Flow-through Measurements Research Articles

Multi-Component Sensor Coatings for Identification and Quantification of Four Chemical Isomers: Ethylbenzene and M-, P-, O-Xylene in Water

Introduction The eight-carbon aromatic isomers ethylbenzene and m-, p-, and o-xylene are difficult to separate from one another due to similarities in molecular structure and physicochemical properties. Separating these isomers is often necessary for industrial chemical synthesis [1]. Additionally, each isomer displays slightly different toxicity [2]. However, in drinking water guidelines, only data for total xylenes is provided because separate quantification of each isomer without the use of sophisticated spectroscopic or chromatographic methods is difficult. Furthermore, for most sensors based on sorption into polymer coatings, polymer/water partition coefficients for these analytes are much lower than polymer/air partition coefficients, resulting in low sensitivity and poor selectivity in their liquid-phase sensing.One method for addressing the above issues is to design multi-component sensor coatings that highlight the small variations in isomer structures. Such coatings can be designed by selecting coating components based on their chemical and physical properties, as well as the properties of the target analytes [3]. Properly designed coatings will show favorable sensing parameters (sensitivity, partial selectivity) in liquid-phase measurements compared to commercially available single-component polymers.Initial results indicate that selectivity of multi-component coatings can be significantly higher, thus enabling identification of chemical isomers, which were previously not (or barely) distinguishable in the liquid phase, with limits of detection in the low parts-per-billion (ppb) by weight. Furthermore, by utilizing advanced sensor signal processing [4] to analyze sensor data, minute response differences between the isomers ethylbenzene and the three xylenes can be uniquely identified, even in solutions of multiple analytes. Sensor Coating Design The design of chemical sensor coatings should select properties of the coating components, in light of the target analytes, that predict and control sensing behavior. The sensing mechanism utilized here relies on bulk absorption of target analytes into polymer coatings. Polarity/dipole moment and polarizability of coating and target isomers affect the absorption process and, as a result, the sensitivity of the coated sensor to the analyte. Multi-component coatings using polymer-plasticizer blends to generate Hansen solubility parameters (HSP) that favor strong coating-analyte interactions, i.e. favorable coating/water analyte partition coefficients, were designed for this work. These coatings exhibit significantly increased sensitivity and partial selectivity to target isomers compared to single-component polymers, such as poly(epichlorohydrin) or poly(isobutylene). As a result, minute variations in analyte properties (polarity/dipole moment, polarizability, etc.) can be detected at lower analyte concentrations. The designed coatings consist of blends of polystyrene (PS) and one of two plasticizers, diisooctyl azelate (DIOA) or ditridecyl phthalate (DTP). Identification of ethylbenzene and xylene is demonstrated for each polymer-plasticizer pair, with sensitivities for ethylbenzene and each xylene isomer in good agreement with trends in dipole moments and polarizabilities. Method Solutions of multi-component coatings were prepared with varying plasticizer-to-polymer weight ratios (given below) and with varying concentrations of polymer-plasticizer blend in the solvent. Coatings were deposited onto SH-SAW sensor devices via spin coating for use in direct liquid-phase measurements. Coating thicknesses were determined by profilometry. Coated sensors were exposed to diluted aqueous solutions of target analytes in flow-through measurements. The concentrations of analyte solutions were independently confirmed using a gas-chromatograph photoionization detector (GC-PID) system. Frequency responses of coated sensors are used to extract sensing parameters such as sensitivity, response time constant, and viscoelastic properties of the coatings. Extracted sensing parameters for each isomer serve as inputs for an advanced estimation-theory-based sensor signal-processing technique that quantifies mixtures. Results and Conclusions Table 1 shows relative energy difference (RED) values for pairs of coatings and analytes calculated using Equation 1, as well as dipole moment, polarizability, and measured sensitivity and response time constant for each isomer. The polymer-plasticizer blend coatings selected are 17.5% DIOA-PS and 30% DTP-PS. RED values for each pair of materials are well below 1.0, indicating excellent miscibility. While differences between isomers are relatively small, the measured variation in responses is highlighted with an appropriate multivariate signal-processing method. The extracted average sensitivity and average response time constant for each coating/analyte pair, shown in Table 1, correlate well with the trends in analytes’ dipole moments and polarizabilities. High sensitivities to ethylbenzene and xylene isomers are observed. Responses of the DIOA-PS coating to ethylbenzene and total xylenes are easily distinguishable from one another. Figure 1 shows single-analyte response curves for the DTP-PS coating for ethylbenzene and m-, p-, and o-xylene. Sensing parameters were extracted from the responses, thus allowing minute differences to be clearly observed. It is demonstrated that DTP-PS coatings show partial selectivity between ethylbenzene, m-, p-, and o-xylene. Figure 2 shows the response curve of a multi-analyte solution of the three xylene isomers, with estimated and measured concentrations for each isomer in the mixture in Table 2. Experimental responses and extracted results strongly support that selectivity to each xylene isomer can be achieved with appropriate sensor coating design.

Measuring hydraulic fracture apertures: a comparison of methods

Abstract. Hydraulic fracture apertures predominantly control fluid transport in fractured rock masses. Hence, the objective of the current study is to investigate and compare three different laboratory-scale methods to determine hydraulic apertures in fractured (Fontainebleau and Flechtinger) sandstone samples with negligible matrix permeability. Direct measurements were performed by using a flow-through apparatus and a transient-airflow permeameter. In addition, a microscope camera permitted measuring the mechanical fracture apertures from which the corresponding hydraulic apertures were indirectly derived by applying various empirical correlations. Single fractures in the sample cores were generated artificially either by axial splitting or by a saw cut resulting in hydraulic apertures that ranged between 8 and 66 µm. Hydraulic apertures, accurately determined by the flow-through apparatus, are used to compare results obtained by the other methods. The transient-airflow permeameter delivers accurate values, particularly when repeated measurements along the full fracture width are performed. In this case, the derived mean hydraulic fracture apertures are in excellent quantitative agreement. When hydraulic apertures are calculated indirectly from optically determined mechanical apertures using empirical equations, they show larger variations that are difficult to compare with the flow-through-derived results. Variations in hydraulic apertures as observed between methods are almost certainly related to differences in sampled fracture volume. Overall, using direct flow-through measurements as a reference, this study demonstrates the applicability of portable methods to determine hydraulic fracture apertures at both the laboratory and outcrop scales.

Anodic alumina membrane capacitive sensors for detection of vapors

Here we report membrane capacitive sensors based on anodic aluminum oxide (AAO) Au/AAO/Au structures fabricated by aluminum anodization, followed by gold electrodes sputtering on the countersides of porous ceramic membrane. Electrochemical impedance spectroscopy with AC amplitude 5–100 mV in the frequency range of 1–1000 Hz was utilized for sensor characterization in the presence of water and organic vapors in a full range of P/P0. The sensors illustrate ultimate sensitivity to ambient environment with exponential-scale capacitance relation to vapors content resulting in typical 4–6 orders of magnitude response signal change for 15–85% P/P0 range at a single AC frequency, and up to 7 orders of magnitude response range for 0–100% P/P0 pressure range with using two different AC frequencies. In case of water vapors, the sensitivity increases from ~0.5 nF/RH% at ~20 RH% to over ~1.0 μF/RH% at ~80 RH%. The sensors are capable for highly accurate sensing of gas humidity as well as any dissociative vapors with pKa <30. They are also sensible to polar components with high enough dipole moment or polarizability. The capacitance is affected by any adsorbed molecules, including those having zero dipole moment. The data for sensor response to CH3OH, C2H5OH, CH2ClCHF2, i-C4H10 depending on partial pressures is provided. Due to high porosity (10–30%) and gaseous permeance (up to 200 m3(STP) m-2 bar-1 h-1) the sensors offer fast response rate and a possibility for flow-through measurements, providing also a mass-flow response option, which was tested with SF6, CO2, N2 and He. The basic principles of dielectric loss sensor and the equivalent scheme were proposed for sensor operation in different environment, allowing estimating sensor response.

Multi-Component Sensor Coatings for Identification and Quantification of Four Chemical Isomers: Ethylbenzene and M-, P-, O-Xylene in Water

Introduction The eight-carbon aromatic isomers ethylbenzene and m-, p-, and o-xylene are difficult to separate from one another due to similarities in molecular structure and physicochemical properties. Separating these isomers is often necessary for industrial chemical synthesis [1]. Additionally, each isomer displays slightly different toxicity [2]. However, in drinking water guidelines, only data for total xylenes is provided because separate quantification of each isomer without the use of sophisticated spectroscopic or chromatographic methods is difficult. Furthermore, for most sensors based on sorption into polymer coatings, polymer/water partition coefficients for these analytes are much lower than polymer/air partition coefficients, resulting in low sensitivity and poor selectivity in their liquid-phase sensing.One method for addressing the above issues is to design multi-component sensor coatings that highlight the small variations in isomer structures. Such coatings can be designed by selecting coating components based on their chemical and physical properties, as well as the properties of the target analytes [3]. Properly designed coatings will show favorable sensing parameters (sensitivity, partial selectivity) in liquid-phase measurements compared to commercially available single-component polymers. Initial results indicate that selectivity of multi-component coatings can be significantly higher, thus enabling identification of chemical isomers, which were previously not (or barely) distinguishable in the liquid phase, with limits of detection in the low parts-per-billion (ppb) by weight. Furthermore, by utilizing advanced sensor signal processing [4] to analyze sensor data, minute response differences between the isomers ethylbenzene and the three xylenes can be uniquely identified, even in solutions of multiple analytes. Sensor Coating Design The design of chemical sensor coatings should select properties of the coating components, in light of the target analytes, that predict and control sensing behavior. The sensing mechanism utilized here relies on bulk absorption of target analytes into polymer coatings. Polarity/dipole moment and polarizability of coating and target isomers affect the absorption process and, as a result, the sensitivity of the coated sensor to the analyte. Multi-component coatings using polymer-plasticizer blends to generate Hansen solubility parameters (HSP) that favor strong coating-analyte interactions, i.e. favorable coating/water analyte partition coefficients, were designed for this work. These coatings exhibit significantly increased sensitivity and partial selectivity to target isomers compared to single-component polymers, such as poly(epichlorohydrin) or poly(isobutylene). As a result, minute variations in analyte properties (polarity/dipole moment, polarizability, etc.) can be detected at lower analyte concentrations. The designed coatings consist of blends of polystyrene (PS) and one of two plasticizers, diisooctyl azelate (DIOA) or ditridecyl phthalate (DTP). Identification of ethylbenzene and xylene is demonstrated for each polymer-plasticizer pair, with sensitivities for ethylbenzene and each xylene isomer in good agreement with trends in dipole moments and polarizabilities. Method Solutions of multi-component coatings were prepared with varying plasticizer-to-polymer weight ratios (given below) and with varying concentrations of polymer-plasticizer blend in the solvent. Coatings were deposited onto SH-SAW sensor devices via spin coating for use in direct liquid-phase measurements. Coating thicknesses were determined by profilometry. Coated sensors were exposed to diluted aqueous solutions of target analytes in flow-through measurements. The concentrations of analyte solutions were independently confirmed using a gas-chromatograph photoionization detector (GC-PID) system. Frequency responses of coated sensors are used to extract sensing parameters such as sensitivity, response time constant, and viscoelastic properties of the coatings. Extracted sensing parameters for each isomer serve as inputs for an advanced estimation-theory-based sensor signal-processing technique that quantifies mixtures. Results and Conclusions Table 1 shows relative energy difference (RED) values for pairs of coatings and analytes calculated using Equation 1, as well as dipole moment, polarizability, and measured sensitivity and response time constant for each isomer. The polymer-plasticizer blend coatings selected are 17.5% DIOA-PS and 30% DTP-PS. RED values for each pair of materials are well below 1.0, indicating excellent miscibility. While differences between isomers are relatively small, the measured variation in responses is highlighted with an appropriate multivariate signal-processing method. The extracted average sensitivity and average response time constant for each coating/analyte pair, shown in Table 1, correlate well with the trends in analytes’ dipole moments and polarizabilities. High sensitivities to ethylbenzene and xylene isomers are observed. Responses of the DIOA-PS coating to ethylbenzene and total xylenes are easily distinguishable from one another. Figure 1 shows single-analyte response curves for the DTP-PS coating for ethylbenzene and m-, p-, and o-xylene. Sensing parameters were extracted from the responses, thus allowing minute differences to be clearly observed. It is demonstrated that DTP-PS coatings show partial selectivity between ethylbenzene, m-, p-, and o-xylene. Figure 2 shows the response curve of a multi-analyte solution of the three xylene isomers, with estimated and measured concentrations for each isomer in the mixture in Table 2. Experimental responses and extracted results strongly support that selectivity to each xylene isomer can be achieved with appropriate sensor coating design.

Gas permeability tests on core plugs from unconventional reservoir rocks under controlled stress: A comparison of different transient methods

Accurate and routinely applicable methods to determine porosities and permeability coefficients are needed in order to ensure effective hydrocarbon recovery in shale and tight sandstone plays. In this study 129 gas uptake measurements (“GRI method”, “inflow” experiments) were performed on core plugs from three unconventional reservoir lithotypes (oil shales, gas shales and tight gas sandstones) under elevated effective stress conditions. The results were compared to those from “flow-through” tests (standard pulse decay) under similar experimental conditions, e.g. the same gas type and pore pressure range. The samples covered a porosity range from 1.3% to 12%. Equilibration times ranged from 102 s to 104 s and permeability coefficients from 10−18 to 10−21 m2. In order to successfully determine apparent gas permeability coefficients and porosities and to reliably interpret fluid dynamic effects from gas uptake data it is necessary to ensure a sufficiently high excess pressure drop during the uptake tests. This can be controlled by adjustment of the reservoir to pore volume ratio and initial differential pressure. Permeability coefficients derived from uptake tests on all six samples do not show any systematic deviations from those obtained from flow-through measurements. Best results were achieved for a core plug from the Lower Palaeozoic Alum Shale (Djupvik, Öland, Sweden), where Klinkenberg regressions of inflow and flow-through differ only by 4% (slope) and 10% (y-axis intercept). Here, the gas storage capacity ratio was ≈2.5 and excess pressure drops ranged from 0.1 to 1.2 MPa. Generally, measurement errors were lowest when excess pressure drops during uptake were at least 0.05 MPa for all samples. Excess pressure drops of less than 0.05 MPa resulted in coefficients of variance of single apparent gas permeabilities of ≈10%–100%, whereas excess pressure drops of >0.05 MPa resulted in coefficients of variance of ≈2%–15%. We show that it is possible to adjust the initial conditions of inflow measurements such, that Klinkenberg-corrected permeability coefficients and gas slippage factors can be readily determined. This will contribute significantly to a better understanding of the effects of anisotropy and/or the pore structure on the transport properties of unconventional lithotypes under elevated stress conditions. However, standard deviations of single apparent permeability coefficients derived from inflow experiments are higher by up to one order of magnitude than for those obtained from flow-through tests under all tested conditions.

Investigations of the applicability of a new accountancy tool in a closed tritium loop

A commonly used activity monitoring method for tritium accountancy and process monitoring in tritium technology is ionization counting. Despite the wide use of ionization chambers (IC), they have several drawbacks like a strong gas species and pressure dependency. Furthermore, if compact systems are needed, there is also the necessity for process gas pressures >10kPa. To encounter these drawbacks, the TRitium Activity Chamber Experiment (TRACE) has been developed at the Tritium Laboratory Karlsruhe (TLK) as a compact tritium monitor based on the beta induced X-ray spectrometry (BIXS) principle.TRACE can be used as an accountancy tool in tritium-processing facilities like the KArlsruhe TRItium Neutrino (KATRIN) experiment. In contrast to ICs TRACE shows a linear response to pressure changes up to approx. 1kPa. The results of performed flow-through measurements confirm that TRACE is a complement for ICs in the low-pressure regime. Furthermore the gas species dependency of TRACE is investigated both with tritium measurements and with Monte Carlo simulations.

Measuring the mechanical efficiency of a working cardiac muscle sample at body temperature using a flow-through calorimeter.

We have developed a new `work-loop calorimeter' that is capable of measuring, simultaneously, the work-done and heat production of isolated cardiac muscle samples at body temperature. Through the innovative use of thermoelectric modules as temperature sensors, the development of a low-noise fluid-flow system, and implementation of precise temperature control, the heat resolution of this device is 10 nW, an improvement by a factor of ten over previous designs. These advances have allowed us to conduct the first flow-through measurements of work output and heat dissipation from cardiac tissue at body temperature. The mechanical efficiency is found to vary with peak stress, and reaches a peak value of approximately 15 %, a figure similar to that observed in cardiac muscle at lower temperatures.

Mechanical expansion of steel tubing as a solution to leaky wellbores.

Wellbore cement, a procedural component of wellbore completion operations, primarily provides zonal isolation and mechanical support of the metal pipe (casing), and protects metal components from corrosive fluids. These are essential for uncompromised wellbore integrity. Cements can undergo multiple forms of failure, such as debonding at the cement/rock and cement/metal interfaces, fracturing, and defects within the cement matrix. Failures and defects within the cement will ultimately lead to fluid migration, resulting in inter-zonal fluid migration and premature well abandonment. Currently, there are over 1.8 million operating wells worldwide and over one third of these wells have leak related problems defined as Sustained Casing Pressure (SCP). The focus of this research was to develop an experimental setup at bench-scale to explore the effect of mechanical manipulation of wellbore casing-cement composite samples as a potential technology for the remediation of gas leaks. The experimental methodology utilized in this study enabled formation of an impermeable seal at the pipe/cement interface in a simulated wellbore system. Successful nitrogen gas flow-through measurements demonstrated that an existing microannulus was sealed at laboratory experimental conditions and fluid flow prevented by mechanical manipulation of the metal/cement composite sample. Furthermore, this methodology can be applied not only for the remediation of leaky wellbores, but also in plugging and abandonment procedures as well as wellbore completions technology, and potentially preventing negative impacts of wellbores on subsurface and surface environments.

Mechanical Expansion of Steel Tubing as a Solution to Leaky Wellbores

Wellbore cement, a procedural component of wellbore completion operations, primarily provides zonal isolation and mechanical support of the metal pipe (casing), and protects metal components from corrosive fluids. These are essential for uncompromised wellbore integrity. Cements can undergo multiple forms of failure, such as debonding at the cement/rock and cement/metal interfaces, fracturing, and defects within the cement matrix. Failures and defects within the cement will ultimately lead to fluid migration, resulting in inter-zonal fluid migration and premature well abandonment. Currently, there are over 1.8 million operating wells worldwide and over one third of these wells have leak related problems defined as Sustained Casing Pressure (SCP)1. The focus of this research was to develop an experimental setup at bench-scale to explore the effect of mechanical manipulation of wellbore casing-cement composite samples as a potential technology for the remediation of gas leaks. The experimental methodology utilized in this study enabled formation of an impermeable seal at the pipe/cement interface in a simulated wellbore system. Successful nitrogen gas flow-through measurements demonstrated that an existing microannulus was sealed at laboratory experimental conditions and fluid flow prevented by mechanical manipulation of the metal/cement composite sample. Furthermore, this methodology can be applied not only for the remediation of leaky wellbores, but also in plugging and abandonment procedures as well as wellbore completions technology, and potentially preventing negative impacts of wellbores on subsurface and surface environments.

Periodic heartbeat reversals cause cardiogenic inspiration and expiration with coupled spiracle leakage in resting blowfliesCalliphora vicinaR.-D.

Respiration in insects is thought to be independent of the circulatory system because insects typically lack respiratory pigments and because oxygen transport occurs in the gaseous phase through a ramified tracheal system by diffusion and convection directly to the tissues. In the blowfly, as in other insects with periodic heartbeat reversal, the haemolymph is periodically shifted between the anterior body and abdomen, exerting alternating pressure changes on the compliant tracheae in the thorax and in the abdomen. Simultaneous pressure and O2 optode measurements show that, during negative pressure periods, the tracheal partial pressure of oxygen (PO2) increases by 0.5 kPa. In the quiescent fly, tracheal PO2 is rather high (17.5-18.9 kPa), although the thoracic spiracles remain constricted. Microscopic video recordings and reflectance measurements revealed that the dorsal soft edges of the valve lips of the second spiracle leave a very small leak, which is passively widened during backward pulses of the heart. Thus, negative pressure, combined with increased leakage of the spiracle Sp2 valve enable inspiration in the thorax. The positive pressure periods are correlated with a new type of convective CO2 micro-bursts as shown in flow-through measurements. The bulk of the CO2 is, however, released after longer interbursts in macro-bursts with actively opening valves reminiscent of the open phase in a cyclic gas exchange. When the valves open, the PO2 in the thoracic air sacs unexpectedly drops by a mean of 2.75±1.09 kPa, suggesting a displacement of O2 by the transient accumulation of CO2 in the tracheal system before its release.

Underway sampling of marine inherent optical properties on the Tara Oceans expedition as a novel resource for ocean color satellite data product validation

Developing and validating data records from operational ocean color satellite instruments requires substantial volumes of high quality in situ data. In the absence of broad, institutionally supported field programs, organizations such as the NASA Ocean Biology Processing Group seek opportunistic datasets for use in their operational satellite calibration and validation activities. The publicly available, global biogeochemical dataset collected as part of the two and a half year Tara Oceans expedition provides one such opportunity. We showed how the inline measurements of hyperspectral absorption and attenuation coefficients collected onboard the R/V Tara can be used to evaluate near-surface estimates of chlorophyll-a, spectral particulate backscattering coefficients, particulate organic carbon, and particle size classes derived from the NASA Moderate Resolution Imaging Spectroradiometer onboard Aqua (MODISA). The predominant strength of such flow-through measurements is their sampling rate—the 375 days of measurements resulted in 165 viable MODISA-to-in situ match-ups, compared to 13 from discrete water sampling. While the need to apply bio-optical models to estimate biogeochemical quantities of interest from spectroscopy remains a weakness, we demonstrated how discrete samples can be used in combination with flow-through measurements to create data records of sufficient quality to conduct first order evaluations of satellite-derived data products. Given an emerging agency desire to rapidly evaluate new satellite missions, our results have significant implications on how calibration and validation teams for these missions will be constructed.

Contactless Impedance Sensors and Their Application to Flow Measurements

The paper provides a critical discussion of the present state of the theory of high-frequency impedance sensors (now mostly called contactless impedance or conductivity sensors), the principal approaches employed in designing impedance flow-through cells and their operational parameters. In addition to characterization of traditional types of impedance sensors, the article is concerned with the use of less common sensors, such as cells with wire electrodes or planar cells. There is a detailed discussion of the effect of the individual operational parameters (width and shape of the electrodes, detection gap, frequency and amplitude of the input signal) on the response of the detector. The most important problems to be resolved in coupling these devices with flow-through measurements in the liquid phase are also discussed. Examples are given of cell designs for continuous flow and flow-injection analyses and of detection systems for miniaturized liquid chromatography and capillary electrophoresis. New directions for the use of these sensors in molecular biology and chemical reactors and some directions for future development are outlined.

Sizing mitigation wetlands in agricultural watersheds

In this study, we investigated use of microcosms to supplement field studies for establishing the size of wetlands required to mitigate nitrate pollution in agricultural watersheds. Wetlands investigated in this study were located in San Joaquin Valley (California, USA) and demonstrated mean nitrate-nitrogen mass removal efficiencies ranging between 10 and 34%. Mean areal nitrate removal rates (J) ranged from 142 to 380 mg-N m(-2) d(-1). First-order rate constants determined from field data had a high variance, with confidence intervals greater than 57% of mean values. Sediments and rooted plants from one site were placed in a flow-through microcosm and measurements of nitrate removal kinetics were made and compared with field results. The apparent half-saturation constant (K(m)) and maximum removal rate (J(max)) for nitrate-nitrogen were 43.8 mg/L and 4.11 g m(-2) d(-1) in the microcosm. The first-order rate constant from the microcosm (10.4 cm d(-1)) was in close agreement with the value for the field site (11.9 cm d(-1)) and had a confidence interval of less than 16%. Using this improved first-order rate constant, it was determined that between 1.3 and 3.6% of the land in the watershed should be managed as mitigation wetland, with the area required dependent on the level of nitrate reduction desired and how closely the wetland design approximates plug-flow.

Photo-physiological variability in phytoplankton chlorophyll fluorescence and assessment of chlorophyll concentration

Photo-physiological variability of in vivo chlorophyll fluorescence (CF) per unit of chlorophyll concentration (CC) is analyzed using a biophysical model to improve the accuracy of CC assessments. Field measurements of CF and photosystem II (PSII) photochemical yield (PY) with the Advanced Laser Fluorometer (ALF) in the Delaware and Chesapeake Bays are analyzed vs. high-performance liquid chromatography (HPLC) CC retrievals. It is shown that isolation from ambient light, PSII saturating excitation, optimized phytoplankton exposure to excitation, and phytoplankton dark adaptation may provide accurate in vivo CC fluorescence measurements (R2 = 0.90-0.95 vs. HPLC retrievals). For in situ or flow-through measurements that do not allow for dark adaptation, concurrent PY measurements can be used to adjust for CF non-photochemical quenching (NPQ) and improve the accuracy of CC fluorescence assessments. Field evaluation has shown the NPQ-invariance of CF/PY and CF(PY-1-1) parameters and their high correlation with HPLC CC retrievals (R2 = 0.74-0.96), while the NPQ-affected CF measurements correlated poorly with CC (R2 = -0.22).

Oxygen convective uptakes in gas exchange cycles in early diapause pupae of Pieris brassicae

Oxygen convective uptakes in gas exchange cycles were directly recorded in early diapause pupae of Pieris brassicae L. (Lepidoptera; Pieridae) by means of O2 coulometric respirometry. This method was combined with flow-through CO2 respirometry, the two systems being switchable one to the other. During recording with both systems, measurements were also taken with infrared actography. The pupae displayed short discontinuous gas exchange cycles lasting 40-70 min. No true C phase was found by flow-through measurements; instead, flutter opening of the spiracles with discrete convective O2 uptakes began shortly after the O phase whereas CO2 release was suppressed by the inward directed passive suction ventilation. The F phase was characterized by a series of small CO2 bursts (flutter events). Between these bursts, novel sub-phase `miniflutter' was observed, which consisted of six to 10 miniature inspirations without any CO2 emission. During the flow-through measurements, oxygen convective uptakes were indirectly recorded by the infrared actograph as sudden extensions (lengthening) of the abdominal segments at each spiracular microopening.

Simultaneous spectrophotometric flow-through measurements of pH, carbon dioxide fugacity, and total inorganic carbon in seawater

An autonomous multi-parameter flow-through CO 2 system has been developed to simultaneously measure surface seawater pH, carbon dioxide fugacity ( fCO 2), and total dissolved inorganic carbon (DIC). All three measurements are based on spectrophotometric determinations of solution pH at multiple wavelengths using sulfonephthalein indicators. The pH optical cell is machined from a PEEK polymer rod bearing a bore-hole with an optical pathlength of ∼15 cm. The fCO 2 optical cell consists of Teflon AF 2400 (DuPont) capillary tubing sealed within the bore-hole of a PEEK rod. This Teflon AF tubing is filled with a standard indicator solution with a fixed total alkalinity, and forms a liquid core waveguide (LCW). The LCW functions as both a long pathlength (∼15 cm) optical cell and a membrane that equilibrates the internal standard solution with external seawater. fCO 2 is then determined by measuring the pH of the internal solution. DIC is measured by determining the pH of standard internal solutions in equilibrium with seawater that has been acidified to convert all forms of DIC to CO 2. The system runs repetitive measurement cycles with a sampling frequency of ∼7 samples (21 measurements) per hour. The system was used for underway measurements of sea surface pH, fCO 2, and DIC during the CLIVAR/CO 2 A16S cruise in the South Atlantic Ocean in 2005. The field precisions were evaluated to be 0.0008 units for pH, 0.9 μatm for fCO 2, and 2.4 μmol kg −1 for DIC. These field precisions are close to those obtained in the laboratory. Direct comparison of our measurements and measurements obtained using established standard methods revealed that the system achieved field agreements of 0.0012 ± 0.0042 units for pH, 1.0 ± 2.5 μatm for fCO 2, and 2.2 ± 6.0 μmol kg −1 for DIC. This system integrates spectrophotometric measurements of multiple CO 2 parameters into a single package suitable for observations of both seawater and freshwater.

Piezoelectric immunosensors for polychlorinated biphenyls operating in aqueous and organic phases

The piezoelectric quartz crystal operating in the active mode was used as a transducer for construction of immunosensors for determination polychlorinated biphenyls (PCB). An apparatus for flow-through measurements with piezosensors in pure organic phase was constructed. The anti-PCB polyclonal antibody was immobilized in an oriented way via protein A on a smooth gold surface. The antibody high cross-reactivity for 2,4,4′-trichlorobiphenyl, 4,4′-dichlorobiphenyl and 3,3′,4,4′-tetrachlorbiphenyl allowed for a specific determination of these congeners in samples. PCBs were determined either directly or using competition with a tracer, synthesized from polystyrene particles by covalent attachment of 4,4′-dichlorobiphenyl (DCB). The direct piezoelectric immunosensor operated in phosphate buffer with 5% dimethylsulphoxide. It was possible to detect coplanar PCBs in the range 1–50 ppm. A higher detection limit is compensated here by the low cost and short time of analysis, below 20 min. The same immunorecognition layer can be used repeatedly. Furthermore, kinetic analysis based on a non-linear fitting of the recorded binding transients allowed for a detailed characterization of immunoaffinity interactions. For the more sensitive competitive assay, experiments were carried out directly in pure organic solvents. The most hydrophobic solvent, toluene, was selected due to the highest signal responses. The immunoreaction proceeded also quite well in the presence of dichloromethane and chloroform. However, rather low responses were obtained with acetonitrile and dimethylsulphoxide. The optimized method allowed us to detect PCBs in the range from 6 ppb to 1 ppm within 30 min using raw toluene extracts of soil samples without any purification or pre-concentration steps.

Evaluation of two Mg2+-selective electrodes by means of a flow-through device.

Monitoring the ionized magnesium (Mg2+) concentration in critically ill patients can prevent development of serious and potentially fatal complications. The analyzers KONE Microlyte 6 (KONE Instruments, Espoo, Finland) and NOVA CRT (NOVA Biomedical, Waltham, MA, USA) provide the discontinuous measurement of Mg2+ and were evaluated in several studies. It was our objective to integrate the Mg2+-selective electrodes into a device for continuous on-line measurements. This device is suitable not only for research but also for a specific evaluation of electrode characteristics. It allowed us to compare the genuine electrodes and reference systems independently of their specific analyzers. Precision, accuracy, response time, limit of detection, drift and interferences were assessed by continuous flow-through measurements and discussed in comparison to the results of previous studies. The NOVA electrode proved to be superior regarding accuracy, sensitivity and selectivity, especially with respect to calcium. It was demonstrated that current commercial serum-like control materials were not appropriate for quality control of the assessed Mg2+-electrodes. However, despite the fact that the electrodes are commercially used for discontinuous measurements, both sensor types can be used for continuous on-line measurements in an extracorporeal circulation in a rat model. The NOVA electrode showed superior characteristics with this application as well. This study should also be understood as a contribution to the development of devices for online analyzers used in point-of-care-testing.

Quantitative approach to field-flow fractionation for the characterization of supermicron particles

Field-flow fractionation is a separation technique for macromolecular species; over more than 2 decades, it has been studied mostly for enhancing its separation capabilities in terms of wider applicability, improved selectivity, and reduced analysis time. Most of the efforts have been focused on qualitative aspects of fractionation, while the quantitative aspects have been scarcely exploited. However, a quantitative approach to field-flow fractionation is an unavoidable task in the framework of a general optimization of this technique, particularly when preparative applications are sought. In this work, an overview of quantitative aspects of gravitational field-flow fractionation for the analysis of supermicron particles is presented. In particular, a derivation of the Lambert–Beer law for flow-through measurements is applied to real-time conversion of the detector signal response into sample mass or concentration. In the proposed approach, particle size distribution curves are numerically related to sample mass and to the level of sample recovery derived together from a single fractionation. © 1997 John Wiley & Sons, Inc. J Micro Sep 9: 545–556, 1997

Influence of O2- and H2O2-detection on the electroanalytic reliability of L-lactate- and ?-D-glucose-biosensors at flow-through measurements in reference serum

Electroanalytical flow-through measurements with L-lactate- and β-D-glucose-biosensors using reference sera showed that only by an ion-impermeable but gas-permeable PTFE membrane separating enzyme membrane and electrochemical measuring cell, the high selectivity of oxidases can fully be utilized. For clinical-chemical serum analysis biosensors with O2-detectors are to be preferred which are at least equivalent to photometric comparing methods. Too high values found in measurements using H2O2-detectors are caused by undesired reactands being anodically converted. At O2-sensitive enzymatic L-lactate- and β-D-glucose-biosensors, inevitable biological fouling by O2-consuming microorganisms can be controlled by the use of glutardialdehyde.