Anomalies in evaporative light scattering detection.

A two-dimensional (2-D) "heart-cutting" HPLC system was used to fractionate oligostyrenes into the respective diastereoisomers. For samples of known composition, the response of an ultraviolet (UV) absorbance detector followed the anticipated pattern. The response of an evaporative light-scattering (ELSD) detector on the other hand indicated quite different concentrations for the two diastereoisomers, relative to what was anticipated and what was indicated by the UV detector. Whereas approximately the same concentration was indicated by UV, ELSD in some cases indicated no detection of the later eluting isomer. The magnitude of the errors depended on both the molecular weight and the tacticity of the diastereomers. These anomalies appear to be an artifact of power transform functions imbedded within the firmware processor of the ELSD, invisible to the user.

Application of power functions to chromatographic data for the enhancement of signal to noise ratios and separation resolution.

Chromatographic detection responses are recorded digitally. A peak is represented ideally by a Guassian distribution. Raising a Guassian distribution to the power 'n' increases the height of the peak to that power, but decreases the standard deviation by radicaln. Hence there is an increasing disparity in detection responses as the signal moves from low level noise, with a corresponding decrease in peak width. This increases the S/N ratio and increases peak to peak resolution. The ramifications of these factors are that poor resolution in complex chromatographic data can be improved, and low signal responses embedded at near noise levels can be enhanced. The application of this data treatment process is potentially very useful in 2D-HPLC where sample dilution occurs between dimension, reducing signal response, and in the application of post-reaction detection methods, where band broadening is increased by virtue of reaction coils. In this work power functions applied to chromatographic data are discussed in the context of (a) complex separation problems, (b) 2D-HPLC separations, and (c) post-column reaction detectors.

A membraneless gas diffusion unit: design and its application to determination of ethanol in liquors by spectrophotometric flow injection.

This work presents new design of a gas diffusion unit, called 'membraneless gas diffusion (MGD) unit', which, unlike a conventional gas diffusion (GD) unit, allows selective detection of volatile compounds to be made without the need of a hydrophobic membrane. A flow injection method was developed employing the MGD unit to determine ethanol in alcoholic drinks based on the reduction of dichromate by ethanol vapor. Results clearly demonstrated that the MGD unit was suitable for determination of ethanol in beer, wine and distilled liquors. Detection limit (3S/N) of MGD unit was lower than the GD unit (GD: 0.68%, v/v; MGD: 0.27%, v/v). The MGD design makes the system more sensitive as mass transfer is more efficient than that of GD and thus, MGD can perfectly replace membrane-based designs.

Two-Dimensional detection in ion chromatography: sequential conductometry after suppression and passive hydroxide introduction.

An improved method that uses sequential suppressed and nonsuppressed IC for the sensitive detection of both common anions and very weak acid anions is described. After suppressed conductometric detection of an electrolytically generated hydroxide eluent and an electrolytic suppressor, the eluent is passed into a membrane device where KOH is passively introduced into the eluent stream using Donnan forbidden leakage. A second conductivity detector then measures the conductivity of the stream. The background conductance of the second detector is typically maintained at a relatively low level of 20-30 microS/ cm. The weak acids are converted to potassium salts that are fully ionized and are detected against a low KOH background as negative peaks. The applicability of different commercially available cation exchange membranes was studied. Device configurations investigated include planar, tubular, and a filament-filled annular helical (FFAH) device. The FFAH device provided more effective mixing of the penetrated hydroxide with the eluent stream, resulting in a noise level of < or = 7 nS/cm and a band dispersion value of less than 82 microL. Optimal design and performance data are presented.

Continuous automated measurement of hexavalent chromium in airborne particulate matter.

An automated continuous instrument for the collection and measurement of aerosol Cr(VI) is described. The system alternately collects the sample on one of two glass fiber filters. After 15-min sample collection on one filter, the sampling switches over to the second filter. The freshly sampled filter is washed for 8.5 min, and the washings are preconcentrated on a minicolumn packed with anion exchange resin. The washed filter is dried with filtered hot air for the next 6.5 min so that it is ready for sampling at the end of the 15-min cycle. The preconcentrated Cr(VI) on the column is eluted with 0.1 M sodium perchlorate and then reacted with sym-1,5-diphenylcarbazide prior to absorbance detection with a light emitting diode-based dedicated flow-through absorbance detector. The detection limit (S/N = 3) is 5 ng of Cr(VI)/m3, orders of magnitude lower than current regulatory requirements. The instrument operates unattended over long periods. In continuous round-the-clock operation, filter replacement frequency is every 24-72 h, depending on dust loading. The system is portable for facile field deployment and permits fully automated rapid determinations at a very low analysis cost per sample.

Fluorometric field instrument for continuous measurement of atmospheric hydrogen sulfide.

A sensitive (limit of detection approximately <100 pptv at S/N = 3), fully automated, portable (32 x 25 x 38 cm, 4.5 kg) instrument has been designed for continuous field measurement of atmospheric hydrogen sulfide. Air is sampled by a PTFE membrane-based diffusion scrubber and collected into an aLkaline fluorescein mercuric acetate (FMA) solution flowing under a controlled and constant pneumatic pressure. The collected sulfide quenches the fluorescence that is measured with a miniature blue LED photodiode-based fluorescence detector. Acquisition and interpretation of signal and all flow control are carried out via a mininotebook personal computer (PC) using custom software written in HP-VEE. The instrument provides for self-calibration and zero functions using an on-board permeation tube enclosed in a thermostated block, at any preprogrammed desired interval. During sampling, the computed H2S concentration is stored every 2 min. The complete system, including the PC, is operated in the field by a 12-V marine battery. The system was field tested near oil field operations in West Texas and showed good correlations with a concurrently operated lead acetate tape-based commercial sampler, with a response speed and time resolution much better than that of the latter instrument.

A study of cardio-pulmonary efficiency in different categories of runners.

Selected short distance runners, middle distance runners and long distance runners were subjected to graded exercise on a treadmill. The maximum aerobic power (VO2 max) and other indices related to oxygen transport system viz. heart rate, ventilation volume, breathing reserve, dyspnoeic index, O2 pulse and RQ were recorded at respective VO2 max work loads, and the values were compared. Long distance runners and middle distance runners showed a significantly higher VO2 max than the short distance runners when VO2 max was expressed per unit of body weight. Among the endurance runners, long distance runners had a significantly lower resting pulse rate as well as the maximum heart rate during work than the middle distance runners. On comparison, Ventilation Volume, Breathing reserve, Dyspnoeic index, O2 pulse and RQ at VO2 max work loads do not differ significantly among different categories of runners.

Ion chromatographic determination of acidity.

The practice of determining acid concentrations by titrations has remained unchanged for more than a century. We introduce a new approach to the determination of acid concentrations based on cation exchange chromatography. We demonstrate the ability of sulfonated styrene-divinylbenzene based stationary phases to separate the hydrogen ion from other monovalent cations. The eluent is a dilute solution of a neutral salt, sometimes containing a small concentration of the corresponding acid, e.g., sodium ethanesulfonate, pH adjusted with ethanesulfonic acid. The high equivalent conductance (approximately 350 S.cm2/equiv) of H+ and relatively low eluent concentration allows sensitive conductometric detection of H+, down to the 50 microM level under favorable conditions. The conductometric response to H+ can be linear over a wide range of H+ concentrations, from sub-millimolar to several molar concentrations. The system allows the rapid quantitation of strong acids; weak acids can also be determined depending on pKa and injected concentration. The determinations of several strong and weak acids are presented along with factors that govern their chromatographic analysis.

Simultaneous flow-injection measurement of hydroxide, chloride, hypochlorite and chlorate in Chlor-alkali cell effluents.

A flow injection method is reported for the simultaneous determination of hydroxide, chloride, hypochlorite, and chlorate ions that exist in Chlor-alkali cell effluents in concentrations ranging from sub-millimolar to several molar. The hydroxide concentration is determined by the heat of neutralization of the injected sample into an acidic carrier stream and the chloride concentration is calculated from the measured conductance data. For the measurement of hypochlorite and chlorate, colorimetric iodometry is used. Iodide is oxidized to iodine by OCl(-) and ClO(3)(-) in acid solutions. While room temperature is sufficient for the reaction between OCl(-) and I(-), the reaction between ClO(3)(-) and I(-) requires an elevated temperature. The different reaction requirements are utilized to differentiate between NaOCl and NaClO(3), respectively.

Wet effluent parallel plate diffusion denuder coupled capillary ion chromatograph for the determination of atmospheric trace gases.

We describe an inexpensive, compact parallel plate diffusion denuder coupled capillary IC system for the determination of soluble ionogenic atmospheric trace gases. The active sampling area (0.6x10 cm) of the denuder is formed in a novel manner by thermally bonding silica gel particles to the surface of Plexiglas plates. The effluent liquid from the parallel plate diffusion denuder is collected and preconcentrated on a capillary preconcentrator column before analysis using a capillary ion chromatograph. Using SO(2) as the test gas, collection efficiency is essentially quantitative at air sampling rates up to 500 ml min(-1). The system provides a limit of detection (LOD) of 1.6 parts per trillion for SO(2) for a 10 min sampling period.

Optical fiber coupled light emitting diode based absorbance detector with a reflective flow cell.

We present a versatile, optical fiber coupled light emitting diode (LED) light source based flow-through optical absorbance detector. The LED source is readily changeable. Optical fibers are used to carry light from the electronics/display unit to a reflective flow-through cell and back. The cell can thus be located remotely from the electronics unit and the umbilical connection is not susceptible to electrical noise. The noise level of this detector with LEDs of different emission maxima were observed to be in the range of 3-20 muAU under actual use conditions, with a maximum short term drift of 4 muAU/min after the initial warm-up period. When the analyte absorbance is well matched with the source emission characteristics, the detector response is linear with concentration over at least two orders of magnitude. The liquid flow path through the cell is linear with a large exit aperture such that bubbles are not trapped in the optical path. The optical arrangement is such that the incident light crosses the liquid flow orthogonally and is reflected back by a rear mirror to the receiver fiber. This arrangement reduces the refractive index sensitivity by an order of magnitude relative to conventional Z-path flow cells.

Transversely illuminated liquid core waveguide based fluorescence detection Fluorometric flow injection determination of aqueous ammonium/ammonia.

The analytical performance of a new type of fluorescence detector, based on a transversely illuminated liquid core waveguide (LCW), has been investigated using the determination of NH(3)/NH(4)(+) as the 1-sulfonatoisoindole. With a very inexpensive combination of a miniature Hg blacklight as an excitation source, a colored plastic sheet as the emission filter, and an integrated blue sensitized photodiode-operational amplifier as the detector (totaling <$100 in hardware cost), we were able to achieve a limit of detection (LOD) of 35 nM (1.6 pmol) NH(3) with a linear dynamic range up to 60 muM NH(3). Details of detector construction and performance are given.

Determination of oxidative stability of oils and fats.

In a new approach to evaluating the oxidative stability of oils and fats, the consumption of oxygen by a sample confined in a reactor of adjustable temperature is monitored with a gas-phase flow injection analysis (FIA) system. Temperature-dependent data are collected in a low-oxygen-content atmosphere. For a variety of samples, log(oxygen consumption) is linearly related to the reciprocal of the absolute temperature (minimum linear r(2) > 0.99). This makes it possible to extrapolate the temperature-dependent data to predict the stability of the samples at other temperatures, e.g., typical ambient storage temperatures at which the direct determination of oxidative stability would be too slow for most samples. The proposed method is instrumentally simple and is easily automated. The sample throughput rate is an order of magnitude faster relative to current alternatives; temperature-dependent stability characterization for a sample (three temperatures, triplicate measurement at each temperature) requires ≤ 2 h. The reproducibility of the results is excellent. For a cottonseed-oil sample studied over 3 days, the slope and intercept of the log(O(2) consumption) vs 1/T linear plot (for all the 45 measurements made) exhibited uncertainties of 2.1% and 2.0% for the slope and the intercept, respectively, with a linear r(2) value of 0.9929. In a high-temperature (160 °C) oxidation experiment with various oils, the oxygen consumption was well-correlated (linear r(2) 0.9692) with the concomitant decrease in iodine absorption number (IAN). In contrast, it was poorly and negatively correlated with an increase in the peroxide value.

Luminescence detection with a liquid core waveguide.

A new fluoropolymer tube is proposed as the basis of a novel class of liquid core waveguide-based luminescence detectors. Both chemiluminescence and photoluminescence detectors are possible. In the latter case, illumination is transverse to the main axis of the tube. With such a geometry, it is even possible to operate without monochromators, although limits of detection do improve with the incorporation of monochromators. The nature of the design is such that it is particularly simple to fabricate detectors in a flow-through configuration and where the light from the cell is coupled to a photodetector by an optical fiber. No focusing optics are necessary. A number of applications are illustrated. Attainable limits (LODs, S/N = 3) of detection include 150 pM fluorescein with a 254-nm excitation source, 200 amol of fluorescein in a capillary electrophoresis setup with excitation by two blue light-emitting diodes, 35 nM NH(3) as the isoindole derivative in a flow injection analysis system using a photodiode detector, 50 nM methylene blue and 1 nM Rhodamine 560 using respectively red and green LED arrays and an avalanche photodiode and a PMT in a FIA configuration, 100 parts per trillion by volume gaseous formaldehyde as the Hantzsch reaction product with cyclohexanedione using a diffusion scrubber, 2.7 µM and 17 nM hypochlorite based on its chemiluminescence reaction with luminol with photodiode and PMT detectors, respectively, and 1 ppm SO(4)(2)(-) based on nephelometric detection at 470 nm. The approach described herein leads to particularly simple and inexpensive luminescence detectors with excellent sensitivity.

Measurement of diffusive flux of ammonia from water.

An instrument was developed for the measurement of gaseous ammonia concentration, NH(3(sw,eq)), in equilibrium with surface waters, notably ocean water. The instrument measures the ammonia flux from a flowing water surface under defined conditions and allows the calculation of NH(3(sw,eq)) from the principles of Fickian diffusion. The flux collector resembles a wetted parallel plate denuder previously developed for air sampling. The sample under study runs on one plate of the device; the ammonia released from the sample is collected by a slow flow of a receptor liquid on the other plate. The NH(3) + NH(4)(+) (hereinafter called N(T)) in the effluent receptor liquid is preconcentrated on a silica gel column and subsequently measured by a fluorometric flow injection analysis (FIA) system. With a 6-min cycle (4-min load, 2-min inject), the analytical system can measure down to 0.3 nM N(T) in the receptor liquid. Coupled with the flux collector, it is sufficiently sensitive to measure the ammonia flux from seawater. The instrument design is such that it is little affected by ambient ammonia. In both laboratory (N(T) 0.2-50 µM), and field investigations (N(T) 0.18-1.7 µM) good linearity between the ammonia flux and the N(T) concentration in seawater (spiked, synthetic, natural) was observed, although aged seawater, with depleted N(T) content, behaves in an unusual fashion upon N(T) addition, showing the existence of an "ammonia demand". NH(3(sw,eq)) levels from ocean water measured in the Coconut Island Laboratory, HI, ranged from 6.6 to 33 nmol/m(3) with an average of 17.4 ± 6.9 nmol/m(3), in comparison to 2.8-21 nmol/m(3) (average 10 ± 7 nmol/m(3)) NH(3(sw,eq)) values previously reported for the Central Pacific Ocean (Quinn, P. K.; et al. J. Geophys. Res. 1990, 95, 16405-16416).

Fluorometric fiber optic drop sensor for atmospheric hydrogen sulfide.

A fluorometric technique based on a liquid drop excited from its interior by an optical fiber is described for the measurement of low concentrations of atmospheric hydrogen sulfide (H(2)S). A drop of alkaline fluorescein mercuric acetate (FMA) solution is suspended in a flowing air sample stream and serves as a renewable sensor. An optical fiber contained within the conduit that forms the drop, brings in the excitation beam; the fluorescence emission is measured by an inexpensive photodiode positioned close to the drop. As H(2)S in the sample is collected by the alkaline drop, it reacts rapidly with FMA resulting in a significant decrease in fluorescence intensity, proportional to the concentration of H(2)S sampled. The chemistry of this uniquely selective reaction has been well established for many years; the present technique permits a simple fast inexpensive near real-time measurement with very little reagent consumption. Even without prolonged sampling/preconcentration steps, limits of detection (LODs) in the double digit ppbv range is readily attainable.

Renewable liquid film-based electrochemical sensor for gaseous hydroperoxides.

Electrochemical sensors for hydroperoxides based on thin flowing films were investigated. The sensor is composed of two segments of Nafion tubing put on a silver wire. A small portion of the silver wire is exposed and is chloridized to function as the reference electrode. One Nafion segment has a Pt-wire coil wrapped on it to function as the counter electrode and the other has a similar Pt-Rh wire coil that functions as the working electrode. A collection solution flows as a thin film on the sensor surface and also functions as the collection medium. Hydrogen peroxide and cumene hydroperoxide were examined as test compounds. The former can be oxidatively determined with a Pt-Rh electrode over a large range (ppb-ppm) without any significant influence of relative humidity. By using a technique to stop the liquid flow, the sensitivity can be further improved. Cumene hydroperoxide, an industrially important hydroperoxide, can be determined easily with a relative precision of better than 5% in the vapor phase over simulated process reaction mixtures containing percentage levels of the analyte by reduction on a Pd electrode. The sensor is simple and inexpensive to fabricate and requires only a suitably equipped personal computer for operation.

Chromatography on water-ice.

Ice contains a thin film of water on its surface, the thickness ranging from nanometer to micrometer levels, depending on the bulk temperature and the composition of the solution used in making the ice. It follows that water held on the surface of an ice particle should endow a column packed with microparticulate ice the properties of a chromatographic column containing a pellicular packing. We demonstrate here the normal phase separation of two dyes on a column packed with millimeter-size ice particles, held at -18 °C.

Capillary Ion Chromatography with On-Line High-Pressure Electrodialytic NaOH Eluent Production and Gradient Generation.

A small inexpensive system is described that allows high-performance suppressed anion chromatography on a capillary scale. A fully computer-controlled stepper motor-driven syringe-type dispenser, equipped with a 500 µL-capacity glass syringe is capable of pumping at pressures up to 1000 psi when equipped with an appropriate inlet check valve. Fused-silica capillary columns ∼50 cm in length and 180 µm i.d., packed in-house with a commercial packing, provide excellent performance, significantly exceeding the efficiencies observed for the same packing in commercially available 2 mm bore format. The system operates with a pressure drop of <800 psi at a flow rate of 2 µL/min. The system utilizes a novel electrodialytic NaOH eluent generator that is deployed on the high-pressure side of the pump and thus requires no special measures for electrolytic gas removal. This device permits both isocratic and gradient operation with excellent eluent purity; the NaOH concentration is generated linearly with applied current with near-Faradaic efficiency, up to a concentration of at least 100 mM.