph (µGC) for autonomous, in situ determinations of volatile organic compounds. The PCF module has been optimized specifically for the determination of trichloroethylene (TCE) vapors at low- or sub-parts-per-billion concentrations in the presence of common indoor air co-contaminants in residences at risk of vapor intrusion (VI) from surrounding TCE-contaminated soil. It consists of three adsorbent-packed devices arranged in series: a pre-trap of conventional (tubular metal) design for capturing interferences with vapor pressures <3 torr; a high-volume sampler, also of conventional design, for capturing (and transferring) TCE and other compounds with vapor pressures within the range of ~3 to 95 torr; and a microfocuser (µF) consisting of a micromachined Si chamber with an integrated microheater for focusing and injecting samples into the separation module. The adsorbent masses, sampling and desorption flow rates, and heating profiles required for selective, quantitative capture and transfer/injection of TCE are determined for each of the devices, and the assembled PCF module is used to analyze a test atmosphere containing 200 parts-per-trillion of TCE and 27 relevant co-contaminants with a conventional downstream capillary column and electron-capture detector. An average TCE transfer efficiency of 107% is achieved for a 20 L air sample, with a preconcentration factor of ~800,000.

Microfabricated thermal modulator for comprehensive two-dimensional micro gas chromatography: design, thermal modeling, and preliminary testing.

In comprehensive two-dimensional gas chromatography (GC x GC), a modulator is placed at the juncture between two separation columns to focus and re-inject eluting mixture components, thereby enhancing the resolution and the selectivity of analytes. As part of an effort to develop a microGC x microGC prototype, in this report we present the design, fabrication, thermal operation, and initial testing of a two-stage microscale thermal modulator (microTM). The microTM contains two sequential serpentine Pyrex-on-Si microchannels (stages) that cryogenically trap analytes eluting from the first-dimension column and thermally inject them into the second-dimension column in a rapid, programmable manner. For each modulation cycle (typically 5 s for cooling with refrigeration work of 200 J and 100 ms for heating at 10 W), the microTM is kept approximately at -50 degrees C by a solid-state thermoelectric cooling unit placed within a few tens of micrometres of the device, and heated to 250 degrees C at 2800 degrees C s(-1) by integrated resistive microheaters and then cooled back to -50 degrees C at 250 degrees C s(-1). Thermal crosstalk between the two stages is less than 9%. A lumped heat transfer model is used to analyze the device design with respect to the rates of heating and cooling, power dissipation, and inter-stage thermal crosstalk as a function of Pyrex-membrane thickness, air-gap depth, and stage separation distance. Experimental results are in agreement with trends predicted by the model. Preliminary tests using a conventional capillary column interfaced to the microTM demonstrate the capability for enhanced sensitivity and resolution as well as the modulation of a mixture of alkanes.