Sample records for concentration analytical

  1. Trace level detection of analytes using artificial olfactometry

    NASA Technical Reports Server (NTRS)

    Lewis, Nathan S. (Inventor); Severin, Erik J. (Inventor); Wong, Bernard (Inventor)

    2002-01-01

    The present invention provides a device for detecting the presence of an analyte, such as for example, a lightweight device, including: a sample chamber having a fluid inlet port for the influx of the analyte; a fluid concentrator in flow communication with the sample chamber wherein the fluid concentrator has an absorbent material capable of absorbing the analyte and capable of desorbing a concentrated analyte; and an array of sensors in fluid communication with the concentrated analyte to be released from the fluid concentrator.

  2. Calibration-free concentration analysis for an analyte prone to self-association.

    PubMed

    Imamura, Hiroshi; Honda, Shinya

    2017-01-01

    Calibration-free concentration analysis (CFCA) based on surface plasmon resonance uses the diffusion coefficient of an analyte to determine the concentration of that analyte in a bulk solution. In general, CFCA is avoided when investigating analytes prone to self-association, as the heterogeneous diffusion coefficient results in a loss of precision. The derivation for self-association of the analyte was presented here. By using the diffusion coefficient for the monomeric state, CFCA provides the lowest possible concentration even though the analyte is self-associated. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. Techniques for sensing methanol concentration in aqueous environments

    NASA Technical Reports Server (NTRS)

    Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Valdez, Thomas I. (Inventor)

    2001-01-01

    An analyte concentration sensor that is capable of fast and reliable sensing of analyte concentration in aqueous environments with high concentrations of the analyte. Preferably, the present invention is a methanol concentration sensor device coupled to a fuel metering control system for use in a liquid direct-feed fuel cell.

  4. A generic standard additions based method to determine endogenous analyte concentrations by immunoassays to overcome complex biological matrix interference.

    PubMed

    Pang, Susan; Cowen, Simon

    2017-12-13

    We describe a novel generic method to derive the unknown endogenous concentrations of analyte within complex biological matrices (e.g. serum or plasma) based upon the relationship between the immunoassay signal response of a biological test sample spiked with known analyte concentrations and the log transformed estimated total concentration. If the estimated total analyte concentration is correct, a portion of the sigmoid on a log-log plot is very close to linear, allowing the unknown endogenous concentration to be estimated using a numerical method. This approach obviates conventional relative quantification using an internal standard curve and need for calibrant diluent, and takes into account the individual matrix interference on the immunoassay by spiking the test sample itself. This technique is based on standard additions for chemical analytes. Unknown endogenous analyte concentrations within even 2-fold diluted human plasma may be determined reliably using as few as four reaction wells.

  5. Analyte species and concentration identification using differentially functionalized microcantilever arrays and artificial neural networks

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Senesac, Larry R; Datskos, Panos G; Sepaniak, Michael J

    2006-01-01

    In the present work, we have performed analyte species and concentration identification using an array of ten differentially functionalized microcantilevers coupled with a back-propagation artificial neural network pattern recognition algorithm. The array consists of ten nanostructured silicon microcantilevers functionalized by polymeric and gas chromatography phases and macrocyclic receptors as spatially dense, differentially responding sensing layers for identification and quantitation of individual analyte(s) and their binary mixtures. The array response (i.e. cantilever bending) to analyte vapor was measured by an optical readout scheme and the responses were recorded for a selection of individual analytes as well as several binary mixtures. Anmore » artificial neural network (ANN) was designed and trained to recognize not only the individual analytes and binary mixtures, but also to determine the concentration of individual components in a mixture. To the best of our knowledge, ANNs have not been applied to microcantilever array responses previously to determine concentrations of individual analytes. The trained ANN correctly identified the eleven test analyte(s) as individual components, most with probabilities greater than 97%, whereas it did not misidentify an unknown (untrained) analyte. Demonstrated unique aspects of this work include an ability to measure binary mixtures and provide both qualitative (identification) and quantitative (concentration) information with array-ANN-based sensor methodologies.« less

  6. Aquatic concentrations of chemical analytes compared to ...

    EPA Pesticide Factsheets

    We describe screening level estimates of potential aquatic toxicity posed by 227 chemical analytes that were measured in 25 ambient water samples collected as part of a joint USGS/USEPA drinking water plant study. Measured concentrations were compared to biological effect concentration (EC) estimates, including USEPA aquatic life criteria, effective plasma concentrations of pharmaceuticals, published toxicity data summarized in the USEPA ECOTOX database, and chemical structure-based predictions. Potential dietary exposures were estimated using a generic 3-tiered food web accumulation scenario. For many analytes, few or no measured effect data were found, and for some analytes, reporting limits exceeded EC estimates, limiting the scope of conclusions. Results suggest occasional occurrence above ECs for copper, aluminum, strontium, lead, uranium, and nitrate. Sparse effect data for manganese, antimony, and vanadium suggest that these analytes may occur above ECs, but additional effect data would be desirable to corroborate EC estimates. These conclusions were not affected by bioaccumulation estimates. No organic analyte concentrations were found to exceed EC estimates, but ten analytes had concentrations in excess of 1/10th of their respective EC: triclocarban, norverapamil, progesterone, atrazine, metolachlor, triclosan, para-nonylphenol, ibuprofen, venlafaxine, and amitriptyline, suggesting more detailed characterization of these analytes. Purpose: to provide sc

  7. Aquatic concentrations of chemical analytes compared to ecotoxicity estimates

    USGS Publications Warehouse

    Kostich, Mitchell S.; Flick, Robert W.; Angela L. Batt,; Mash, Heath E.; Boone, J. Scott; Furlong, Edward T.; Kolpin, Dana W.; Glassmeyer, Susan T.

    2017-01-01

    We describe screening level estimates of potential aquatic toxicity posed by 227 chemical analytes that were measured in 25 ambient water samples collected as part of a joint USGS/USEPA drinking water plant study. Measured concentrations were compared to biological effect concentration (EC) estimates, including USEPA aquatic life criteria, effective plasma concentrations of pharmaceuticals, published toxicity data summarized in the USEPA ECOTOX database, and chemical structure-based predictions. Potential dietary exposures were estimated using a generic 3-tiered food web accumulation scenario. For many analytes, few or no measured effect data were found, and for some analytes, reporting limits exceeded EC estimates, limiting the scope of conclusions. Results suggest occasional occurrence above ECs for copper, aluminum, strontium, lead, uranium, and nitrate. Sparse effect data for manganese, antimony, and vanadium suggest that these analytes may occur above ECs, but additional effect data would be desirable to corroborate EC estimates. These conclusions were not affected by bioaccumulation estimates. No organic analyte concentrations were found to exceed EC estimates, but ten analytes had concentrations in excess of 1/10th of their respective EC: triclocarban, norverapamil, progesterone, atrazine, metolachlor, triclosan, para-nonylphenol, ibuprofen, venlafaxine, and amitriptyline, suggesting more detailed characterization of these analytes.

  8. Aquatic concentrations of chemical analytes compared to ecotoxicity estimates.

    PubMed

    Kostich, Mitchell S; Flick, Robert W; Batt, Angela L; Mash, Heath E; Boone, J Scott; Furlong, Edward T; Kolpin, Dana W; Glassmeyer, Susan T

    2017-02-01

    We describe screening level estimates of potential aquatic toxicity posed by 227 chemical analytes that were measured in 25 ambient water samples collected as part of a joint USGS/USEPA drinking water plant study. Measured concentrations were compared to biological effect concentration (EC) estimates, including USEPA aquatic life criteria, effective plasma concentrations of pharmaceuticals, published toxicity data summarized in the USEPA ECOTOX database, and chemical structure-based predictions. Potential dietary exposures were estimated using a generic 3-tiered food web accumulation scenario. For many analytes, few or no measured effect data were found, and for some analytes, reporting limits exceeded EC estimates, limiting the scope of conclusions. Results suggest occasional occurrence above ECs for copper, aluminum, strontium, lead, uranium, and nitrate. Sparse effect data for manganese, antimony, and vanadium suggest that these analytes may occur above ECs, but additional effect data would be desirable to corroborate EC estimates. These conclusions were not affected by bioaccumulation estimates. No organic analyte concentrations were found to exceed EC estimates, but ten analytes had concentrations in excess of 1/10th of their respective EC: triclocarban, norverapamil, progesterone, atrazine, metolachlor, triclosan, para-nonylphenol, ibuprofen, venlafaxine, and amitriptyline, suggesting more detailed characterization of these analytes. Published by Elsevier B.V.

  9. Modeling microelectrode biosensors: free-flow calibration can substantially underestimate tissue concentrations

    PubMed Central

    Wall, Mark J.

    2016-01-01

    Microelectrode amperometric biosensors are widely used to measure concentrations of analytes in solution and tissue including acetylcholine, adenosine, glucose, and glutamate. A great deal of experimental and modeling effort has been directed at quantifying the response of the biosensors themselves; however, the influence that the macroscopic tissue environment has on biosensor response has not been subjected to the same level of scrutiny. Here we identify an important issue in the way microelectrode biosensors are calibrated that is likely to have led to underestimations of analyte tissue concentrations. Concentration in tissue is typically determined by comparing the biosensor signal to that measured in free-flow calibration conditions. In a free-flow environment the concentration of the analyte at the outer surface of the biosensor can be considered constant. However, in tissue the analyte reaches the biosensor surface by diffusion through the extracellular space. Because the enzymes in the biosensor break down the analyte, a density gradient is set up resulting in a significantly lower concentration of analyte near the biosensor surface. This effect is compounded by the diminished volume fraction (porosity) and reduction in the diffusion coefficient due to obstructions (tortuosity) in tissue. We demonstrate this effect through modeling and experimentally verify our predictions in diffusive environments. NEW & NOTEWORTHY Microelectrode biosensors are typically calibrated in a free-flow environment where the concentrations at the biosensor surface are constant. However, when in tissue, the analyte reaches the biosensor via diffusion and so analyte breakdown by the biosensor results in a concentration gradient and consequently a lower concentration around the biosensor. This effect means that naive free-flow calibration will underestimate tissue concentration. We develop mathematical models to better quantify the discrepancy between the calibration and tissue environment and experimentally verify our key predictions. PMID:27927788

  10. Modeling microelectrode biosensors: free-flow calibration can substantially underestimate tissue concentrations.

    PubMed

    Newton, Adam J H; Wall, Mark J; Richardson, Magnus J E

    2017-03-01

    Microelectrode amperometric biosensors are widely used to measure concentrations of analytes in solution and tissue including acetylcholine, adenosine, glucose, and glutamate. A great deal of experimental and modeling effort has been directed at quantifying the response of the biosensors themselves; however, the influence that the macroscopic tissue environment has on biosensor response has not been subjected to the same level of scrutiny. Here we identify an important issue in the way microelectrode biosensors are calibrated that is likely to have led to underestimations of analyte tissue concentrations. Concentration in tissue is typically determined by comparing the biosensor signal to that measured in free-flow calibration conditions. In a free-flow environment the concentration of the analyte at the outer surface of the biosensor can be considered constant. However, in tissue the analyte reaches the biosensor surface by diffusion through the extracellular space. Because the enzymes in the biosensor break down the analyte, a density gradient is set up resulting in a significantly lower concentration of analyte near the biosensor surface. This effect is compounded by the diminished volume fraction (porosity) and reduction in the diffusion coefficient due to obstructions (tortuosity) in tissue. We demonstrate this effect through modeling and experimentally verify our predictions in diffusive environments. NEW & NOTEWORTHY Microelectrode biosensors are typically calibrated in a free-flow environment where the concentrations at the biosensor surface are constant. However, when in tissue, the analyte reaches the biosensor via diffusion and so analyte breakdown by the biosensor results in a concentration gradient and consequently a lower concentration around the biosensor. This effect means that naive free-flow calibration will underestimate tissue concentration. We develop mathematical models to better quantify the discrepancy between the calibration and tissue environment and experimentally verify our key predictions. Copyright © 2017 the American Physiological Society.

  11. Estimation of the uncertainty of analyte concentration from the measurement uncertainty.

    PubMed

    Brown, Simon; Cooke, Delwyn G; Blackwell, Leonard F

    2015-09-01

    Ligand-binding assays, such as immunoassays, are usually analysed using standard curves based on the four-parameter and five-parameter logistic models. An estimate of the uncertainty of an analyte concentration obtained from such curves is needed for confidence intervals or precision profiles. Using a numerical simulation approach, it is shown that the uncertainty of the analyte concentration estimate becomes significant at the extremes of the concentration range and that this is affected significantly by the steepness of the standard curve. We also provide expressions for the coefficient of variation of the analyte concentration estimate from which confidence intervals and the precision profile can be obtained. Using three examples, we show that the expressions perform well.

  12. Analyte discrimination from chemiresistor response kinetics.

    PubMed

    Read, Douglas H; Martin, James E

    2010-08-15

    Chemiresistors are polymer-based sensors that transduce the sorption of a volatile organic compound into a resistance change. Like other polymer-based gas sensors that function through sorption, chemiresistors can be selective for analytes on the basis of the affinity of the analyte for the polymer. However, a single sensor cannot, in and of itself, discriminate between analytes, since a small concentration of an analyte that has a high affinity for the polymer might give the same response as a high concentration of another analyte with a low affinity. In this paper we use a field-structured chemiresistor to demonstrate that its response kinetics can be used to discriminate between analytes, even between those that have identical chemical affinities for the polymer phase of the sensor. The response kinetics is shown to be independent of the analyte concentration, and thus the magnitude of the sensor response, but is found to vary inversely with the analyte's saturation vapor pressure. Saturation vapor pressures often vary greatly from analyte to analyte, so analysis of the response kinetics offers a powerful method for obtaining analyte discrimination from a single sensor.

  13. Nonlinear Analyte Concentration Gradients for One-Step Kinetic Analysis Employing Optical Microring Resonators

    PubMed Central

    Marty, Michael T.; Kuhnline Sloan, Courtney D.; Bailey, Ryan C.; Sligar, Stephen G.

    2012-01-01

    Conventional methods to probe the binding kinetics of macromolecules at biosensor surfaces employ a stepwise titration of analyte concentrations and measure the association and dissociation to the immobilized ligand at each concentration level. It has previously been shown that kinetic rates can be measured in a single step by monitoring binding as the analyte concentration increases over time in a linear gradient. We report here the application of nonlinear analyte concentration gradients for determining kinetic rates and equilibrium binding affinities in a single experiment. A versatile nonlinear gradient maker is presented, which is easily applied to microfluidic systems. Simulations validate that accurate kinetic rates can be extracted for a wide range of association and dissociation rates, gradient slopes and curvatures, and with models for mass transport. The nonlinear analyte gradient method is demonstrated with a silicon photonic microring resonator platform to measure prostate specific antigen-antibody binding kinetics. PMID:22686186

  14. Nonlinear analyte concentration gradients for one-step kinetic analysis employing optical microring resonators.

    PubMed

    Marty, Michael T; Sloan, Courtney D Kuhnline; Bailey, Ryan C; Sligar, Stephen G

    2012-07-03

    Conventional methods to probe the binding kinetics of macromolecules at biosensor surfaces employ a stepwise titration of analyte concentrations and measure the association and dissociation to the immobilized ligand at each concentration level. It has previously been shown that kinetic rates can be measured in a single step by monitoring binding as the analyte concentration increases over time in a linear gradient. We report here the application of nonlinear analyte concentration gradients for determining kinetic rates and equilibrium binding affinities in a single experiment. A versatile nonlinear gradient maker is presented, which is easily applied to microfluidic systems. Simulations validate that accurate kinetic rates can be extracted for a wide range of association and dissociation rates, gradient slopes, and curvatures, and with models for mass transport. The nonlinear analyte gradient method is demonstrated with a silicon photonic microring resonator platform to measure prostate specific antigen-antibody binding kinetics.

  15. Targeted Analyte Detection by Standard Addition Improves Detection Limits in MALDI Mass Spectrometry

    PubMed Central

    Eshghi, Shadi Toghi; Li, Xingde; Zhang, Hui

    2014-01-01

    Matrix-assisted laser desorption/ionization has proven an effective tool for fast and accurate determination of many molecules. However, the detector sensitivity and chemical noise compromise the detection of many invaluable low-abundance molecules from biological and clinical samples. To challenge this limitation, we developed a targeted analyte detection (TAD) technique. In TAD, the target analyte is selectively elevated by spiking a known amount of that analyte into the sample, thereby raising its concentration above the noise level, where we take advantage of the improved sensitivity to detect the presence of the endogenous analyte in the sample. We assessed TAD on three peptides in simple and complex background solutions with various exogenous analyte concentrations in two MALDI matrices. TAD successfully improved the limit of detection (LOD) of target analytes when the target peptides were added to the sample in a concentration close to optimum concentration. The optimum exogenous concentration was estimated through a quantitative method to be approximately equal to the original LOD for each target. Also, we showed that TAD could achieve LOD improvements on an average of 3-fold in a simple and 2-fold in a complex sample. TAD provides a straightforward assay to improve the LOD of generic target analytes without the need for costly hardware modifications. PMID:22877355

  16. Targeted analyte detection by standard addition improves detection limits in matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Toghi Eshghi, Shadi; Li, Xingde; Zhang, Hui

    2012-09-18

    Matrix-assisted laser desorption/ionization (MALDI) has proven an effective tool for fast and accurate determination of many molecules. However, the detector sensitivity and chemical noise compromise the detection of many invaluable low-abundance molecules from biological and clinical samples. To challenge this limitation, we developed a targeted analyte detection (TAD) technique. In TAD, the target analyte is selectively elevated by spiking a known amount of that analyte into the sample, thereby raising its concentration above the noise level, where we take advantage of the improved sensitivity to detect the presence of the endogenous analyte in the sample. We assessed TAD on three peptides in simple and complex background solutions with various exogenous analyte concentrations in two MALDI matrices. TAD successfully improved the limit of detection (LOD) of target analytes when the target peptides were added to the sample in a concentration close to optimum concentration. The optimum exogenous concentration was estimated through a quantitative method to be approximately equal to the original LOD for each target. Also, we showed that TAD could achieve LOD improvements on an average of 3-fold in a simple and 2-fold in a complex sample. TAD provides a straightforward assay to improve the LOD of generic target analytes without the need for costly hardware modifications.

  17. The Statistical Value of Raw Fluorescence Signal in Luminex xMAP Based Multiplex Immunoassays

    PubMed Central

    Breen, Edmond J.; Tan, Woei; Khan, Alamgir

    2016-01-01

    Tissue samples (plasma, saliva, serum or urine) from 169 patients classified as either normal or having one of seven possible diseases are analysed across three 96-well plates for the presences of 37 analytes using cytokine inflammation multiplexed immunoassay panels. Censoring for concentration data caused problems for analysis of the low abundant analytes. Using fluorescence analysis over concentration based analysis allowed analysis of these low abundant analytes. Mixed-effects analysis on the resulting fluorescence and concentration responses reveals a combination of censoring and mapping the fluorescence responses to concentration values, through a 5PL curve, changed observed analyte concentrations. Simulation verifies this, by showing a dependence on the mean florescence response and its distribution on the observed analyte concentration levels. Differences from normality, in the fluorescence responses, can lead to differences in concentration estimates and unreliable probabilities for treatment effects. It is seen that when fluorescence responses are normally distributed, probabilities of treatment effects for fluorescence based t-tests has greater statistical power than the same probabilities from concentration based t-tests. We add evidence that the fluorescence response, unlike concentration values, doesn’t require censoring and we show with respect to differential analysis on the fluorescence responses that background correction is not required. PMID:27243383

  18. Trace level detection of analytes using artificial olfactometry

    NASA Technical Reports Server (NTRS)

    Wong, Bernard (Inventor); Lewis, Nathan S. (Inventor); Severin, Erik J. (Inventor)

    2001-01-01

    The present invention provides a device for detecting the presence of an analyte, wherein said analyte is a microorganism marker gas. The device comprises a sample chamber having a fluid inlet port for the influx of the microorganism marker gas; a fluid concentrator in flow communication with the sample chamber, wherein the fluid concentrator has an absorbent material capable of absorbing the microorganism marker gas and thereafter releasing a concentrated microorganism marker gas; and an array of sensors in fluid communication with the concentrated microorganism marker gas. The sensor array detects and identifies the marker gas upon its release from fluid concentrate.

  19. Precision and bias of selected analytes reported by the National Atmospheric Deposition Program and National Trends Network, 1983; and January 1980 through September 1984

    USGS Publications Warehouse

    Schroder, L.J.; Bricker, A.W.; Willoughby, T.C.

    1985-01-01

    Blind-audit samples with known analyte concentrations have been prepared by the U.S. Geological Survey and distributed to the National Atmospheric Deposition Program 's Central Analytical Laboratory. The difference between the National Atmospheric Deposition Program and National Trends Network reported analyte concentrations and known analyte concentrations have been calculated, and the bias has been determined. Calcium, magnesium , sodium, and chloride were biased at the 99-percent confidence limit; potassium and sulfate were unbiased at the 99-percent confidence limit, for 1983 results. Relative-percent differences between the measured and known analyte concentration for calcium , magnesium, sodium, potassium, chloride, and sulfate have been calculated for 1983. The median relative percent difference for calcium was 17.0; magnesium was 6.4; sodium was 10.8; potassium was 6.4; chloride was 17.2; and sulfate was -5.3. These relative percent differences should be used to correct the 1983 data before user-analysis of the data. Variances have been calculated for calcium, magnesium, sodium, potassium, chloride, and sulfate determinations. These variances should be applicable to natural-sample analyte concentrations reported by the National Atmospheric Deposition Program and National Trends Network for calendar year 1983. (USGS)

  20. 10 CFR 26.168 - Blind performance testing.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... analyte and must be certified by immunoassay and confirmatory testing; (2) Drug positive. These samples must contain a measurable amount of the target drug or analyte in concentrations ranging between 150... performance test sample must contain a measurable amount of the target drug or analyte in concentrations...

  1. 10 CFR 26.168 - Blind performance testing.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... analyte and must be certified by immunoassay and confirmatory testing; (2) Drug positive. These samples must contain a measurable amount of the target drug or analyte in concentrations ranging between 150... performance test sample must contain a measurable amount of the target drug or analyte in concentrations...

  2. 10 CFR 26.168 - Blind performance testing.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... analyte and must be certified by immunoassay and confirmatory testing; (2) Drug positive. These samples must contain a measurable amount of the target drug or analyte in concentrations ranging between 150... performance test sample must contain a measurable amount of the target drug or analyte in concentrations...

  3. 10 CFR 26.168 - Blind performance testing.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... analyte and must be certified by immunoassay and confirmatory testing; (2) Drug positive. These samples must contain a measurable amount of the target drug or analyte in concentrations ranging between 150... performance test sample must contain a measurable amount of the target drug or analyte in concentrations...

  4. 10 CFR 26.168 - Blind performance testing.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... analyte and must be certified by immunoassay and confirmatory testing; (2) Drug positive. These samples must contain a measurable amount of the target drug or analyte in concentrations ranging between 150... performance test sample must contain a measurable amount of the target drug or analyte in concentrations...

  5. Simultaneous Spectrophotometric Determination of Rifampicin, Isoniazid and Pyrazinamide in a Single Step

    PubMed Central

    Asadpour-Zeynali, Karim; Saeb, Elhameh

    2016-01-01

    Three antituberculosis medications are investigated in this work consist of rifampicin, isoniazid and pyrazinamide. The ultra violet (UV) spectra of these compounds are overlapped, thus use of suitable chemometric methods are helpful for simultaneous spectrophotometric determination of them. A generalized version of net analyte signal standard addition method (GNASSAM) was used for determination of three antituberculosis medications as a model system. In generalized net analyte signal standard addition method only one standard solution was prepared for all analytes. This standard solution contains a mixture of all analytes of interest, and the addition of such solution to sample, causes increases in net analyte signal of each analyte which are proportional to the concentrations of analytes in added standards solution. For determination of concentration of each analyte in some synthetic mixtures, the UV spectra of pure analytes and each sample were recorded in the range of 210 nm-550 nm. The standard addition procedure was performed for each sample and the UV spectrum was recorded after each addition and finally the results were analyzed by net analyte signal method. Obtained concentrations show acceptable performance of GNASSAM in these cases. PMID:28243267

  6. The case for visual analytics of arsenic concentrations in foods.

    PubMed

    Johnson, Matilda O; Cohly, Hari H P; Isokpehi, Raphael D; Awofolu, Omotayo R

    2010-05-01

    Arsenic is a naturally occurring toxic metal and its presence in food could be a potential risk to the health of both humans and animals. Prolonged ingestion of arsenic contaminated water may result in manifestations of toxicity in all systems of the body. Visual Analytics is a multidisciplinary field that is defined as the science of analytical reasoning facilitated by interactive visual interfaces. The concentrations of arsenic vary in foods making it impractical and impossible to provide regulatory limit for each food. This review article presents a case for the use of visual analytics approaches to provide comparative assessment of arsenic in various foods. The topics covered include (i) metabolism of arsenic in the human body; (ii) arsenic concentrations in various foods; (ii) factors affecting arsenic uptake in plants; (ii) introduction to visual analytics; and (iv) benefits of visual analytics for comparative assessment of arsenic concentration in foods. Visual analytics can provide an information superstructure of arsenic in various foods to permit insightful comparative risk assessment of the diverse and continually expanding data on arsenic in food groups in the context of country of study or origin, year of study, method of analysis and arsenic species.

  7. The Case for Visual Analytics of Arsenic Concentrations in Foods

    PubMed Central

    Johnson, Matilda O.; Cohly, Hari H.P.; Isokpehi, Raphael D.; Awofolu, Omotayo R.

    2010-01-01

    Arsenic is a naturally occurring toxic metal and its presence in food could be a potential risk to the health of both humans and animals. Prolonged ingestion of arsenic contaminated water may result in manifestations of toxicity in all systems of the body. Visual Analytics is a multidisciplinary field that is defined as the science of analytical reasoning facilitated by interactive visual interfaces. The concentrations of arsenic vary in foods making it impractical and impossible to provide regulatory limit for each food. This review article presents a case for the use of visual analytics approaches to provide comparative assessment of arsenic in various foods. The topics covered include (i) metabolism of arsenic in the human body; (ii) arsenic concentrations in various foods; (ii) factors affecting arsenic uptake in plants; (ii) introduction to visual analytics; and (iv) benefits of visual analytics for comparative assessment of arsenic concentration in foods. Visual analytics can provide an information superstructure of arsenic in various foods to permit insightful comparative risk assessment of the diverse and continually expanding data on arsenic in food groups in the context of country of study or origin, year of study, method of analysis and arsenic species. PMID:20623005

  8. Evaluation of Vitamin D3 and D2 Stability in Fortified Flat Bread Samples During Dough Fermentation, Baking and Storage.

    PubMed

    Tabibian, Mehrnaz; Torbati, Mohammadali; Afshar Mogaddam, Mohammad Reza; Mirlohi, Maryam; Sadeghi, Malihe; Mohtadinia, Javad

    2017-06-01

    Purpose: Vitamin D, a fat-soluble secosteroid, has a significant role in bone metabolism and helps calcium absorption in the body. Since vitamin D concentration is altered in fortified foods and dietary supplements, the actual amount of vitamin D may differ from the label value. Methods: In this study, the concentrations of vitamin D 2 and D 3 of fortified bread sample were analytically determined. For this purpose, dough or homogenized bread sample was saponified using potassium hydroxide solution (30%, w/v) at 80°C, and the saponified analytes were extracted into n -heptane followed by liquid-liquid extraction. Then n -heptane fraction was evaporated to dryness and the sample was reconstituted in methanol. The effect of different parameters was evaluated by one variable at one-time strategy. Results: The analytes concentrations were evaluated in dough fermentation, baking and storage steps. The effect of temperature in dough fermentation and baking was evaluated at the range of 5-30 and 200-250°C, respectively. Also, the fermentation time was studied in the range of 0-120 min. The analytes concentrations were followed for 1 to 5 days after baking. The results indicated that dough fermentation temperature has no significant effect on the concentration of the analytes. On the other hand, when the dough fermentation time and baking temperature are increased, the analytes concentrations are decreased. Also, the storage duration of the spiked bread samples decreased the analytes concentrations after one day. Conclusion: Based on the obtained results, baking the dough at high temperatures lead to decrease in vitamin levels.

  9. Evaluation of Vitamin D3 and D2 Stability in Fortified Flat Bread Samples During Dough Fermentation, Baking and Storage

    PubMed Central

    Tabibian, Mehrnaz; Torbati, Mohammadali; Afshar Mogaddam, Mohammad Reza; Mirlohi, Maryam; Sadeghi, Malihe; Mohtadinia, Javad

    2017-01-01

    Purpose: Vitamin D, a fat-soluble secosteroid, has a significant role in bone metabolism and helps calcium absorption in the body. Since vitamin D concentration is altered in fortified foods and dietary supplements, the actual amount of vitamin D may differ from the label value. Methods: In this study, the concentrations of vitamin D2 and D3 of fortified bread sample were analytically determined. For this purpose, dough or homogenized bread sample was saponified using potassium hydroxide solution (30%, w/v) at 80°C, and the saponified analytes were extracted into n-heptane followed by liquid-liquid extraction. Then n-heptane fraction was evaporated to dryness and the sample was reconstituted in methanol. The effect of different parameters was evaluated by one variable at one-time strategy. Results: The analytes concentrations were evaluated in dough fermentation, baking and storage steps. The effect of temperature in dough fermentation and baking was evaluated at the range of 5-30 and 200-250°C, respectively. Also, the fermentation time was studied in the range of 0-120 min. The analytes concentrations were followed for 1 to 5 days after baking. The results indicated that dough fermentation temperature has no significant effect on the concentration of the analytes. On the other hand, when the dough fermentation time and baking temperature are increased, the analytes concentrations are decreased. Also, the storage duration of the spiked bread samples decreased the analytes concentrations after one day. Conclusion: Based on the obtained results, baking the dough at high temperatures lead to decrease in vitamin levels. PMID:28761835

  10. Nanoporous membranes enable concentration and transport in fully wet paper-based assays.

    PubMed

    Gong, Max M; Zhang, Pei; MacDonald, Brendan D; Sinton, David

    2014-08-19

    Low-cost paper-based assays are emerging as the platform for diagnostics worldwide. Paper does not, however, readily enable advanced functionality required for complex diagnostics, such as analyte concentration and controlled analyte transport. That is, after the initial wetting, no further analyte manipulation is possible. Here, we demonstrate active concentration and transport of analytes in fully wet paper-based assays by leveraging nanoporous material (mean pore diameter ≈ 4 nm) and ion concentration polarization. Two classes of devices are developed, an external stamp-like device with the nanoporous material separate from the paper-based assay, and an in-paper device patterned with the nanoporous material. Experimental results demonstrate up to 40-fold concentration of a fluorescent tracer in fully wet paper, and directional transport of the tracer over centimeters with efficiencies up to 96%. In-paper devices are applied to concentrate protein and colored dye, extending their limits of detection from ∼10 to ∼2 pmol/mL and from ∼40 to ∼10 μM, respectively. This approach is demonstrated in nitrocellulose membrane as well as paper, and the added cost of the nanoporous material is very low at ∼0.015 USD per device. The result is a major advance in analyte concentration and manipulation for the growing field of low-cost paper-based assays.

  11. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Owens, W.W.; Sullivan, H.H.

    Electroless nicke-plate characteristics are substantially influenced by percent phosphorous concentrations. Available ASTM analytical methods are designed for phosphorous concentrations of less than one percent compared to the 4.0 to 20.0% concentrations common in electroless nickel plate. A variety of analytical adaptations are applied through the industry resulting in poor data continuity. This paper presents a statistical comparison of five analytical methods and recommends accurate and precise procedures for use in percent phosphorous determinations in electroless nickel plate. 2 figures, 1 table.

  12. Ultrasonic analyte concentration and application in flow cytometry

    DOEpatents

    Kaduchak, Gregory; Goddard, Greg; Salzman, Gary; Sinha, Dipen; Martin, John C.; Kwiatkowski, Christopher; Graves, Steven

    2014-07-22

    The present invention includes an apparatus and corresponding method for concentrating analytes within a fluid flowing through a tube using acoustic radiation pressure. The apparatus includes a function generator that outputs a radio frequency electrical signal to a transducer that transforms the radio frequency electric signal to an acoustic signal and couples the acoustic signal to the tube. The acoustic signal is converted within the tube to acoustic pressure that concentrates the analytes within the fluid.

  13. Ultrasonic analyte concentration and application in flow cytometry

    DOEpatents

    Kaduchak, Gregory [Los Alamos, NM; Goddard, Greg [Los Alamos, NM; Salzman, Gary [White Rock, NM; Sinha, Dipen [Los Alamos, NM; Martin, John C [Los Alamos, NM; Kwiatkowski, Christopher [Los Alamos, NM; Graves, Steven [San Juan Pueblo, NM

    2008-03-11

    The present invention includes an apparatus and corresponding method for concentrating analytes within a fluid flowing through a tube using acoustic radiation pressure. The apparatus includes a function generator that outputs a radio frequency electrical signal to a transducer that transforms the radio frequency electric signal to an acoustic signal and couples the acoustic signal to the tube. The acoustic signal is converted within the tube to acoustic pressure that concentrates the analytes within the fluid.

  14. Ultrasonic analyte concentration and application in flow cytometry

    DOEpatents

    Kaduchak, Gregory; Goddard, Greg; Salzman, Gary; Sinha, Dipen; Martin, John C.; Kwiatkowski, Christopher; Graves, Steven

    2015-07-07

    The present invention includes an apparatus and corresponding method for concentrating analytes within a fluid flowing through a tube using acoustic radiation pressure. The apparatus includes a function generator that outputs a radio frequency electrical signal to a transducer that transforms the radio frequency electric signal to an acoustic signal and couples the acoustic signal to the tube. The acoustic signal is converted within the tube to acoustic pressure that concentrates the analytes within the fluid.

  15. Fourier Transform Infrared Absorption Spectroscopy for Quantitative Analysis of Gas Mixtures at Low Temperatures for Homeland Security Applications.

    PubMed

    Meier, D C; Benkstein, K D; Hurst, W S; Chu, P M

    2017-05-01

    Performance standard specifications for point chemical vapor detectors are established in ASTM E 2885-13 and ASTM E 2933-13. The performance evaluation of the detectors requires the accurate delivery of known concentrations of the chemical target to the system under test. Referee methods enable the analyte test concentration and associated uncertainties in the analyte test concentration to be validated by independent analysis, which is especially important for reactive analytes. This work extends the capability of a previously demonstrated method for using Fourier transform infrared (FT-IR) absorption spectroscopy for quantitatively evaluating the composition of vapor streams containing hazardous materials at Acute Exposure Guideline Levels (AEGL) to include test conditions colder than laboratory ambient temperatures. The described method covers the use of primary reference spectra to establish analyte concentrations, the generation of secondary reference spectra suitable for measuring analyte concentrations under specified testing environments, and the use of additional reference spectra and spectral profile strategies to mitigate the uncertainties due to impurities and water condensation within the low-temperature (7 °C, -5 °C) test cell. Important benefits of this approach include verification of the test analyte concentration with characterized uncertainties by in situ measurements co-located with the detector under test, near-real-time feedback, and broad applicability to toxic industrial chemicals.

  16. Fourier Transform Infrared Absorption Spectroscopy for Quantitative Analysis of Gas Mixtures at Low Temperatures for Homeland Security Applications

    PubMed Central

    Meier, D.C.; Benkstein, K.D.; Hurst, W.S.; Chu, P.M.

    2016-01-01

    Performance standard specifications for point chemical vapor detectors are established in ASTM E 2885-13 and ASTM E 2933-13. The performance evaluation of the detectors requires the accurate delivery of known concentrations of the chemical target to the system under test. Referee methods enable the analyte test concentration and associated uncertainties in the analyte test concentration to be validated by independent analysis, which is especially important for reactive analytes. This work extends the capability of a previously demonstrated method for using Fourier transform infrared (FT-IR) absorption spectroscopy for quantitatively evaluating the composition of vapor streams containing hazardous materials at Acute Exposure Guideline Levels (AEGL) to include test conditions colder than laboratory ambient temperatures. The described method covers the use of primary reference spectra to establish analyte concentrations, the generation of secondary reference spectra suitable for measuring analyte concentrations under specified testing environments, and the use of additional reference spectra and spectral profile strategies to mitigate the uncertainties due to impurities and water condensation within the low-temperature (7 °C, −5 °C) test cell. Important benefits of this approach include verification of the test analyte concentration with characterized uncertainties by in situ measurements co-located with the detector under test, near-real-time feedback, and broad applicability to toxic industrial chemicals. PMID:28090126

  17. Post-analytical stability of 23 common chemistry and immunochemistry analytes in incurred samples.

    PubMed

    Nielsen, Betina Klint; Frederiksen, Tina; Friis-Hansen, Lennart; Larsen, Pia Bükmann

    2017-12-01

    Storage of blood samples after centrifugation, decapping and initial sampling allows ordering of additional blood tests. The pre-analytic stability of biochemistry and immunochemistry analytes has been studied in detail, but little is known about the post-analytical stability in incurred samples. We examined the stability of 23 routine analytes on the Dimension Vista® (Siemens Healthineers, Denmark): 42-60 routine samples in lithium-heparin gel tubes (Vacutainer, BD, USA) were centrifuged at 3000×g for 10min. Immediately after centrifugation, initial concentration of analytes were measured in duplicate (t=0). The tubes were stored decapped at room temperature and re-analyzed after 2, 4, 6, 8 and 10h in singletons. The concentration from reanalysis were normalized to initial concentration (t=0). Internal acceptance criteria for bias and total error were used to determine stability of each analyte. Additionally, evaporation from the decapped blood collection tubes and the residual platelet count in the plasma after centrifugation were quantified. We report a post-analytical stability of most routine analytes of ≥8h and do therefore - with few exceptions - suggest a standard 8hour-time limit for reordering and reanalysis of analytes in incurred samples. Copyright © 2017 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

  18. Evaporative concentration on a paper-based device to concentrate analytes in a biological fluid.

    PubMed

    Wong, Sharon Y; Cabodi, Mario; Rolland, Jason; Klapperich, Catherine M

    2014-12-16

    We report the first demonstration of using heat on a paper device to rapidly concentrate a clinically relevant analyte of interest from a biological fluid. Our technology relies on the application of localized heat to a paper strip to evaporate off hundreds of microliters of liquid to concentrate the target analyte. This method can be used to enrich for a target analyte that is present at low concentrations within a biological fluid to enhance the sensitivity of downstream detection methods. We demonstrate our method by concentrating the tuberculosis-specific glycolipid, lipoarabinomannan (LAM), a promising urinary biomarker for the detection and diagnosis of tuberculosis. We show that the heat does not compromise the subsequent immunodetectability of LAM, and in 20 min, the tuberculosis biomarker was concentrated by nearly 20-fold in simulated urine. Our method requires only 500 mW of power, and sample flow is self-driven via capillary action. As such, our technology can be readily integrated into portable, battery-powered, instrument-free diagnostic devices intended for use in low-resource settings.

  19. Ammonia Monitor

    NASA Technical Reports Server (NTRS)

    Sauer, Richard L. (Inventor); Akse, James R. (Inventor); Thompson, John O. (Inventor); Atwater, James E. (Inventor)

    1999-01-01

    Ammonia monitor and method of use are disclosed. A continuous, real-time determination of the concentration of ammonia in an aqueous process stream is possible over a wide dynamic range of concentrations. No reagents are required because pH is controlled by an in-line solid-phase base. Ammonia is selectively transported across a membrane from the process stream to an analytical stream to an analytical stream under pH control. The specific electrical conductance of the analytical stream is measured and used to determine the concentration of ammonia.

  20. Confocal Raman Microscopy for pH-Gradient Preconcentration and Quantitative Analyte Detection in Optically Trapped Phospholipid Vesicles.

    PubMed

    Hardcastle, Chris D; Harris, Joel M

    2015-08-04

    The ability of a vesicle membrane to preserve a pH gradient, while allowing for diffusion of neutral molecules across the phospholipid bilayer, can provide the isolation and preconcentration of ionizable compounds within the vesicle interior. In this work, confocal Raman microscopy is used to observe (in situ) the pH-gradient preconcentration of compounds into individual optically trapped vesicles that provide sub-femtoliter collectors for small-volume samples. The concentration of analyte accumulated in the vesicle interior is determined relative to a perchlorate-ion internal standard, preloaded into the vesicle along with a high-concentration buffer. As a guide to the experiments, a model for the transfer of analyte into the vesicle based on acid-base equilibria is developed to predict the concentration enrichment as a function of source-phase pH and analyte concentration. To test the concept, the accumulation of benzyldimethylamine (BDMA) was measured within individual 1 μm phospholipid vesicles having a stable initial pH that is 7 units lower than the source phase. For low analyte concentrations in the source phase (100 nM), a concentration enrichment into the vesicle interior of (5.2 ± 0.4) × 10(5) was observed, in agreement with the model predictions. Detection of BDMA from a 25 nM source-phase sample was demonstrated, a noteworthy result for an unenhanced Raman scattering measurement. The developed model accurately predicts the falloff of enrichment (and measurement sensitivity) at higher analyte concentrations, where the transfer of greater amounts of BDMA into the vesicle titrates the internal buffer and decreases the pH gradient. The predictable calibration response over 4 orders of magnitude in source-phase concentration makes it suitable for quantitative analysis of ionizable compounds from small-volume samples. The kinetics of analyte accumulation are relatively fast (∼15 min) and are consistent with the rate of transfer of a polar aromatic molecule across a gel-phase phospholipid membrane.

  1. 40 CFR 136.2 - Definitions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... of the Act. (f) Detection limit means the minimum concentration of an analyte (substance) that can be measured and reported with a 99% confidence that the analyte concentration is greater than zero as...

  2. 40 CFR 136.2 - Definitions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... of the Act. (f) Detection limit means the minimum concentration of an analyte (substance) that can be measured and reported with a 99% confidence that the analyte concentration is greater than zero as...

  3. 40 CFR 136.2 - Definitions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... of the Act. (f) Detection limit means the minimum concentration of an analyte (substance) that can be measured and reported with a 99% confidence that the analyte concentration is greater than zero as...

  4. 40 CFR 136.2 - Definitions.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... of the Act. (f) Detection limit means the minimum concentration of an analyte (substance) that can be measured and reported with a 99% confidence that the analyte concentration is greater than zero as...

  5. 40 CFR 136.2 - Definitions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... of the Act. (f) Detection limit means the minimum concentration of an analyte (substance) that can be measured and reported with a 99% confidence that the analyte concentration is greater than zero as...

  6. An evaluation of nitrogen and phosphorus responses to rain events in a forested watershed

    NASA Astrophysics Data System (ADS)

    Steadman, C.; Argerich, A.; Bladon, K. D.; Johnson, S. L.

    2017-12-01

    Nitrogen (N) and phosphorus (P) exhibit differential responses to storm events which reflect complex, hydrologically-driven biogeochemical activity in a watershed. However, the magnitude of the responses change throughout the year indicating that they may be strongly influenced by antecedent precipitation conditions. To evaluate N and P responses to storms, we collected storm samples from four subwatersheds in a small forested watershed over a 12-month period as well as climate and hydrologic data. We quantified dissolved nitrate (NO3-), ammonium (NH4+), total dissolved nitrogen (TDN), soluble reactive phosphorus (SRP), and total dissolved phosphorus (TDP) concentrations and exports in 300 samples and examined responses across subwatersheds and storms. To assess the influence of potential drivers, we generated a series of models with discharge, instantaneous rain, and cumulative rain as explanatory variables for analyte concentrations. We also constructed models with cumulative rain as the explanatory variable for analyte exports. There was strong evidence (p < .05) that cumulative rain or the cumulative rain-subwatershed interaction were important for all analyte exports and concentrations. In contrast, evidence was weak for the significance of instantaneous rain for any analyte concentrations while discharge or the discharge-subwatershed interaction was significant for NO3- and NH4+, respectively. Of all factors, cumulative rain was the most relevant to explain analyte concentrations (i.e., showed the highest pseudo-R2), except for NH4+, for which discharge was more relevant. There was significant spatial and temporal variability for all analyte concentrations with the exception of NH4+, which showed little variability storm-to-storm. Maximum NO3- concentration occurred at the onset of the wet season while SRP had the lowest concentration during the same time period. Differential responses of analytes evidence distinct influences of hydrologically-driven biogeochemical activity on individual analytes. However, strong correlations with cumulative rain suggest that insight may be gained through consideration of coarser factors such as antecedent precipitation conditions which may serve to integrate complexities of the hillslope, improving understanding of N and P variability.

  7. MIT CSAIL and Lincoln Laboratory Task Force Report

    DTIC Science & Technology

    2016-08-01

    projects have been very diverse, spanning several areas of CSAIL concentration, including robotics, big data analytics , wireless communications...spanning several areas of CSAIL concentration, including robotics, big data analytics , wireless communications, computing architectures and...to machine learning systems and algorithms, such as recommender systems, and “Big Data ” analytics . Advanced computing architectures broadly refer to

  8. Integrated Gas Sensing System of SWCNT and Cellulose Polymer Concentrator for Benzene, Toluene, and Xylenes

    PubMed Central

    Im, Jisun; Sterner, Elizabeth S.; Swager, Timothy M.

    2016-01-01

    An integrated cellulose polymer concentrator/single-walled carbon nanotube (SWCNT) sensing system is demonstrated to detect benzene, toluene, and xylenes (BTX) vapors. The sensing system consists of functionalized cellulose as a selective concentrator disposed directly on top of a conductive SWCNT sensing layer. Functionalized cellulose concentrator (top layer) selectively adsorbs the target analyte and delivers the concentrated analyte as near as possible to the SWCNT sensing layer (bottom layer), which enables the simultaneous concentrating and sensing within a few seconds. The selectivity can be achieved by functionalizing cellulose acetate with a pentafluorophenylacetyl selector that interacts strongly with the target BTX analytes. A new design of the integrated cellulose concentrator/SWCNT sensing system allows high sensitivity with limits of detection for benzene, toluene, and m-xylene vapors of 55 ppm, 19 ppm, and 14 ppm, respectively, selectivity, and fast responses (<10 s to reach equilibrium), exhibiting the potential ability for on-site, real-time sensing applications. The sensing mechanism involves the selective adsorption of analytes in the concentrator film, which in turn mediates changes in the electronic potentials at the polymer-SWCNT interface and potentially changes in the tunneling barriers between nanotubes. PMID:26848660

  9. Adjustment of pesticide concentrations for temporal changes in analytical recovery, 1992–2010

    USGS Publications Warehouse

    Martin, Jeffrey D.; Eberle, Michael

    2011-01-01

    Recovery is the proportion of a target analyte that is quantified by an analytical method and is a primary indicator of the analytical bias of a measurement. Recovery is measured by analysis of quality-control (QC) water samples that have known amounts of target analytes added ("spiked" QC samples). For pesticides, recovery is the measured amount of pesticide in the spiked QC sample expressed as a percentage of the amount spiked, ideally 100 percent. Temporal changes in recovery have the potential to adversely affect time-trend analysis of pesticide concentrations by introducing trends in apparent environmental concentrations that are caused by trends in performance of the analytical method rather than by trends in pesticide use or other environmental conditions. This report presents data and models related to the recovery of 44 pesticides and 8 pesticide degradates (hereafter referred to as "pesticides") that were selected for a national analysis of time trends in pesticide concentrations in streams. Water samples were analyzed for these pesticides from 1992 through 2010 by gas chromatography/mass spectrometry. Recovery was measured by analysis of pesticide-spiked QC water samples. Models of recovery, based on robust, locally weighted scatterplot smooths (lowess smooths) of matrix spikes, were developed separately for groundwater and stream-water samples. The models of recovery can be used to adjust concentrations of pesticides measured in groundwater or stream-water samples to 100 percent recovery to compensate for temporal changes in the performance (bias) of the analytical method.

  10. Performance evaluation soil samples utilizing encapsulation technology

    DOEpatents

    Dahlgran, J.R.

    1999-08-17

    Performance evaluation soil samples and method of their preparation uses encapsulation technology to encapsulate analytes which are introduced into a soil matrix for analysis and evaluation by analytical laboratories. Target analytes are mixed in an appropriate solvent at predetermined concentrations. The mixture is emulsified in a solution of polymeric film forming material. The emulsified solution is polymerized to form microcapsules. The microcapsules are recovered, quantitated and introduced into a soil matrix in a predetermined ratio to form soil samples with the desired analyte concentration. 1 fig.

  11. Performance evaluation soil samples utilizing encapsulation technology

    DOEpatents

    Dahlgran, James R.

    1999-01-01

    Performance evaluation soil samples and method of their preparation using encapsulation technology to encapsulate analytes which are introduced into a soil matrix for analysis and evaluation by analytical laboratories. Target analytes are mixed in an appropriate solvent at predetermined concentrations. The mixture is emulsified in a solution of polymeric film forming material. The emulsified solution is polymerized to form microcapsules. The microcapsules are recovered, quantitated and introduced into a soil matrix in a predetermined ratio to form soil samples with the desired analyte concentration.

  12. Electrochemical concentration measurements for multianalyte mixtures in simulated electrorefiner salt

    NASA Astrophysics Data System (ADS)

    Rappleye, Devin Spencer

    The development of electroanalytical techniques in multianalyte molten salt mixtures, such as those found in used nuclear fuel electrorefiners, would enable in situ, real-time concentration measurements. Such measurements are beneficial for process monitoring, optimization and control, as well as for international safeguards and nuclear material accountancy. Electroanalytical work in molten salts has been limited to single-analyte mixtures with a few exceptions. This work builds upon the knowledge of molten salt electrochemistry by performing electrochemical measurements on molten eutectic LiCl-KCl salt mixture containing two analytes, developing techniques for quantitatively analyzing the measured signals even with an additional signal from another analyte, correlating signals to concentration and identifying improvements in experimental and analytical methodologies. (Abstract shortened by ProQuest.).

  13. Elemental composition of airborne particulates and source identification - An extensive one year survey. [in Cleveland, OH

    NASA Technical Reports Server (NTRS)

    King, R. B.; Fordyce, J. S.; Antoine, A. C.; Leibecki, H. F.; Neustadter, H. E.; Sidik, S. M.

    1976-01-01

    Concentrations of 60 chemical elements in the airborne particulate matter were measured at 16 sites in Cleveland, OH over a 1 year period during 1971 and 1972 (45 to 50 sampling days). Analytical methods used included instrumental neutron activation, emission spectroscopy, and combustion techniques. Uncertainties in the concentrations associated with the sampling procedures, the analytical methods, the use of several analytical facilities, and samples with concentrations below the detection limits are evaluated in detail. The data are discussed in relation to other studies and source origins. The trace constituent concentrations as a function of wind direction are used to suggest a practical method for air pollution source identification.

  14. Dynamic response of gold nanoparticle chemiresistors to organic analytes in aqueous solution.

    PubMed

    Müller, Karl-Heinz; Chow, Edith; Wieczorek, Lech; Raguse, Burkhard; Cooper, James S; Hubble, Lee J

    2011-10-28

    We investigate the response dynamics of 1-hexanethiol-functionalized gold nanoparticle chemiresistors exposed to the analyte octane in aqueous solution. The dynamic response is studied as a function of the analyte-water flow velocity, the thickness of the gold nanoparticle film and the analyte concentration. A theoretical model for analyte limited mass-transport is used to model the analyte diffusion into the film, the partitioning of the analyte into the 1-hexanethiol capping layers and the subsequent swelling of the film. The degree of swelling is then used to calculate the increase of the electron tunnel resistance between adjacent nanoparticles which determines the resistance change of the film. In particular, the effect of the nonlinear relationship between resistance and swelling on the dynamic response is investigated at high analyte concentration. Good agreement between experiment and the theoretical model is achieved. This journal is © the Owner Societies 2011

  15. 75 FR 5722 - Procedures for Transportation Workplace Drug and Alcohol Testing Programs

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-04

    ... drugs in a DOT drug test. You must not test ``DOT specimens'' for any other drugs. (a) Marijuana... test analyte concentration analyte concentration Marijuana metabolites 50 ng/mL THCA \\1\\ 15 ng/mL...

  16. Stripping Voltammetry

    NASA Astrophysics Data System (ADS)

    Lovrić, Milivoj

    Electrochemical stripping means the oxidative or reductive removal of atoms, ions, or compounds from an electrode surface (or from the electrode body, as in the case of liquid mercury electrodes with dissolved metals) [1-5]. In general, these atoms, ions, or compounds have been preliminarily immobilized on the surface of an inert electrode (or within it) as the result of a preconcentration step, while the products of the electrochemical stripping will dissolve in the electrolytic solution. Often the product of the electrochemical stripping is identical to the analyte before the preconcentration. However, there are exemptions to these rules. Electroanalytical stripping methods comprise two steps: first, the accumulation of a dissolved analyte onto, or in, the working electrode, and, second, the subsequent stripping of the accumulated substance by a voltammetric [3, 5], potentiometric [6, 7], or coulometric [8] technique. In stripping voltammetry, the condition is that there are two independent linear relationships: the first one between the activity of accumulated substance and the concentration of analyte in the sample, and the second between the maximum stripping current and the accumulated substance activity. Hence, a cumulative linear relationship between the maximum response and the analyte concentration exists. However, the electrode capacity for the analyte accumulation is limited and the condition of linearity is satisfied only well below the electrode saturation. For this reason, stripping voltammetry is used mainly in trace analysis. The limit of detection depends on the factor of proportionality between the activity of the accumulated substance and the bulk concentration of the analyte. This factor is a constant in the case of a chemical accumulation, but for electrochemical accumulation it depends on the electrode potential. The factor of proportionality between the maximum stripping current and the analyte concentration is rarely known exactly. In fact, it is frequently ignored. For the analysis it suffices to establish the linear relationship empirically. The slope of this relationship may vary from one sample to another because of different influences of the matrix. In this case the concentration of the analyte is determined by the method of standard additions [1]. After measuring the response of the sample, the concentration of the analyte is deliberately increased by adding a certain volume of its standard solution. The response is measured again, and this procedure is repeated three or four times. The unknown concentration is determined by extrapolation of the regression line to the concentration axis [9]. However, in many analytical methods, the final measurement is performed in a standard matrix that allows the construction of a calibration plot. Still, the slope of this plot depends on the active area of the working electrode surface. Each solid electrode needs a separate calibration plot, and that plot must be checked from time to time because of possible deterioration of the electrode surface [2].

  17. What we-authors, reviewers and editors of scientific work-can learn from the analytical history of biological 3-nitrotyrosine.

    PubMed

    Tsikas, Dimitrios

    2017-07-15

    Tyrosine and tyrosine residues in proteins are attacked by the reactive oxygen and nitrogen species peroxynitrite (O=N-OO - ) to generate 3-nitrotyrosine (3-NT) and 3-nitrotyrosine-proteins (3-NTProt), respectively. 3-NT and 3-NTProt are widely accepted as biomarkers of nitr(os)ative stress. Over the years many different analytical methods have been reported for 3-NT and 3-NTProt. Reported concentrations often differ by more than three orders of magnitude, indicative of serious analytical problems. Strategies to overcome pre-analytical and analytical shortcomings and pitfalls have been proposed. The present review investigated whether recently published work on the quantitative measurement of biological 3-nitrotyrosine did adequately consider the analytical past of this biomolecule. 3-Nitrotyrosine was taken as a representative of biomolecules that occur in biological samples in the pM-to-nM concentration range. This examination revealed that in many cases the main protagonists involved in the publication of scientific work, i.e., authors, reviewers and editors, failed to do so. Learning from the analytical history of 3-nitrotyrosine means advancing analytical and biological science and implies the following key issues. (1) Choosing the most reliable analytical approach in terms of sensitivity and accuracy; presently this is best feasible by stable-isotope dilution tandem mass spectrometry coupled with gas chromatography (GC-MS/MS) or liquid chromatography (LC-MS/MS). (2) Minimizing artificial formation of 3-nitrotyrosine during sample work up, a major pitfall in 3-nitrotyrosine analysis. (3) Validating adequately the final method in the intendent biological matrix and the established concentration range. (4) Inviting experts in the field for critical evaluation of the novelty and reliability of the proposed analytical method, placing special emphasis on the compliance of the analytical outcome with 3-nitrotyrosine concentrations obtained by validated GC-MS/MS and LC-MS/MS methods. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Use of multiple colorimetric indicators for paper-based microfluidic devices.

    PubMed

    Dungchai, Wijitar; Chailapakul, Orawon; Henry, Charles S

    2010-08-03

    We report here the use of multiple indicators for a single analyte for paper-based microfluidic devices (microPAD) in an effort to improve the ability to visually discriminate between analyte concentrations. In existing microPADs, a single dye system is used for the measurement of a single analyte. In our approach, devices are designed to simultaneously quantify analytes using multiple indicators for each analyte improving the accuracy of the assay. The use of multiple indicators for a single analyte allows for different indicator colors to be generated at different analyte concentration ranges as well as increasing the ability to better visually discriminate colors. The principle of our devices is based on the oxidation of indicators by hydrogen peroxide produced by oxidase enzymes specific for each analyte. Each indicator reacts at different peroxide concentrations and therefore analyte concentrations, giving an extended range of operation. To demonstrate the utility of our approach, the mixture of 4-aminoantipyrine and 3,5-dichloro-2-hydroxy-benzenesulfonic acid, o-dianisidine dihydrochloride, potassium iodide, acid black, and acid yellow were chosen as the indicators for simultaneous semi-quantitative measurement of glucose, lactate, and uric acid on a microPAD. Our approach was successfully applied to quantify glucose (0.5-20 mM), lactate (1-25 mM), and uric acid (0.1-7 mM) in clinically relevant ranges. The determination of glucose, lactate, and uric acid in control serum and urine samples was also performed to demonstrate the applicability of this device for biological sample analysis. Finally results for the multi-indicator and single indicator system were compared using untrained readers to demonstrate the improvements in accuracy achieved with the new system. 2010 Elsevier B.V. All rights reserved.

  19. Current Protocols in Pharmacology

    PubMed Central

    2016-01-01

    Determination of drug or drug metabolite concentrations in biological samples, particularly in serum or plasma, is fundamental to describing the relationships between administered dose, route of administration, and time after dose to the drug concentrations achieved and to the observed effects of the drug. A well-characterized, accurate analytical method is needed, but it must also be established that the analyte concentration in the sample at the time of analysis is the same as the concentration at sample acquisition. Drugs and metabolites may be susceptible to degradation in samples due to metabolism or to physical and chemical processes, resulting in a lower measured concentration than was in the original sample. Careful examination of analyte stability during processing and storage and adjustment of procedures and conditions to maximize that stability are a critical part of method validation for the analysis, and can ensure the accuracy of the measured concentrations. PMID:27960029

  20. Simulation of a model nanopore sensor: Ion competition underlies device behavior.

    PubMed

    Mádai, Eszter; Valiskó, Mónika; Dallos, András; Boda, Dezső

    2017-12-28

    We study a model nanopore sensor with which a very low concentration of analyte molecules can be detected on the basis of the selective binding of the analyte molecules to the binding sites on the pore wall. The bound analyte ions partially replace the current-carrier cations in a thermodynamic competition. This competition depends both on the properties of the nanopore and the concentrations of the competing ions (through their chemical potentials). The output signal given by the device is the current reduction caused by the presence of the analyte ions. The concentration of the analyte ions can be determined through calibration curves. We model the binding site with the square-well potential and the electrolyte as charged hard spheres in an implicit background solvent. We study the system with a hybrid method in which we compute the ion flux with the Nernst-Planck (NP) equation coupled with the Local Equilibrium Monte Carlo (LEMC) simulation technique. The resulting NP+LEMC method is able to handle both strong ionic correlations inside the pore (including finite size of ions) and bulk concentrations as low as micromolar. We analyze the effect of bulk ion concentrations, pore parameters, binding site parameters, electrolyte properties, and voltage on the behavior of the device.

  1. Simulation of a model nanopore sensor: Ion competition underlies device behavior

    NASA Astrophysics Data System (ADS)

    Mádai, Eszter; Valiskó, Mónika; Dallos, András; Boda, Dezső

    2017-12-01

    We study a model nanopore sensor with which a very low concentration of analyte molecules can be detected on the basis of the selective binding of the analyte molecules to the binding sites on the pore wall. The bound analyte ions partially replace the current-carrier cations in a thermodynamic competition. This competition depends both on the properties of the nanopore and the concentrations of the competing ions (through their chemical potentials). The output signal given by the device is the current reduction caused by the presence of the analyte ions. The concentration of the analyte ions can be determined through calibration curves. We model the binding site with the square-well potential and the electrolyte as charged hard spheres in an implicit background solvent. We study the system with a hybrid method in which we compute the ion flux with the Nernst-Planck (NP) equation coupled with the Local Equilibrium Monte Carlo (LEMC) simulation technique. The resulting NP+LEMC method is able to handle both strong ionic correlations inside the pore (including finite size of ions) and bulk concentrations as low as micromolar. We analyze the effect of bulk ion concentrations, pore parameters, binding site parameters, electrolyte properties, and voltage on the behavior of the device.

  2. Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of selected carbamate pesticides in water by high-performance liquid chromatography

    USGS Publications Warehouse

    Werner, S.L.; Johnson, S.M.

    1994-01-01

    As part of its primary responsibility concerning water as a national resource, the U.S. Geological Survey collects and analyzes samples of ground water and surface water to determine water quality. This report describes the method used since June 1987 to determine selected total-recoverable carbamate pesticides present in water samples. High- performance liquid chromatography is used to separate N-methyl carbamates, N-methyl carbamoyloximes, and an N-phenyl carbamate which have been extracted from water and concentrated in dichloromethane. Analytes, surrogate compounds, and reference compounds are eluted from the analytical column within 25 minutes. Two modes of analyte detection are used: (1) a photodiode-array detector measures and records ultraviolet-absorbance profiles, and (2) a fluorescence detector measures and records fluorescence from an analyte derivative produced when analyte hydrolysis is combined with chemical derivatization. Analytes are identified and confirmed in a three-stage process by use of chromatographic retention time, ultraviolet (UV) spectral comparison, and derivatization/fluorescence detection. Quantitative results are based on the integration of single-wavelength UV-absorbance chromatograms and on comparison with calibration curves derived from external analyte standards that are run with samples as part of an instrumental analytical sequence. Estimated method detection limits vary for each analyte, depending on the sample matrix conditions, and range from 0.5 microgram per liter to as low as 0.01 microgram per liter. Reporting levels for all analytes have been set at 0.5 microgram per liter for this method. Corrections on the basis of percentage recoveries of analytes spiked into distilled water are not applied to values calculated for analyte concentration in samples. These values for analyte concentrations instead indicate the quantities recovered by the method from a particular sample matrix.

  3. Limits of linearity and detection for some drugs of abuse.

    PubMed

    Needleman, S B; Romberg, R W

    1990-01-01

    The limits of linearity (LOL) and detection (LOD) are important factors in establishing the reliability of an analytical procedure for accurately assaying drug concentrations in urine specimens. Multiple analyses of analyte over an extended range of concentrations provide a measure of the ability of the analytical procedure to correctly identify known quantities of drug in a biofluid matrix. Each of the seven drugs of abuse gives linear analytical responses from concentrations at or near their LOD to concentrations several-fold higher than those generally encountered in the drug screening laboratory. The upper LOL exceeds the Department of Navy (DON) cutoff values by factors of approximately 2 to 160. The LOD varies from 0.4 to 5.0% of the DON cutoff value for each drug. The limit of quantitation (LOQ) is calculated as the LOD + 7 SD. The range for LOL is greater for drugs analyzed with deuterated internal standards compared with those using conventional internal standards. For THC acid, cocaine, PCP, and morphine, LOLs are 8 to 160-fold greater than the defined cutoff concentrations. For the other drugs, the LOL's are only 2 to 4-fold greater than the defined cutoff concentrations.

  4. Influence of Analyte Concentration on Stability Constant Values Determined by Capillary Electrophoresis.

    PubMed

    Sursyakova, Viktoria V; Burmakina, Galina V; Rubaylo, Anatoly I

    2016-08-01

    The influence of analyte concentration when compared with the concentration of a charged ligand in background electrolyte (BGE) on the measured values of electrophoretic mobilities and stability constants (association, binding or formation constants) is studied using capillary electrophoresis (CE) and a dynamic mathematical simulator of CE. The study is performed using labile complexes (with fast kinetics) of iron (III) and 5-sulfosalicylate ions (ISC) as an example. It is shown that because the ligand concentration in the analyte zone is not equal to that in BGE, considerable changes in the migration times and electrophoretic mobilities are observed, resulting in systematic errors in the stability constant values. Of crucial significance is the slope of the dependence of the electrophoretic mobility decrease on the ligand equilibrium concentration. Without prior information on this dependence to accurately evaluate the stability constants for similar systems, the total ligand concentration must be at least >50-100 times higher than the total concentration of analyte. Experimental ISC peak fronting and the difference between the direction of the experimental pH dependence of the electrophoretic mobility decrease and the mathematical simulation allow assuming the presence of capillary wall interaction. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  5. Aquatic concentrations of chemical analytes compared to ecotoxicity estimates

    EPA Science Inventory

    We describe screening level estimates of potential aquatic toxicity posed by 227 chemical analytes that were measured in 25 ambient water samples collected as part of a joint USGS/USEPA drinking water plant study. Measured concentrations were compared to biological effect concent...

  6. Substrate mass transfer: analytical approach for immobilized enzyme reactions

    NASA Astrophysics Data System (ADS)

    Senthamarai, R.; Saibavani, T. N.

    2018-04-01

    In this paper, the boundary value problem in immobilized enzyme reactions is formulated and approximate expression for substrate concentration without external mass transfer resistance is presented. He’s variational iteration method is used to give approximate and analytical solutions of non-linear differential equation containing a non linear term related to enzymatic reaction. The relevant analytical solution for the dimensionless substrate concentration profile is discussed in terms of dimensionless reaction parameters α and β.

  7. RE-EVALUATION OF APPLICABILITY OF AGENCY SAMPLE HOLDING TIMES

    EPA Science Inventory

    Holding times are the length of time a sample can be stored after collection and prior to analysis without significantly affecting the analytical results. Holding times vary with the analyte, sample matrix, and analytical methodology used to quantify the analytes concentration. ...

  8. Quality-assurance results for field pH and specific-conductance measurements, and for laboratory analysis, National Atmospheric Deposition Program and National Trends Network; January 1980-September 1984

    USGS Publications Warehouse

    Schroder, L.J.; Brooks, M.H.; Malo, B.A.; Willoughby, T.C.

    1986-01-01

    Five intersite comparison studies for the field determination of pH and specific conductance, using simulated-precipitation samples, were conducted by the U.S.G.S. for the National Atmospheric Deposition Program and National Trends Network. These comparisons were performed to estimate the precision of pH and specific conductance determinations made by sampling-site operators. Simulated-precipitation samples were prepared from nitric acid and deionized water. The estimated standard deviation for site-operator determination of pH was 0.25 for pH values ranging from 3.79 to 4.64; the estimated standard deviation for specific conductance was 4.6 microsiemens/cm at 25 C for specific-conductance values ranging from 10.4 to 59.0 microsiemens/cm at 25 C. Performance-audit samples with known analyte concentrations were prepared by the U.S.G.S.and distributed to the National Atmospheric Deposition Program 's Central Analytical Laboratory. The differences between the National Atmospheric Deposition Program and national Trends Network-reported analyte concentrations and known analyte concentrations were calculated, and the bias and precision were determined. For 1983, concentrations of calcium, magnesium, sodium, and chloride were biased at the 99% confidence limit; concentrations of potassium and sulfate were unbiased at the 99% confidence limit. Four analytical laboratories routinely analyzing precipitation were evaluated in their analysis of identical natural- and simulated precipitation samples. Analyte bias for each laboratory was examined using analysis of variance coupled with Duncan 's multiple-range test on data produced by these laboratories, from the analysis of identical simulated-precipitation samples. Analyte precision for each laboratory has been estimated by calculating a pooled variance for each analyte. Interlaboratory comparability results may be used to normalize natural-precipitation chemistry data obtained from two or more of these laboratories. (Author 's abstract)

  9. Enhancing reproducibility of SALDI MS detection by concentrating analytes within laser spot.

    PubMed

    Teng, Fei; Zhu, Qunyan; Wang, Yalei; Du, Juan; Lu, Nan

    2018-03-01

    Surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI TOF MS) has become one of the most important analytical methods due to its less interference at low molecular weight range. However, it is still a challenge to obtain a good reproducibility of SALDI TOF MS because of the inhomogeneous distribution of analyte molecules induced by coffee ring effect. We propose a universal and reliable method to eliminate the coffee ring effect by concentrating all the analyte molecules within the laser spot. This method exhibits an excellent reproducibility of spot-to-spot and substrate-to-substrate, and the relative standard deviations (RSDs) for different concentrations are lower than 12.6%. It also performs good linear dependency (R 2 > 0.98) in the log-log plot with the concentration range of 1nM to 1μM, and the limit of detection for R6G is down to 1fmol. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. PNEUMATIC MICROVALVE FOR ELECTROKINETIC SAMPLE PRECONCENTRATION AND CAPILLARY ELECTROPHORESIS INJECTION

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Cong, Yongzheng; Rausch, Sarah J.; Geng, Tao

    2014-10-27

    Here we show that a closed pneumatic microvalve on a PDMS chip can serve as a semipermeable membrane under an applied potential, enabling current to pass through while blocking the passage of charged analytes. Enrichment of both anionic and cationic species has been demonstrated, and concentration factors of ~70 have been achieved in just 8 s. Once analytes are concentrated, the valve is briefly opened and the sample is hydrodynamically injected onto an integrated microchip or capillary electrophoresis (CE) column. In contrast to existing preconcentration approaches, the membrane-based method described here enables both rapid analyte concentration as well as highmore » resolution separations.« less

  11. Ratio of sequential chromatograms for quantitative analysis and peak deconvolution: Application to standard addition method and process monitoring

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Synovec, R.E.; Johnson, E.L.; Bahowick, T.J.

    1990-08-01

    This paper describes a new technique for data analysis in chromatography, based on taking the point-by-point ratio of sequential chromatograms that have been base line corrected. This ratio chromatogram provides a robust means for the identification and the quantitation of analytes. In addition, the appearance of an interferent is made highly visible, even when it coelutes with desired analytes. For quantitative analysis, the region of the ratio chromatogram corresponding to the pure elution of an analyte is identified and is used to calculate a ratio value equal to the ratio of concentrations of the analyte in sequential injections. For themore » ratio value calculation, a variance-weighted average is used, which compensates for the varying signal-to-noise ratio. This ratio value, or equivalently the percent change in concentration, is the basis of a chromatographic standard addition method and an algorithm to monitor analyte concentration in a process stream. In the case of overlapped peaks, a spiking procedure is used to calculate both the original concentration of an analyte and its signal contribution to the original chromatogram. Thus, quantitation and curve resolution may be performed simultaneously, without peak modeling or curve fitting. These concepts are demonstrated by using data from ion chromatography, but the technique should be applicable to all chromatographic techniques.« less

  12. Contaminants of emerging concern in a large temperate estuary.

    PubMed

    Meador, James P; Yeh, Andrew; Young, Graham; Gallagher, Evan P

    2016-06-01

    This study was designed to assess the occurrence and concentrations of a broad range of contaminants of emerging concern (CECs) from three local estuaries within a large estuarine ecosystem. In addition to effluent from two wastewater treatment plants (WWTP), we sampled water and whole-body juvenile Chinook salmon (Oncorhynchus tshawytscha) and Pacific staghorn sculpin (Leptocottus armatus) in estuaries receiving effluent. We analyzed these matrices for 150 compounds, which included pharmaceuticals, personal care products (PPCPs), and several industrial compounds. Collectively, we detected 81 analytes in effluent, 25 analytes in estuary water, and 42 analytes in fish tissue. A number of compounds, including sertraline, triclosan, estrone, fluoxetine, metformin, and nonylphenol were detected in water and tissue at concentrations that may cause adverse effects in fish. Interestingly, 29 CEC analytes were detected in effluent and fish tissue, but not in estuarine waters, indicating a high potential for bioaccumulation for these compounds. Although concentrations of most detected analytes were present at relatively low concentrations, our analysis revealed that overall CEC inputs to each estuary amount to several kilograms of these compounds per day. This study is unique because we report on CEC concentrations in estuarine waters and whole-body fish, which are both uncommon in the literature. A noteworthy finding was the preferential bioaccumulation of CECs in free-ranging juvenile Chinook salmon relative to staghorn sculpin, a benthic species with relatively high site fidelity. Published by Elsevier Ltd.

  13. An analytical and experimental evaluation of a Fresnel lens solar concentrator

    NASA Technical Reports Server (NTRS)

    Hastings, L. J.; Allums, S. A.; Cosby, R. M.

    1976-01-01

    An analytical and experimental evaluation of line focusing Fresnel lenses with application potential in the 200 to 370 C range was studied. Analytical techniques were formulated to assess the solar transmission and imaging properties of a grooves down lens. Experimentation was based on a 56 cm wide, f/1.0 lens. A Sun tracking heliostat provided a nonmoving solar source. Measured data indicated more spreading at the profile base than analytically predicted, resulting in a peak concentration 18 percent lower than the computed peak of 57. The measured and computed transmittances were 85 and 87 percent, respectively. Preliminary testing with a subsequent lens indicated that modified manufacturing techniques corrected the profile spreading problem and should enable improved analytical experimental correlation.

  14. Application of laser Raman spectroscopy in concentration measurements of multiple analytes in human body fluids

    NASA Astrophysics Data System (ADS)

    Qu, Jianan Y.; Suria, David; Wilson, Brian C.

    1998-05-01

    The primary goal of these studies was to demonstrate that NIR Raman spectroscopy is feasible as a rapid and reagentless analytic method for clinical diagnostics. Raman spectra were collected on human serum and urine samples using a 785 nm excitation laser and a single-stage holographic spectrometer. A partial east squares method was used to predict the analyte concentrations of interest. The actual concentrations were determined by a standard clinical chemistry. The prediction accuracy of total protein, albumin, triglyceride and glucose in human sera ranged from 1.5 percent to 5 percent which is greatly acceptable for clinical diagnostics. The concentration measurements of acetaminophen, ethanol and codeine inhuman urine have demonstrated the potential of NIR Raman technology in screening of therapeutic drugs and substances of abuse.

  15. Least Square Regression Method for Estimating Gas Concentration in an Electronic Nose System

    PubMed Central

    Khalaf, Walaa; Pace, Calogero; Gaudioso, Manlio

    2009-01-01

    We describe an Electronic Nose (ENose) system which is able to identify the type of analyte and to estimate its concentration. The system consists of seven sensors, five of them being gas sensors (supplied with different heater voltage values), the remainder being a temperature and a humidity sensor, respectively. To identify a new analyte sample and then to estimate its concentration, we use both some machine learning techniques and the least square regression principle. In fact, we apply two different training models; the first one is based on the Support Vector Machine (SVM) approach and is aimed at teaching the system how to discriminate among different gases, while the second one uses the least squares regression approach to predict the concentration of each type of analyte. PMID:22573980

  16. Steady-state protein focusing in carrier ampholyte based isoelectric focusing: Part I-Analytical solution.

    PubMed

    Shim, Jaesool; Yoo, Kisoo; Dutta, Prashanta

    2017-03-01

    The determination of an analytical solution to find the steady-state protein concentration distribution in IEF is very challenging due to the nonlinear coupling between mass and charge conservation equations. In this study, approximate analytical solutions are obtained for steady-state protein distribution in carrier ampholyte based IEF. Similar to the work of Svensson, the final concentration profile for proteins is assumed to be Gaussian, but appropriate expressions are presented in order to obtain the effective electric field and pH gradient in the focused protein band region. Analytical results are found from iterative solutions of a system of coupled algebraic equations using only several iterations for IEF separation of three plasma proteins: albumin, cardiac troponin I, and hemoglobin. The analytical results are compared with numerically predicted results for IEF, showing excellent agreement. Analytically obtained electric field and ionic conductivity distributions show significant deviation from their nominal values, which is essential in finding the protein focusing behavior at isoelectric points. These analytical solutions can be used to determine steady-state protein concentration distribution for experiment design of IEF considering any number of proteins and ampholytes. Moreover, the model presented herein can be used to find the conductivity, electric field, and pH field. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Pesticide data for selected Wyoming streams, 1976-78

    USGS Publications Warehouse

    Butler, David L.

    1987-01-01

    In 1976, the U.S. Geological Survey, in cooperation with the Wyoming Department of Agriculture, started a monitoring program to determine pesticide concentrations in Wyoming streams. This program was incorporated into the water-quality data-collection system already in operation. Samples were collected at 20 sites for analysis of various insecticides, herbicides, polychlorinated biphenyls, and polychlorinated napthalenes.\\The results through 1978 revealed small concentrations of pesticides in water and bottom-material samples were DDE (39 percent of the concentrations equal to or greater than the minimum reported concentrations of the analytical methods), DDD (20 percent), dieldrin (21 percent), and polychlorinated biphenyls (29 percent). The herbicides most commonly found in water samples were 2,4-D (29 percent of the concentrations equal to or greater than the minimum reported concentrations of the analytical method) and picloram (23 percent). Most concentrations were significantly less than concentrations thought to be harmful to freshwater aquatic life based on available toxicity data. However for some pesticides, U.S. Environmental Protection Agency water-quality criteria for freshwater aquatic life are based on bioaccumulation factors that result in criteria concentrations less than the minimum reported concentrations of the analytical methods. It is not known if certain pesticides were present at concentrations less than the minimum reported concentrations that exceeded these criteria.

  18. Superhydrophobic Analyte Concentration Utilizing Colloid-Pillar Array SERS Substrates

    DOE PAGES

    Wallace, Ryan A.; Charlton, Jennifer J.; Kirchner, Teresa B.; ...

    2014-11-04

    In order to detect a few molecules present in a large sample it is important to know the trace components in the medicinal and environmental sample. Surface enhanced Raman spectroscopy (SERS) is a technique that can be utilized to detect molecules at very low absolute numbers. However, detection at trace concentration levels in real samples requires properly designed delivery and detection systems. Moreover, the following work involves superhydrophobic surfaces that includes silicon pillar arrays formed by lithographic and dewetting protocols. In order to generate the necessary plasmonic substrate for SERS detection, simple and flow stable Ag colloid was added tomore » the functionalized pillar array system via soaking. The pillars are used native and with hydrophobic modification. The pillars provide a means to concentrate analyte via superhydrophobic droplet evaporation effects. A 100-fold concentration of analyte was estimated, with a limit of detection of 2.9 10-12 M for mitoxantrone dihydrochloride. Additionally, analytes were delivered to the surface via a multiplex approach in order to demonstrate an ability to control droplet size and placement for scaled-up applications in real world applications. Finally, a concentration process involving transport and sequestration based on surface treatment selective wicking is demonstrated.« less

  19. Measuring solids concentration in stormwater runoff: comparison of analytical methods.

    PubMed

    Clark, Shirley E; Siu, Christina Y S

    2008-01-15

    Stormwater suspended solids typically are quantified using one of two methods: aliquot/subsample analysis (total suspended solids [TSS]) or whole-sample analysis (suspended solids concentration [SSC]). Interproject comparisons are difficult because of inconsistencies in the methods and in their application. To address this concern, the suspended solids content has been measured using both methodologies in many current projects, but the question remains about how to compare these values with historical water-quality data where the analytical methodology is unknown. This research was undertaken to determine the effect of analytical methodology on the relationship between these two methods of determination of the suspended solids concentration, including the effect of aliquot selection/collection method and of particle size distribution (PSD). The results showed that SSC was best able to represent the known sample concentration and that the results were independent of the sample's PSD. Correlations between the results and the known sample concentration could be established for TSS samples, but they were highly dependent on the sample's PSD and on the aliquot collection technique. These results emphasize the need to report not only the analytical method but also the particle size information on the solids in stormwater runoff.

  20. Superhydrophobic Analyte Concentration Utilizing Colloid-Pillar Array SERS Substrates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wallace, Ryan A.; Charlton, Jennifer J.; Kirchner, Teresa B.

    In order to detect a few molecules present in a large sample it is important to know the trace components in the medicinal and environmental sample. Surface enhanced Raman spectroscopy (SERS) is a technique that can be utilized to detect molecules at very low absolute numbers. However, detection at trace concentration levels in real samples requires properly designed delivery and detection systems. Moreover, the following work involves superhydrophobic surfaces that includes silicon pillar arrays formed by lithographic and dewetting protocols. In order to generate the necessary plasmonic substrate for SERS detection, simple and flow stable Ag colloid was added tomore » the functionalized pillar array system via soaking. The pillars are used native and with hydrophobic modification. The pillars provide a means to concentrate analyte via superhydrophobic droplet evaporation effects. A 100-fold concentration of analyte was estimated, with a limit of detection of 2.9 10-12 M for mitoxantrone dihydrochloride. Additionally, analytes were delivered to the surface via a multiplex approach in order to demonstrate an ability to control droplet size and placement for scaled-up applications in real world applications. Finally, a concentration process involving transport and sequestration based on surface treatment selective wicking is demonstrated.« less

  1. Analyte sensing mediated by adapter/carrier molecules

    DOEpatents

    Bayley, Hagan; Braha, Orit; Gu, LiQun

    2002-07-30

    This invention relates to an improved method and system for sensing of one or more analytes. A host molecule, which serves as an adapter/carrier, is used to facilitate interaction between the analyte and the sensor element. A detectable signal is produced reflecting the identity and concentration of analyte present.

  2. Method of and apparatus for determining the similarity of a biological analyte from a model constructed from known biological fluids

    DOEpatents

    Robinson, Mark R.; Ward, Kenneth J.; Eaton, Robert P.; Haaland, David M.

    1990-01-01

    The characteristics of a biological fluid sample having an analyte are determined from a model constructed from plural known biological fluid samples. The model is a function of the concentration of materials in the known fluid samples as a function of absorption of wideband infrared energy. The wideband infrared energy is coupled to the analyte containing sample so there is differential absorption of the infrared energy as a function of the wavelength of the wideband infrared energy incident on the analyte containing sample. The differential absorption causes intensity variations of the infrared energy incident on the analyte containing sample as a function of sample wavelength of the energy, and concentration of the unknown analyte is determined from the thus-derived intensity variations of the infrared energy as a function of wavelength from the model absorption versus wavelength function.

  3. Determination of Aluminum in Dialysis Concentrates by Atomic Absorption Spectrometry after Coprecipitation with Lanthanum Phosphate.

    PubMed

    Selvi, Emine Kılıçkaya; Şahin, Uğur; Şahan, Serkan

    2017-01-01

    This method was developed for the determination of trace amounts of aluminum(III) in dialysis concentrates using atomic absorption spectrometry after coprecipitation with lanthanum phosphate. The analytical parameters that influenced the quantitative coprecipitation of analyte including amount of lanthanum, amount of phosfate, pH and duration time were optimized. The % recoveries of the analyte ion were in the range of 95-105 % with limit of detection (3s) of 0.5 µg l -1 . Preconcentration factor was found as 1000 and Relative Standard Deviation (RSD) % value obtained from model solutions was 2.5% for 0.02 mg L -1 . The accuracy of the method was evaluated with standard reference material (CWW-TMD Waste Water). The method was also applied to most concentrated acidic and basic dialysis concentrates with satisfactory results.

  4. Multiple animal studies for medical chemical defense program in soldier/patient decontamination and drug development on task 85-17: Validation of an analytical method for the detection of soman (GD), mustard (HD), tabun (GA), and VX in wastewater samples. Final report, 13 October 1985-1 January 1989

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Joiner, R.L.; Hayes, L.; Rust, W.

    1989-05-01

    The following report summarizes the development and validation of an analytical method for the analyses of soman (GD), mustard (HD), VX, and tabun (GA) in wastewater. The need for an analytical method that can detect GD, HD, VX, and GA with the necessary sensitivity (< 20 parts per billion (PPB))and selectivity is essential to Medical Research and Evaluation Facility (MREF) operations. The analytical data were generated using liquid-liquid extraction of the wastewater, with the extract being concentrated and analyzed by gas chromatography (GC) methods. The sample preparation and analyses methods were developed in support of ongoing activities within the MREF.more » We have documented the precision and accuracy of the analytical method through an expected working calibration range (3.0 to 60 ppb). The analytical method was statistically evaluated over a range of concentrations to establish a detection limit and quantitation limit for the method. Whenever the true concentration is 8.5 ppb or above, the probability is at least 99.9 percent that the measured concentration will be ppb or above. Thus, 6 ppb could be used as a lower reliability limit for detecting concentrations in excess of 8.5 ppb. In summary, the proposed sample extraction and analyses methods are suitable for quantitative analyses to determine the presence of GD, HD, VX, and GA in wastewater samples. Our findings indicate that we can detect any of these chemical surety materiel (CSM) in water at or below the established U.S. Army Surgeon General's safety levels in drinking water.« less

  5. Modeling Carbon-Black/Polymer Composite Sensors

    PubMed Central

    Lei, Hua; Pitt, William G.; McGrath, Lucas K.; Ho, Clifford K.

    2012-01-01

    Conductive polymer composite sensors have shown great potential in identifying gaseous analytes. To more thoroughly understand the physical and chemical mechanisms of this type of sensor, a mathematical model was developed by combining two sub-models: a conductivity model and a thermodynamic model, which gives a relationship between the vapor concentration of analyte(s) and the change of the sensor signals. In this work, 64 chemiresistors representing eight different carbon concentrations (8–60 vol% carbon) were constructed by depositing thin films of a carbon-black/polyisobutylene composite onto concentric spiral platinum electrodes on a silicon chip. The responses of the sensors were measured in dry air and at various vapor pressures of toluene and trichloroethylene. Three parameters in the conductivity model were determined by fitting the experimental data. It was shown that by applying this model, the sensor responses can be adequately predicted for given vapor pressures; furthermore the analyte vapor concentrations can be estimated based on the sensor responses. This model will guide the improvement of the design and fabrication of conductive polymer composite sensors for detecting and identifying mixtures of organic vapors. PMID:22518071

  6. Signal Enhancement in HPLC/Micro-Coil NMR Using Automated Column Trapping

    PubMed Central

    Djukovic, Danijel; Liu, Shuhui; Henry, Ian; Tobias, Brian; Raftery, Daniel

    2008-01-01

    A new HPLC-NMR system is described that performs analytical separation, pre-concentration, and NMR spectroscopy in rapid succession. The central component of our method is the online pre-concentration sequence that improves the match between post-column analyte peak volume and the micro-coil NMR detection volume. Separated samples are collected on to a C18 guard column with a mobile phase composed of 90% D2O/10% acetonitrile-D3, and back-flashed to the NMR micro-coil probe with 90% acetonitrile-D3/10% D2O. In order to assess the performance of our unit, we separated a standard mixture of 1 mM ibuprofen, naproxen, and phenylbutazone using a commercially available C18 analytical column. The S/N measurements from the NMR acquisitions indicated that we achieved signal enhancement factors up to 10.4 (±1.2)-fold. Furthermore, we observed that pre-concentration factors increased as the injected amount of analyte decreased. The highest concentration enrichment of 14.7 (±2.2)-fold was attained injecting 100 μL solution of 0.2 mM (~4 μg) ibuprofen. PMID:17037915

  7. A multi-band semi-analytical algorithm for estimating chlorophyll-a concentration in the Yellow River Estuary, China.

    PubMed

    Chen, Jun; Quan, Wenting; Cui, Tingwei

    2015-01-01

    In this study, two sample semi-analytical algorithms and one new unified multi-band semi-analytical algorithm (UMSA) for estimating chlorophyll-a (Chla) concentration were constructed by specifying optimal wavelengths. The three sample semi-analytical algorithms, including the three-band semi-analytical algorithm (TSA), four-band semi-analytical algorithm (FSA), and UMSA algorithm, were calibrated and validated by the dataset collected in the Yellow River Estuary between September 1 and 10, 2009. By comparing of the accuracy of assessment of TSA, FSA, and UMSA algorithms, it was found that the UMSA algorithm had a superior performance in comparison with the two other algorithms, TSA and FSA. Using the UMSA algorithm in retrieving Chla concentration in the Yellow River Estuary decreased by 25.54% NRMSE (normalized root mean square error) when compared with the FSA algorithm, and 29.66% NRMSE in comparison with the TSA algorithm. These are very significant improvements upon previous methods. Additionally, the study revealed that the TSA and FSA algorithms are merely more specific forms of the UMSA algorithm. Owing to the special form of the UMSA algorithm, if the same bands were used for both the TSA and UMSA algorithms or FSA and UMSA algorithms, the UMSA algorithm would theoretically produce superior results in comparison with the TSA and FSA algorithms. Thus, good results may also be produced if the UMSA algorithm were to be applied for predicting Chla concentration for datasets of Gitelson et al. (2008) and Le et al. (2009).

  8. Enhancement in the sensitivity of microfluidic enzyme-linked immunosorbent assays through analyte preconcentration.

    PubMed

    Yanagisawa, Naoki; Dutta, Debashis

    2012-08-21

    In this Article, we describe a microfluidic enzyme-linked immunosorbent assay (ELISA) method whose sensitivity can be substantially enhanced through preconcentration of the target analyte around a semipermeable membrane. The reported preconcentration has been accomplished in our current work via electrokinetic means allowing a significant increase in the amount of captured analyte relative to nonspecific binding in the trapping/detection zone. Upon introduction of an enzyme substrate into this region, the rate of generation of the ELISA reaction product (resorufin) was observed to increase by over a factor of 200 for the sample and 2 for the corresponding blank compared to similar assays without analyte trapping. Interestingly, in spite of nonuniformities in the amount of captured analyte along the surface of our analysis channel, the measured fluorescence signal in the preconcentration zone increased linearly with time over an enzyme reaction period of 30 min and at a rate that was proportional to the analyte concentration in the bulk sample. In our current study, the reported technique has been shown to reduce the smallest detectable concentration of the tumor marker CA 19-9 and Blue Tongue Viral antibody by over 2 orders of magnitude compared to immunoassays without analyte preconcentration. When compared to microwell based ELISAs, the reported microfluidic approach not only yielded a similar improvement in the smallest detectable analyte concentration but also reduced the sample consumption in the assay by a factor of 20 (5 μL versus 100 μL).

  9. Wearable physiological systems and technologies for metabolic monitoring.

    PubMed

    Gao, Wei; Brooks, George A; Klonoff, David C

    2018-03-01

    Wearable sensors allow continuous monitoring of metabolites for diabetes, sports medicine, exercise science, and physiology research. These sensors can continuously detect target analytes in skin interstitial fluid (ISF), tears, saliva, and sweat. In this review, we will summarize developments on wearable devices and their potential applications in research, clinical practice, and recreational and sporting activities. Sampling skin ISF can require insertion of a needle into the skin, whereas sweat, tears, and saliva can be sampled by devices worn outside the body. The most widely sampled metabolite from a wearable device is glucose in skin ISF for monitoring diabetes patients. Continuous ISF glucose monitoring allows estimation of the glucose concentration in blood without the pain, inconvenience, and blood waste of fingerstick capillary blood glucose testing. This tool is currently used by diabetes patients to provide information for dosing insulin and determining a diet and exercise plan. Similar technologies for measuring concentrations of other analytes in skin ISF could be used to monitor athletes, emergency responders, warfighters, and others in states of extreme physiological stress. Sweat is a potentially useful substrate for sampling analytes for metabolic monitoring during exercise. Lactate, sodium, potassium, and hydrogen ions can be measured in sweat. Tools for converting the concentrations of these analytes sampled from sweat, tears, and saliva into blood concentrations are being developed. As an understanding of the relationships between the concentrations of analytes in blood and easily sampled body fluid increases, then the benefits of new wearable devices for metabolic monitoring will also increase.

  10. Experimentally validated mathematical model of analyte uptake by permeation passive samplers.

    PubMed

    Salim, F; Ioannidis, M; Górecki, T

    2017-11-15

    A mathematical model describing the sampling process in a permeation-based passive sampler was developed and evaluated numerically. The model was applied to the Waterloo Membrane Sampler (WMS), which employs a polydimethylsiloxane (PDMS) membrane as a permeation barrier, and an adsorbent as a receiving phase. Samplers of this kind are used for sampling volatile organic compounds (VOC) from air and soil gas. The model predicts the spatio-temporal variation of sorbed and free analyte concentrations within the sampler components (membrane, sorbent bed and dead volume), from which the uptake rate throughout the sampling process can be determined. A gradual decline in the uptake rate during the sampling process is predicted, which is more pronounced when sampling higher concentrations. Decline of the uptake rate can be attributed to diminishing analyte concentration gradient within the membrane, which results from resistance to mass transfer and the development of analyte concentration gradients within the sorbent bed. The effects of changing the sampler component dimensions on the rate of this decline in the uptake rate can be predicted from the model. Performance of the model was evaluated experimentally for sampling of toluene vapors under controlled conditions. The model predictions proved close to the experimental values. The model provides a valuable tool to predict changes in the uptake rate during sampling, to assign suitable exposure times at different analyte concentration levels, and to optimize the dimensions of the sampler in a manner that minimizes these changes during the sampling period.

  11. Newborn screening blood spot analysis in the UK: influence of spot size, punch location and haematocrit.

    PubMed

    Lawson, A J; Bernstone, L; Hall, S K

    2016-03-01

    In dried blood spot analysis, punch location and variations in applied sample volume and haematocrit can produce different measured concentrations of analytes. We investigated the magnitude of these effects in newborn screening in the UK. Heparinized blood spiked with thyroid stimulating hormone (TSH), phenylalanine, tyrosine, leucine, methionine, octanoyl carnitine (C8), and immunoreactive trypsinogen (IRT) was spotted onto filter paper: (i) at a constant haematocrit of 50% at various volumes, and (ii) at a range of haematocrits using a constant volume. Subpunches (3.2 mm) of the dried blood spots were then analysed. Compared with a central punch from a 50 µL blood spot with 50% haematocrit, 10 µL spots can have significantly lower measured concentrations of all analytes, with decreases of 15% or more observed for leucine, methionine, phenylalanine, and tyrosine. Punching at the edge of a spot can increase measured concentrations up to 35%. Higher haematocrit decreased measured TSH and C8 yet increased amino acids and IRT by 15% compared with 50% haematocrit. Lower haematocrits had the opposite effect, but only with higher concentrations of some analytes. Differences in blood spot size, haematocrit and punch location substantially affect measured concentrations for analytes used in the UK newborn screening programme, and this could affect false positive and negative rates. To minimize analytical bias, these variables should be controlled or adjusted for where possible. © The Author(s) 2015.

  12. A comparison of tripolar concentric ring electrode and spline Laplacians on a four-layer concentric spherical model.

    PubMed

    Liu, Xiang; Makeyev, Oleksandr; Besio, Walter

    2011-01-01

    We have simulated a four-layer concentric spherical head model. We calculated the spline and tripolar Laplacian estimates and compared them to the analytical Laplacian on the spherical surface. In the simulations we used five different dipole groups and two electrode configurations. The comparison shows that the tripolar Laplacian has higher correlation coefficient to the analytical Laplacian in the electrode configurations tested (19, standard 10/20 locations and 64 electrodes).

  13. Potential sources of analytical bias and error in selected trace element data-quality analyses

    USGS Publications Warehouse

    Paul, Angela P.; Garbarino, John R.; Olsen, Lisa D.; Rosen, Michael R.; Mebane, Christopher A.; Struzeski, Tedmund M.

    2016-09-28

    Potential sources of analytical bias and error associated with laboratory analyses for selected trace elements where concentrations were greater in filtered samples than in paired unfiltered samples were evaluated by U.S. Geological Survey (USGS) Water Quality Specialists in collaboration with the USGS National Water Quality Laboratory (NWQL) and the Branch of Quality Systems (BQS).Causes for trace-element concentrations in filtered samples to exceed those in associated unfiltered samples have been attributed to variability in analytical measurements, analytical bias, sample contamination either in the field or laboratory, and (or) sample-matrix chemistry. These issues have not only been attributed to data generated by the USGS NWQL but have been observed in data generated by other laboratories. This study continues the evaluation of potential analytical bias and error resulting from matrix chemistry and instrument variability by evaluating the performance of seven selected trace elements in paired filtered and unfiltered surface-water and groundwater samples collected from 23 sampling sites of varying chemistries from six States, matrix spike recoveries, and standard reference materials.Filtered and unfiltered samples have been routinely analyzed on separate inductively coupled plasma-mass spectrometry instruments. Unfiltered samples are treated with hydrochloric acid (HCl) during an in-bottle digestion procedure; filtered samples are not routinely treated with HCl as part of the laboratory analytical procedure. To evaluate the influence of HCl on different sample matrices, an aliquot of the filtered samples was treated with HCl. The addition of HCl did little to differentiate the analytical results between filtered samples treated with HCl from those samples left untreated; however, there was a small, but noticeable, decrease in the number of instances where a particular trace-element concentration was greater in a filtered sample than in the associated unfiltered sample for all trace elements except selenium. Accounting for the small dilution effect (2 percent) from the addition of HCl, as required for the in-bottle digestion procedure for unfiltered samples, may be one step toward decreasing the number of instances where trace-element concentrations are greater in filtered samples than in paired unfiltered samples.The laboratory analyses of arsenic, cadmium, lead, and zinc did not appear to be influenced by instrument biases. These trace elements showed similar results on both instruments used to analyze filtered and unfiltered samples. The results for aluminum and molybdenum tended to be higher on the instrument designated to analyze unfiltered samples; the results for selenium tended to be lower. The matrices used to prepare calibration standards were different for the two instruments. The instrument designated for the analysis of unfiltered samples was calibrated using standards prepared in a nitric:hydrochloric acid (HNO3:HCl) matrix. The instrument designated for the analysis of filtered samples was calibrated using standards prepared in a matrix acidified only with HNO3. Matrix chemistry may have influenced the responses of aluminum, molybdenum, and selenium on the two instruments. The best analytical practice is to calibrate instruments using calibration standards prepared in matrices that reasonably match those of the samples being analyzed.Filtered and unfiltered samples were spiked over a range of trace-element concentrations from less than 1 to 58 times ambient concentrations. The greater the magnitude of the trace-element spike concentration relative to the ambient concentration, the greater the likelihood spike recoveries will be within data control guidelines (80–120 percent). Greater variability in spike recoveries occurred when trace elements were spiked at concentrations less than 10 times the ambient concentration. Spike recoveries that were considerably lower than 90 percent often were associated with spiked concentrations substantially lower than what was present in the ambient sample. Because the main purpose of spiking natural water samples with known quantities of a particular analyte is to assess possible matrix effects on analytical results, the results of this study stress the importance of spiking samples at concentrations that are reasonably close to what is expected but sufficiently high to exceed analytical variability. Generally, differences in spike recovery results between paired filtered and unfiltered samples were minimal when samples were analyzed on the same instrument.Analytical results for trace-element concentrations in ambient filtered and unfiltered samples greater than 10 and 40 μg/L, respectively, were within the data-quality objective for precision of ±25 percent. Ambient trace-element concentrations in filtered samples greater than the long-term method detection limits but less than 10 μg/L failed to meet the data-quality objective for precision for at least one trace element in about 54 percent of the samples. Similarly, trace-element concentrations in unfiltered samples greater than the long-term method detection limits but less than 40 μg/L failed to meet this data-quality objective for at least one trace-element analysis in about 58 percent of the samples. Although, aluminum and zinc were particularly problematic, limited re-analyses of filtered and unfiltered samples appeared to improve otherwise failed analytical precision.The evaluation of analytical bias using standard reference materials indicate a slight low bias for results for arsenic, cadmium, selenium, and zinc. Aluminum and molybdenum show signs of high bias. There was no observed bias, as determined using the standard reference materials, during the analysis of lead.

  14. A Proposed Concentration Curriculum Design for Big Data Analytics for Information Systems Students

    ERIC Educational Resources Information Center

    Molluzzo, John C.; Lawler, James P.

    2015-01-01

    Big Data is becoming a critical component of the Information Systems curriculum. Educators are enhancing gradually the concentration curriculum for Big Data in schools of computer science and information systems. This paper proposes a creative curriculum design for Big Data Analytics for a program at a major metropolitan university. The design…

  15. Quantitative Comparison of Three Standardization Methods Using a One-Way ANOVA for Multiple Mean Comparisons

    ERIC Educational Resources Information Center

    Barrows, Russell D.

    2007-01-01

    A one-way ANOVA experiment is performed to determine whether or not the three standardization methods are statistically different in determining the concentration of the three paraffin analytes. The laboratory exercise asks students to combine the three methods in a single analytical procedure of their own design to determine the concentration of…

  16. Superhydrophobic analyte concentration utilizing colloid-pillar array SERS substrates.

    PubMed

    Wallace, Ryan A; Charlton, Jennifer J; Kirchner, Teresa B; Lavrik, Nickolay V; Datskos, Panos G; Sepaniak, Michael J

    2014-12-02

    The ability to detect a few molecules present in a large sample is of great interest for the detection of trace components in both medicinal and environmental samples. Surface enhanced Raman spectroscopy (SERS) is a technique that can be utilized to detect molecules at very low absolute numbers. However, detection at trace concentration levels in real samples requires properly designed delivery and detection systems. The following work involves superhydrophobic surfaces that have as a framework deterministic or stochastic silicon pillar arrays formed by lithographic or metal dewetting protocols, respectively. In order to generate the necessary plasmonic substrate for SERS detection, simple and flow stable Ag colloid was added to the functionalized pillar array system via soaking. Native pillars and pillars with hydrophobic modification are used. The pillars provide a means to concentrate analyte via superhydrophobic droplet evaporation effects. A ≥ 100-fold concentration of analyte was estimated, with a limit of detection of 2.9 × 10(-12) M for mitoxantrone dihydrochloride. Additionally, analytes were delivered to the surface via a multiplex approach in order to demonstrate an ability to control droplet size and placement for scaled-up uses in real world applications. Finally, a concentration process involving transport and sequestration based on surface treatment selective wicking is demonstrated.

  17. Gold nanoparticle based Tuberculosis immunochromatographic assay: the quantitative ESE Quanti analysis of the intensity of test and control lines.

    PubMed

    Mdluli, Phumlani; Tetyana, Phumlani; Sosibo, Ndabenhle; van der Walt, Hendriëtte; Mlambo, Mbuso; Skepu, Amanda; Tshikhudo, Robert

    2014-04-15

    A rapid dual channel lateral flow assay for the detection of Mycobacterium Tuberculosis antibodies (MTB 38 kDa monoclonal antibody) in human blood was developed. The MTB 6-14-38 kDa fusion antigen and anti-Protein A were used as the capture proteins for test and control lines respectively. Protein A labeled 40 nm gold nanoparticles were used as the detection conjugate. Whole blood and serum were spiked with MTB 38 kDa monoclonal antibody to make a positive sample model. The developed lateral flow was used to test MTB 38 kDa monoclonal antibody, and a detection limit of 5 ng/ml was used as a cut-off concentration of the analytes. The effect of the analyte concentration on the MTB lateral flow assay was studied using the variation of the intensity obtained from a ESE Quanti reader. There was a direct correlation between the analyte (MTB 38 kDa monoclonal antibody) concentration and the intensity of the test line. The intensity increased with an increase in the concentration of MTB 38 kDa monoclonal antibody, while in contrast, an increase in analyte concentration decreased the intensity of the control line. © 2013 Published by Elsevier B.V.

  18. Semi-analytical solutions of the Schnakenberg model of a reaction-diffusion cell with feedback

    NASA Astrophysics Data System (ADS)

    Al Noufaey, K. S.

    2018-06-01

    This paper considers the application of a semi-analytical method to the Schnakenberg model of a reaction-diffusion cell. The semi-analytical method is based on the Galerkin method which approximates the original governing partial differential equations as a system of ordinary differential equations. Steady-state curves, bifurcation diagrams and the region of parameter space in which Hopf bifurcations occur are presented for semi-analytical solutions and the numerical solution. The effect of feedback control, via altering various concentrations in the boundary reservoirs in response to concentrations in the cell centre, is examined. It is shown that increasing the magnitude of feedback leads to destabilization of the system, whereas decreasing this parameter to negative values of large magnitude stabilizes the system. The semi-analytical solutions agree well with numerical solutions of the governing equations.

  19. Influence of analytical bias and imprecision on the number of false positive results using Guideline-Driven Medical Decision Limits.

    PubMed

    Hyltoft Petersen, Per; Klee, George G

    2014-03-20

    Diagnostic decisions based on decision limits according to medical guidelines are different from the majority of clinical decisions due to the strict dichotomization of patients into diseased and non-diseased. Consequently, the influence of analytical performance is more critical than for other diagnostic decisions where much other information is included. The aim of this opinion paper is to investigate consequences of analytical quality and other circumstances for the outcome of "Guideline-Driven Medical Decision Limits". Effects of analytical bias and imprecision should be investigated separately and analytical quality specifications should be estimated accordingly. Use of sharp decision limits doesn't consider biological variation and effects of this variation are closely connected with the effects of analytical performance. Such relationships are investigated for the guidelines for HbA1c in diagnosis of diabetes and in risk of coronary heart disease based on serum cholesterol. The effects of a second sampling in diagnosis give dramatic reduction in the effects of analytical quality showing minimal influence of imprecision up to 3 to 5% for two independent samplings, whereas the reduction in bias is more moderate and a 2% increase in concentration doubles the percentage of false positive diagnoses, both for HbA1c and cholesterol. An alternative approach comes from the current application of guidelines for follow-up laboratory tests according to clinical procedure orders, e.g. frequency of parathyroid hormone requests as a function of serum calcium concentrations. Here, the specifications for bias can be evaluated from the functional increase in requests for increasing serum calcium concentrations. In consequence of the difficulties with biological variation and the practical utilization of concentration dependence of frequency of follow-up laboratory tests already in use, a kind of probability function for diagnosis as function of the key-analyte is proposed. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. Reprint of "Influence of analytical bias and imprecision on the number of false positive results using Guideline-Driven Medical Decision Limits".

    PubMed

    Hyltoft Petersen, Per; Klee, George G

    2014-05-15

    Diagnostic decisions based on decision limits according to medical guidelines are different from the majority of clinical decisions due to the strict dichotomization of patients into diseased and non-diseased. Consequently, the influence of analytical performance is more critical than for other diagnostic decisions where much other information is included. The aim of this opinion paper is to investigate consequences of analytical quality and other circumstances for the outcome of "Guideline-Driven Medical Decision Limits". Effects of analytical bias and imprecision should be investigated separately and analytical quality specifications should be estimated accordingly. Use of sharp decision limits doesn't consider biological variation and effects of this variation are closely connected with the effects of analytical performance. Such relationships are investigated for the guidelines for HbA1c in diagnosis of diabetes and in risk of coronary heart disease based on serum cholesterol. The effects of a second sampling in diagnosis give dramatic reduction in the effects of analytical quality showing minimal influence of imprecision up to 3 to 5% for two independent samplings, whereas the reduction in bias is more moderate and a 2% increase in concentration doubles the percentage of false positive diagnoses, both for HbA1c and cholesterol. An alternative approach comes from the current application of guidelines for follow-up laboratory tests according to clinical procedure orders, e.g. frequency of parathyroid hormone requests as a function of serum calcium concentrations. Here, the specifications for bias can be evaluated from the functional increase in requests for increasing serum calcium concentrations. In consequence of the difficulties with biological variation and the practical utilization of concentration dependence of frequency of follow-up laboratory tests already in use, a kind of probability function for diagnosis as function of the key-analyte is proposed. Copyright © 2014. Published by Elsevier B.V.

  1. Biosensing in a microelectrofluidic system using optical whispering-gallery mode spectroscopy

    PubMed Central

    Huang, Lei; Guo, Zhixiong

    2011-01-01

    Label-free detection of biomolecules using an optical whispering-gallery mode sensor in a microelectrofluidic channel is simulated. Negatively charged bovine serum albumin is considered as the model protein analyte. The analyte transport in aqueous solution is controlled by an externally applied electrical field. The finite element method is employed for solving the equations of the charged species transport, the Poisson equation of electric potential, the equations of conservation of momentum and energy, and the Helmholtz equations of electromagnetic waves. The adsorption process of the protein molecules on the microsensor head surface is monitored by the resonance frequency shifts. Frequency shift caused by temperature variation due to Joule heating is analyzed and found to be negligible. The induced shifts behave in a manner similar to Langmuir-like adsorption kinetics; but the time constant increases due to the presence of the external electrical field. A correlation of the frequency shift, the analyte feed concentration in the solution, and the applied voltage gradient is obtained, in which an excellent linear relationship between the frequency shift and the analyte concentration is revealed. The applied voltage gradient enhances significantly the analyte concentration in the vicinity of the sensor surface; thus, the sensor sensitivity which has a power function of the voltage gradient with exponent 2.85 in the controlled voltage range. Simulated detection of extremely low protein concentration to the pico-molar level is carried out. PMID:22662041

  2. A two-dimensional analytical model of vapor intrusion involving vertical heterogeneity.

    PubMed

    Yao, Yijun; Verginelli, Iason; Suuberg, Eric M

    2017-05-01

    In this work, we present an analytical chlorinated vapor intrusion (CVI) model that can estimate source-to-indoor air concentration attenuation by simulating two-dimensional (2-D) vapor concentration profile in vertically heterogeneous soils overlying a homogenous vapor source. The analytical solution describing the 2-D soil gas transport was obtained by applying a modified Schwarz-Christoffel mapping method. A partial field validation showed that the developed model provides results (especially in terms of indoor emission rates) in line with the measured data from a case involving a building overlying a layered soil. In further testing, it was found that the new analytical model can very closely replicate the results of three-dimensional (3-D) numerical models at steady state in scenarios involving layered soils overlying homogenous groundwater sources. By contrast, by adopting a two-layer approach (capillary fringe and vadose zone) as employed in the EPA implementation of the Johnson and Ettinger model, the spatially and temporally averaged indoor concentrations in the case of groundwater sources can be higher than the ones estimated by the numerical model up to two orders of magnitude. In short, the model proposed in this work can represent an easy-to-use tool that can simulate the subsurface soil gas concentration in layered soils overlying a homogenous vapor source while keeping the simplicity of an analytical approach that requires much less computational effort.

  3. A method for direct, semi-quantitative analysis of gas phase samples using gas chromatography-inductively coupled plasma-mass spectrometry

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Carter, Kimberly E; Gerdes, Kirk

    2013-07-01

    A new and complete GC–ICP-MS method is described for direct analysis of trace metals in a gas phase process stream. The proposed method is derived from standard analytical procedures developed for ICP-MS, which are regularly exercised in standard ICP-MS laboratories. In order to implement the method, a series of empirical factors were generated to calibrate detector response with respect to a known concentration of an internal standard analyte. Calibrated responses are ultimately used to determine the concentration of metal analytes in a gas stream using a semi-quantitative algorithm. The method was verified using a traditional gas injection from a GCmore » sampling valve and a standard gas mixture containing either a 1 ppm Xe + Kr mix with helium balance or 100 ppm Xe with helium balance. Data collected for Xe and Kr gas analytes revealed that agreement of 6–20% with the actual concentration can be expected for various experimental conditions. To demonstrate the method using a relevant “unknown” gas mixture, experiments were performed for continuous 4 and 7 hour periods using a Hg-containing sample gas that was co-introduced into the GC sample loop with the xenon gas standard. System performance and detector response to the dilute concentration of the internal standard were pre-determined, which allowed semi-quantitative evaluation of the analyte. The calculated analyte concentrations varied during the course of the 4 hour experiment, particularly during the first hour of the analysis where the actual Hg concentration was under predicted by up to 72%. Calculated concentration improved to within 30–60% for data collected after the first hour of the experiment. Similar results were seen during the 7 hour test with the deviation from the actual concentration being 11–81% during the first hour and then decreasing for the remaining period. The method detection limit (MDL) was determined for the mercury by injecting the sample gas into the system following a period of equilibration. The MDL for Hg was calculated as 6.8 μg · m -3. This work describes the first complete GC–ICP-MS method to directly analyze gas phase samples, and detailed sample calculations and comparisons to conventional ICP-MS methods are provided.« less

  4. Calibrant-Free Analyte Quantitation via a Variable Velocity Flow Cell.

    PubMed

    Beck, Jason G; Skuratovsky, Aleksander; Granger, Michael C; Porter, Marc D

    2017-01-17

    In this paper, we describe a novel method for analyte quantitation that does not rely on calibrants, internal standards, or calibration curves but, rather, leverages the relationship between disparate and predictable surface-directed analyte flux to an array of sensing addresses and a measured resultant signal. To reduce this concept to practice, we fabricated two flow cells such that the mean linear fluid velocity, U, was varied systematically over an array of electrodes positioned along the flow axis. This resulted in a predictable variation of the address-directed flux of a redox analyte, ferrocenedimethanol (FDM). The resultant limiting currents measured at a series of these electrodes, and accurately described by a convective-diffusive transport model, provided a means to calculate an "unknown" concentration without the use of calibrants, internal standards, or a calibration curve. Furthermore, the experiment and concentration calculation only takes minutes to perform. Deviation in calculated FDM concentrations from true values was minimized to less than 0.5% when empirically derived values of U were employed.

  5. Sensor arrays for detecting analytes in fluids

    NASA Technical Reports Server (NTRS)

    Freund, Michael S. (Inventor); Lewis, Nathan S. (Inventor)

    2000-01-01

    A sensor array for detecting an analyte in a fluid, comprising at least first and second chemically sensitive resistors electrically connected to an electrical measuring apparatus, wherein each of the chemically sensitive resistors comprises a mixture of nonconductive material and a conductive material. Each resistor provides an electrical path through the mixture of nonconductive material and the conductive material. The resistors also provide a difference in resistance between the conductive elements when contacted with a fluid comprising an analyte at a first concentration, than when contacted with an analyte at a second different concentration. A broad range of analytes can be detected using the sensors of the present invention. Examples of such analytes include, but are not limited to, alkanes, alkenes, alkynes, dienes, alicyclic hydrocarbons, arenes, alcohols, ethers, ketones, aldehydes, carbonyls, carbanions, polynuclear aromatics, organic derivatives, biomolecules, sugars, isoprenes, isoprenoids and fatty acids. Moreover, applications for the sensors of the present invention include, but are not limited to, environmental toxicology, remediation, biomedicine, material quality control, food monitoring and agricultural monitoring.

  6. An analytical and experimental evaluation of the plano-cylindrical Fresnel lens solar concentrator

    NASA Technical Reports Server (NTRS)

    Hastings, L. J.; Allums, S. L.; Cosby, R. M.

    1976-01-01

    Plastic Fresnel lenses for solar concentration are attractive because of potential for low-cost mass production. An analytical and experimental evaluation of line-focusing Fresnel lenses with application potential in the 200 to 370 C range is reported. Analytical techniques were formulated to assess the solar transmission and imaging properties of a grooves-down lens. Experimentation was based primarily on a 56 cm-wide lens with f-number 1.0. A sun-tracking heliostat provided a non-moving solar source. Measured data indicated more spreading at the profile base than analytically predicted. The measured and computed transmittances were 85 and 87% respectively. Preliminary testing with a second lens (1.85 m) indicated that modified manufacturing techniques corrected the profile spreading problem.

  7. Technical pre-analytical effects on the clinical biochemistry of Atlantic salmon (Salmo salar L.).

    PubMed

    Braceland, M; Houston, K; Ashby, A; Matthews, C; Haining, H; Rodger, H; Eckersall, P D

    2017-01-01

    Clinical biochemistry has long been utilized in human and veterinary medicine as a vital diagnostic tool, but despite occasional studies showing its usefulness in monitoring health status in Atlantic salmon (Salmo salar L.), it has not yet been widely utilized within the aquaculture industry. This is due, in part, to a lack of an agreed protocol for collection and processing of blood prior to analysis. Moreover, while the analytical phase of clinical biochemistry is well controlled, there is a growing understanding that technical pre-analytical variables can influence analyte concentrations or activities. In addition, post-analytical interpretation of treatment effects is variable in the literature, thus making the true effect of sample treatment hard to evaluate. Therefore, a number of pre-analytical treatments have been investigated to examine their effect on analyte concentrations and activities. In addition, reference ranges for salmon plasma biochemical analytes have been established to inform veterinary practitioners and the aquaculture industry of the importance of clinical biochemistry in health and disease monitoring. Furthermore, a standardized protocol for blood collection has been proposed. © 2016 The Authors Journal of Fish Diseases Published by John Wiley & Sons Ltd.

  8. Comparative Chemometric Analysis for Classification of Acids and Bases via a Colorimetric Sensor Array.

    PubMed

    Kangas, Michael J; Burks, Raychelle M; Atwater, Jordyn; Lukowicz, Rachel M; Garver, Billy; Holmes, Andrea E

    2018-02-01

    With the increasing availability of digital imaging devices, colorimetric sensor arrays are rapidly becoming a simple, yet effective tool for the identification and quantification of various analytes. Colorimetric arrays utilize colorimetric data from many colorimetric sensors, with the multidimensional nature of the resulting data necessitating the use of chemometric analysis. Herein, an 8 sensor colorimetric array was used to analyze select acid and basic samples (0.5 - 10 M) to determine which chemometric methods are best suited for classification quantification of analytes within clusters. PCA, HCA, and LDA were used to visualize the data set. All three methods showed well-separated clusters for each of the acid or base analytes and moderate separation between analyte concentrations, indicating that the sensor array can be used to identify and quantify samples. Furthermore, PCA could be used to determine which sensors showed the most effective analyte identification. LDA, KNN, and HQI were used for identification of analyte and concentration. HQI and KNN could be used to correctly identify the analytes in all cases, while LDA correctly identified 95 of 96 analytes correctly. Additional studies demonstrated that controlling for solvent and image effects was unnecessary for all chemometric methods utilized in this study.

  9. A simple analytical method to estimate all exit parameters of a cross-flow air dehumidifier using liquid desiccant.

    PubMed

    Bassuoni, M M

    2014-03-01

    The dehumidifier is a key component in liquid desiccant air-conditioning systems. Analytical solutions have more advantages than numerical solutions in studying the dehumidifier performance parameters. This paper presents the performance results of exit parameters from an analytical model of an adiabatic cross-flow liquid desiccant air dehumidifier. Calcium chloride is used as desiccant material in this investigation. A program performing the analytical solution is developed using the engineering equation solver software. Good accuracy has been found between analytical solution and reliable experimental results with a maximum deviation of +6.63% and -5.65% in the moisture removal rate. The method developed here can be used in the quick prediction of the dehumidifier performance. The exit parameters from the dehumidifier are evaluated under the effects of variables such as air temperature and humidity, desiccant temperature and concentration, and air to desiccant flow rates. The results show that hot humid air and desiccant concentration have the greatest impact on the performance of the dehumidifier. The moisture removal rate is decreased with increasing both air inlet temperature and desiccant temperature while increases with increasing air to solution mass ratio, inlet desiccant concentration, and inlet air humidity ratio.

  10. A modeling approach to compare ΣPCB concentrations between congener-specific analyses

    USGS Publications Warehouse

    Gibson, Polly P.; Mills, Marc A.; Kraus, Johanna M.; Walters, David M.

    2017-01-01

    Changes in analytical methods over time pose problems for assessing long-term trends in environmental contamination by polychlorinated biphenyls (PCBs). Congener-specific analyses vary widely in the number and identity of the 209 distinct PCB chemical configurations (congeners) that are quantified, leading to inconsistencies among summed PCB concentrations (ΣPCB) reported by different studies. Here we present a modeling approach using linear regression to compare ΣPCB concentrations derived from different congener-specific analyses measuring different co-eluting groups. The approach can be used to develop a specific conversion model between any two sets of congener-specific analytical data from similar samples (similar matrix and geographic origin). We demonstrate the method by developing a conversion model for an example data set that includes data from two different analytical methods, a low resolution method quantifying 119 congeners and a high resolution method quantifying all 209 congeners. We used the model to show that the 119-congener set captured most (93%) of the total PCB concentration (i.e., Σ209PCB) in sediment and biological samples. ΣPCB concentrations estimated using the model closely matched measured values (mean relative percent difference = 9.6). General applications of the modeling approach include (a) generating comparable ΣPCB concentrations for samples that were analyzed for different congener sets; and (b) estimating the proportional contribution of different congener sets to ΣPCB. This approach may be especially valuable for enabling comparison of long-term remediation monitoring results even as analytical methods change over time. 

  11. Target analyte quantification by isotope dilution LC-MS/MS directly referring to internal standard concentrations--validation for serum cortisol measurement.

    PubMed

    Maier, Barbara; Vogeser, Michael

    2013-04-01

    Isotope dilution LC-MS/MS methods used in the clinical laboratory typically involve multi-point external calibration in each analytical series. Our aim was to test the hypothesis that determination of target analyte concentrations directly derived from the relation of the target analyte peak area to the peak area of a corresponding stable isotope labelled internal standard compound [direct isotope dilution analysis (DIDA)] may be not inferior to conventional external calibration with respect to accuracy and reproducibility. Quality control samples and human serum pools were analysed in a comparative validation protocol for cortisol as an exemplary analyte by LC-MS/MS. Accuracy and reproducibility were compared between quantification either involving a six-point external calibration function, or a result calculation merely based on peak area ratios of unlabelled and labelled analyte. Both quantification approaches resulted in similar accuracy and reproducibility. For specified analytes, reliable analyte quantification directly derived from the ratio of peak areas of labelled and unlabelled analyte without the need for a time consuming multi-point calibration series is possible. This DIDA approach is of considerable practical importance for the application of LC-MS/MS in the clinical laboratory where short turnaround times often have high priority.

  12. Unexpected Analyte Oxidation during Desorption Electrospray Ionization - Mass Spectrometry

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pasilis, Sofie P; Kertesz, Vilmos; Van Berkel, Gary J

    2008-01-01

    During the analysis of surface spotted analytes using desorption electrospray ionization mass spectrometry (DESI-MS), abundant ions are sometimes observed that appear to be the result of oxygen addition reactions. In this investigation, the effect of sample aging, the ambient lab environment, spray voltage, analyte surface concentration, and surface type on this oxidative modification of spotted analytes, exemplified by tamoxifen and reserpine, during analysis by desorption electrospray ionization mass spectrometry was studied. Simple exposure of the samples to air and to ambient lighting increased the extent of oxidation. Increased spray voltage lead also to increased analyte oxidation, possibly as a resultmore » of oxidative species formed electrochemically at the emitter electrode or in the gas - phase by discharge processes. These oxidative species are carried by the spray and impinge on and react with the sampled analyte during desorption/ionization. The relative abundance of oxidized species was more significant for analysis of deposited analyte having a relatively low surface concentration. Increasing spray solvent flow rate and addition of hydroquinone as a redox buffer to the spray solvent were found to decrease, but not entirely eliminate, analyte oxidation during analysis. The major parameters that both minimize and maximize analyte oxidation were identified and DESI-MS operational recommendations to avoid these unwanted reactions are suggested.« less

  13. Flexible nano- and microliter injections on a single liquid chromatography-mass spectrometry system: Minimizing sample preparation and maximizing linear dynamic range.

    PubMed

    Lubin, Arnaud; Sheng, Sheng; Cabooter, Deirdre; Augustijns, Patrick; Cuyckens, Filip

    2017-11-17

    Lack of knowledge on the expected concentration range or insufficient linear dynamic range of the analytical method applied are common challenges for the analytical scientist. Samples that are above the upper limit of quantification are typically diluted and reanalyzed. The analysis of undiluted highly concentrated samples can cause contamination of the system, while the dilution step is time consuming and as the case for any sample preparation step, also potentially leads to precipitation, adsorption or degradation of the analytes. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. STATISTICAL ANALYSIS OF TANK 5 FLOOR SAMPLE RESULTS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shine, E.

    2012-03-14

    Sampling has been completed for the characterization of the residual material on the floor of Tank 5 in the F-Area Tank Farm at the Savannah River Site (SRS), near Aiken, SC. The sampling was performed by Savannah River Remediation (SRR) LLC using a stratified random sampling plan with volume-proportional compositing. The plan consisted of partitioning the residual material on the floor of Tank 5 into three non-overlapping strata: two strata enclosed accumulations, and a third stratum consisted of a thin layer of material outside the regions of the two accumulations. Each of three composite samples was constructed from five primarymore » sample locations of residual material on the floor of Tank 5. Three of the primary samples were obtained from the stratum containing the thin layer of material, and one primary sample was obtained from each of the two strata containing an accumulation. This report documents the statistical analyses of the analytical results for the composite samples. The objective of the analysis is to determine the mean concentrations and upper 95% confidence (UCL95) bounds for the mean concentrations for a set of analytes in the tank residuals. The statistical procedures employed in the analyses were consistent with the Environmental Protection Agency (EPA) technical guidance by Singh and others [2010]. Savannah River National Laboratory (SRNL) measured the sample bulk density, nonvolatile beta, gross alpha, radionuclide, inorganic, and anion concentrations three times for each of the composite samples. The analyte concentration data were partitioned into three separate groups for further analysis: analytes with every measurement above their minimum detectable concentrations (MDCs), analytes with no measurements above their MDCs, and analytes with a mixture of some measurement results above and below their MDCs. The means, standard deviations, and UCL95s were computed for the analytes in the two groups that had at least some measurements above their MDCs. The identification of distributions and the selection of UCL95 procedures generally followed the protocol in Singh, Armbya, and Singh [2010]. When all of an analyte's measurements lie below their MDCs, only a summary of the MDCs can be provided. The measurement results reported by SRNL are listed in Appendix A, and the results of this analysis are reported in Appendix B. The data were generally found to follow a normal distribution, and to be homogeneous across composite samples.« less

  15. Statistical Analysis of Tank 5 Floor Sample Results

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shine, E. P.

    2013-01-31

    Sampling has been completed for the characterization of the residual material on the floor of Tank 5 in the F-Area Tank Farm at the Savannah River Site (SRS), near Aiken, SC. The sampling was performed by Savannah River Remediation (SRR) LLC using a stratified random sampling plan with volume-proportional compositing. The plan consisted of partitioning the residual material on the floor of Tank 5 into three non-overlapping strata: two strata enclosed accumulations, and a third stratum consisted of a thin layer of material outside the regions of the two accumulations. Each of three composite samples was constructed from five primarymore » sample locations of residual material on the floor of Tank 5. Three of the primary samples were obtained from the stratum containing the thin layer of material, and one primary sample was obtained from each of the two strata containing an accumulation. This report documents the statistical analyses of the analytical results for the composite samples. The objective of the analysis is to determine the mean concentrations and upper 95% confidence (UCL95) bounds for the mean concentrations for a set of analytes in the tank residuals. The statistical procedures employed in the analyses were consistent with the Environmental Protection Agency (EPA) technical guidance by Singh and others [2010]. Savannah River National Laboratory (SRNL) measured the sample bulk density, nonvolatile beta, gross alpha, and the radionuclide1, elemental, and chemical concentrations three times for each of the composite samples. The analyte concentration data were partitioned into three separate groups for further analysis: analytes with every measurement above their minimum detectable concentrations (MDCs), analytes with no measurements above their MDCs, and analytes with a mixture of some measurement results above and below their MDCs. The means, standard deviations, and UCL95s were computed for the analytes in the two groups that had at least some measurements above their MDCs. The identification of distributions and the selection of UCL95 procedures generally followed the protocol in Singh, Armbya, and Singh [2010]. When all of an analyte's measurements lie below their MDCs, only a summary of the MDCs can be provided. The measurement results reported by SRNL are listed, and the results of this analysis are reported. The data were generally found to follow a normal distribution, and to be homogenous across composite samples.« less

  16. Statistical Analysis Of Tank 5 Floor Sample Results

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shine, E. P.

    2012-08-01

    Sampling has been completed for the characterization of the residual material on the floor of Tank 5 in the F-Area Tank Farm at the Savannah River Site (SRS), near Aiken, SC. The sampling was performed by Savannah River Remediation (SRR) LLC using a stratified random sampling plan with volume-proportional compositing. The plan consisted of partitioning the residual material on the floor of Tank 5 into three non-overlapping strata: two strata enclosed accumulations, and a third stratum consisted of a thin layer of material outside the regions of the two accumulations. Each of three composite samples was constructed from five primarymore » sample locations of residual material on the floor of Tank 5. Three of the primary samples were obtained from the stratum containing the thin layer of material, and one primary sample was obtained from each of the two strata containing an accumulation. This report documents the statistical analyses of the analytical results for the composite samples. The objective of the analysis is to determine the mean concentrations and upper 95% confidence (UCL95) bounds for the mean concentrations for a set of analytes in the tank residuals. The statistical procedures employed in the analyses were consistent with the Environmental Protection Agency (EPA) technical guidance by Singh and others [2010]. Savannah River National Laboratory (SRNL) measured the sample bulk density, nonvolatile beta, gross alpha, and the radionuclide, elemental, and chemical concentrations three times for each of the composite samples. The analyte concentration data were partitioned into three separate groups for further analysis: analytes with every measurement above their minimum detectable concentrations (MDCs), analytes with no measurements above their MDCs, and analytes with a mixture of some measurement results above and below their MDCs. The means, standard deviations, and UCL95s were computed for the analytes in the two groups that had at least some measurements above their MDCs. The identification of distributions and the selection of UCL95 procedures generally followed the protocol in Singh, Armbya, and Singh [2010]. When all of an analyte's measurements lie below their MDCs, only a summary of the MDCs can be provided. The measurement results reported by SRNL are listed in Appendix A, and the results of this analysis are reported in Appendix B. The data were generally found to follow a normal distribution, and to be homogenous across composite samples.« less

  17. Analytical solution and simplified analysis of coupled parent-daughter steady-state transport with multirate mass transfer

    Treesearch

    R. Haggerty

    2013-01-01

    In this technical note, a steady-state analytical solution of concentrations of a parent solute reacting to a daughter solute, both of which are undergoing transport and multirate mass transfer, is presented. Although the governing equations are complicated, the resulting solution can be expressed in simple terms. A function of the ratio of concentrations, In (daughter...

  18. Methods and devices for high-throughput dielectrophoretic concentration

    DOEpatents

    Simmons, Blake A.; Cummings, Eric B.; Fiechtner, Gregory J.; Fintschenko, Yolanda; McGraw, Gregory J.; Salmi, Allen

    2010-02-23

    Disclosed herein are methods and devices for assaying and concentrating analytes in a fluid sample using dielectrophoresis. As disclosed, the methods and devices utilize substrates having a plurality of pores through which analytes can be selectively prevented from passing, or inhibited, on application of an appropriate electric field waveform. The pores of the substrate produce nonuniform electric field having local extrema located near the pores. These nonuniform fields drive dielectrophoresis, which produces the inhibition. Arrangements of electrodes and porous substrates support continuous, bulk, multi-dimensional, and staged selective concentration.

  19. Pre-concentration technique for reduction in "Analytical instrument requirement and analysis"

    NASA Astrophysics Data System (ADS)

    Pal, Sangita; Singha, Mousumi; Meena, Sher Singh

    2018-04-01

    Availability of analytical instruments for a methodical detection of known and unknown effluents imposes a serious hindrance in qualification and quantification. Several analytical instruments such as Elemental analyzer, ICP-MS, ICP-AES, EDXRF, ion chromatography, Electro-analytical instruments which are not only expensive but also time consuming, required maintenance, damaged essential parts replacement which are of serious concern. Move over for field study and instant detection installation of these instruments are not convenient to each and every place. Therefore, technique such as pre-concentration of metal ions especially for lean stream elaborated and justified. Chelation/sequestration is the key of immobilization technique which is simple, user friendly, most effective, least expensive, time efficient; easy to carry (10g - 20g vial) to experimental field/site has been demonstrated.

  20. Dependence of yield of nuclear track-biosensors on track radius and analyte concentration

    NASA Astrophysics Data System (ADS)

    García-Arellano, H.; Muñoz H., G.; Fink, D.; Vacik, J.; Hnatowicz, V.; Alfonta, L.; Kiv, A.

    2018-04-01

    In swift heavy ion track-based polymeric biosensor foils with incorporated enzymes one exploits the correlation between the analyte concentration and the sensor current, via the enrichment of charged enzymatic reaction products in the track's confinement. Here we study the influence of the etched track radius on the biosensor's efficiency. These sensors are analyte-specific only if both the track radii and the analyte concentration exceed certain threshold values of ∼15 nm and ∼10-6 M (for glucose sensing), respectively. Below these limits the sensor signal stems un-specifically from any charge carrier. In its proper working regime, the inner track walls are smoothly covered by enzymes and the efficiency is practically radius independent. Theory shows that the measured current should be slightly sub-proportional to the analyte concentration; the measurements roughly reconfirm this. Narrower tracks (∼5-15 nm radius) with reduced enzyme coverage lead to decreasing efficiency. Tiny signals visible when the tracks are etched to effective radii between 0 and ∼5 nm are tentatively ascribed to enzymes bonded to surface-near nano-cracks in the polymer foil, resulting from its degradation due to aging, rather than to the tracks. Precondition for this study was the accurate determination of the etched track radii, which is possible only by a nanofluidic approach. This holds to some extent even for enzyme-covered tracks, though in this case most of the wall charges are compensated by enzyme bonding.

  1. Evaluation of groundwater pollution in a mining area using analytical solution: a case study of the Yimin open-pit mine in China.

    PubMed

    Li, Tianxin; Li, Li; Song, Hongqing; Meng, Linglong; Zhang, Shuli; Huang, Gang

    2016-01-01

    This study focused on using analytical and numerical models to develop and manage groundwater resources, and predict the effects of management measurements in the groundwater system. Movement of contaminants can be studied based on groundwater flow characteristics. This study can be used for prediction of ion concentration and evaluation of groundwater pollution as the theoretical basis. The Yimin open-pit mine is located in the northern part of the Inner Mongolia Autonomous Region of China. High concentrations of iron and manganese are observed in Yimin open-pit mine because of exploitation and pumping that have increased the concentration of the ions in groundwater. In this study, iron was considered as an index of contamination, and the solute model was calibrated using concentration observations from 14 wells in 2014. The groundwater flow model and analytical solutions were used in this study to forecast pollution concentration and variation trend after calibration. With continuous pumping, contaminants will migrate, and become enriched, towards the wellhead in the flow direction. The concentration of the contaminants and the range of pollution increase with the flow rate increased. The suitable flow rate of single well should be <380 m/day at Yimin open-pit for the standard value of pollution concentration.

  2. Determination of steroid hormones and related compounds in filtered and unfiltered water by solid-phase extraction, derivatization, and gas chromatography with tandem mass spectrometry

    USGS Publications Warehouse

    Foreman, William T.; Gray, James L.; ReVello, Rhiannon C.; Lindley, Chris E.; Losche, Scott A.; Barber, Larry B.

    2012-01-01

    A new analytical method has been developed and implemented at the U.S. Geological Survey National Water Quality Laboratory that determines a suite of 20 steroid hormones and related compounds in filtered water (using laboratory schedule 2434) and in unfiltered water (using laboratory schedule 4434). This report documents the procedures and initial performance data for the method and provides guidance on application of the method and considerations of data quality in relation to data interpretation. The analytical method determines 6 natural and 3 synthetic estrogen compounds, 6 natural androgens, 1 natural and 1 synthetic progestin compound, and 2 sterols: cholesterol and 3--coprostanol. These two sterols have limited biological activity but typically are abundant in wastewater effluents and serve as useful tracers. Bisphenol A, an industrial chemical used primarily to produce polycarbonate plastic and epoxy resins and that has been shown to have estrogenic activity, also is determined by the method. A technique referred to as isotope-dilution quantification is used to improve quantitative accuracy by accounting for sample-specific procedural losses in the determined analyte concentration. Briefly, deuterium- or carbon-13-labeled isotope-dilution standards (IDSs), all of which are direct or chemically similar isotopic analogs of the method analytes, are added to all environmental and quality-control and quality-assurance samples before extraction. Method analytes and IDS compounds are isolated from filtered or unfiltered water by solid-phase extraction onto an octadecylsilyl disk, overlain with a graded glass-fiber filter to facilitate extraction of unfiltered sample matrices. The disks are eluted with methanol, and the extract is evaporated to dryness, reconstituted in solvent, passed through a Florisil solid-phase extraction column to remove polar organic interferences, and again evaporated to dryness in a reaction vial. The method compounds are reacted with activated -methyl--trimethylsilyl trifluoroacetamide at 65 degrees Celsius for 1 hour to form trimethylsilyl or trimethylsilyl-enol ether derivatives that are more amenable to gas chromatographic separation than the underivatized compounds. Analysis is carried out by gas chromatography with tandem mass spectrometry using calibration standards that are derivatized concurrently with the sample extracts. Analyte concentrations are quantified relative to specific IDS compounds in the sample, which directly compensate for procedural losses (incomplete recovery) in the determined and reported analyte concentrations. Thus, reported analyte concentrations (or analyte recoveries for spiked samples) are corrected based on recovery of the corresponding IDS compound during the quantification process. Recovery for each IDS compound is reported for each sample and represents an absolute recovery in a manner comparable to surrogate recoveries for other organic methods used by the National Water Quality Laboratory. Thus, IDS recoveries provide a useful tool for evaluating sample-specific analytical performance from an absolute mass recovery standpoint. IDS absolute recovery will differ and typically be lower than the corresponding analyte’s method recovery in spiked samples. However, additional correction of reported analyte concentrations is unnecessary and inappropriate because the analyte concentration (or recovery) already is compensated for by the isotope-dilution quantification procedure. Method analytes were spiked at 10 and 100 nanograms per liter (ng/L) for most analytes (10 times greater spike levels were used for bisphenol A and 100 times greater spike levels were used for 3--coprostanol and cholesterol) into the following validation-sample matrices: reagent water, wastewater-affected surface water, a secondary-treated wastewater effluent, and a primary (no biological treatment) wastewater effluent. Overall method recovery for all analytes in these matrices averaged 100 percent, with overall relative standard deviation of 28 percent. Mean recoveries of the 20 individual analytes for spiked reagent-water samples prepared along with field samples and analyzed in 2009–2010 ranged from 84–104 percent, with relative standard deviations of 6–36 percent. Concentrations for two analytes, equilin and progesterone, are reported as estimated because these analytes had excessive bias or variability, or both. Additional database coding is applied to other reported analyte data as needed, based on sample-specific IDS recovery performance. Detection levels were derived statistically by fortifying reagent water at six different levels (0.1 to 4 ng/L) and range from about 0.4 to 4 ng/L for 16 analytes. Interim reporting levels applied to analytes in this report range from 0.8 to 8 ng/L. Bisphenol A and the sterols (cholesterol and 3-beta-coprostanol) were consistently detected in laboratory and field blanks. The minimum reporting levels were set at 100 ng/L for bisphenol A and at 200 ng/L for the two sterols to prevent any bias associated with the presence of these compounds in the blanks. A minimum reporting level of 2 ng/L was set for 11-ketotestosterone to minimize false positive risk from an interfering siloxane compound emanating as chromatographic-column bleed, from vial septum material, or from other sources at no more than 1 ng/L.

  3. Hemolysis indexes for biochemical tests and immunoassays on Roche analyzers: determination of allowable interference limits according to different calculation methods.

    PubMed

    Monneret, Denis; Mestari, Fouzi; Atlan, Gregory; Corlouer, Camille; Ramani, Zo; Jaffre, Jeremy; Dever, Sylvie; Fressart, Veronique; Alkouri, Rana; Lamari, Foudil; Devilliers, Catherine; Imbert-Bismut, Françoise; Bonnefont-Rousselot, Dominique

    2015-04-01

    To determine the hemolysis interference on biochemical tests and immunoassays performed on Roche Diagnostics analyzers, according to different maximum allowable limits. Heparinized plasma and serum pools, free of interferences, were overloaded by increasing amounts of a hemoglobin-titrated hemolysate. This interference was evaluated for 45 analytes using Modular(®) and Cobas(®) analyzers. For each parameter, the hemolysis index (HI) corresponding to the traditional ± 10% change of concentrations from baseline (± 10%Δ) was determined, as well as those corresponding to the analytical change limit (ACL), and to the reference change value (RCV). Then, the relative frequencies distribution (% RFD) of hemolyzed tests performed in a hospital laboratory over a 25-day period were established for each HI as allowable limit. Considering the ± 10%Δ, the analyte concentrations enhanced by hemolysis were: Lactate dehydrogenase (LDH), aspartate aminotransferase (AST), folate, potassium, creatine kinase, phosphorus, iron, alanine aminotransferase, lipase, magnesium and triglycerides, decreasingly. The analyte concentrations decreased by hemolysis were: Haptoglobin, high-sensitive troponin T and alkaline phosphatase. Over the 25-day period, the % RFD of tests impacted more than 10%Δ by hemolysis were < 7% for LDH; < 5% for AST, folates and iron; and < 1% for the other analytes. Considering the ACL, HI were lower, giving % RFD substantially increased for many analytes, whereas only four analytes remain sensitive to hemolysis when considering RCV. This study proposes new HI based on different allowable limits, and can therefore serve as a starting point for future harmonization of hemolysis interference evaluation needed in routine laboratory practice.

  4. Thermodiffusion in concentrated ferrofluids: A review and current experimental and numerical results on non-magnetic thermodiffusion

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sprenger, Lisa, E-mail: Lisa.Sprenger@tu-dresden.de; Lange, Adrian; Odenbach, Stefan

    2013-12-15

    Ferrofluids are colloidal suspensions consisting of magnetic nanoparticles dispersed in a carrier liquid. Their thermodiffusive behaviour is rather strong compared to molecular binary mixtures, leading to a Soret coefficient (S{sub T}) of 0.16 K{sup −1}. Former experiments with dilute magnetic fluids have been done with thermogravitational columns or horizontal thermodiffusion cells by different research groups. Considering the horizontal thermodiffusion cell, a former analytical approach has been used to solve the phenomenological diffusion equation in one dimension assuming a constant concentration gradient over the cell's height. The current experimental work is based on the horizontal separation cell and emphasises the comparison ofmore » the concentration development in different concentrated magnetic fluids and at different temperature gradients. The ferrofluid investigated is the kerosene-based EMG905 (Ferrotec) to be compared with the APG513A (Ferrotec), both containing magnetite nanoparticles. The experiments prove that the separation process linearly depends on the temperature gradient and that a constant concentration gradient develops in the setup due to the separation. Analytical one dimensional and numerical three dimensional approaches to solve the diffusion equation are derived to be compared with the solution used so far for dilute fluids to see if formerly made assumptions also hold for higher concentrated fluids. Both, the analytical and numerical solutions, either in a phenomenological or a thermodynamic description, are able to reproduce the separation signal gained from the experiments. The Soret coefficient can then be determined to 0.184 K{sup −1} in the analytical case and 0.29 K{sup −1} in the numerical case. Former theoretical approaches for dilute magnetic fluids underestimate the strength of the separation in the case of a concentrated ferrofluid.« less

  5. Complex analysis of concentrated antibody-gold nanoparticle conjugates' mixtures using asymmetric flow field-flow fractionation.

    PubMed

    Safenkova, Irina V; Slutskaya, Elvira S; Panferov, Vasily G; Zherdev, Anatoly V; Dzantiev, Boris B

    2016-12-16

    Conjugates of gold nanoparticles (GNPs) with antibodies are powerful analytical tools. It is crucial to know the conjugates' state in both the concentrated and mixed solutions used in analytical systems. Herein, we have applied asymmetrical flow field-flow fractionation (AF4) to identify the conjugates' state. The influence of a conjugate's composition and concentration on aggregation was studied in a true analytical solution (a concentrated mixture with stabilizing components). GNPs with an average diameter of 15.3±1.2nm were conjugated by adsorption with eight antibodies of different specificities. We found that, while the GNPs have a zeta potential of -31.6mV, the conjugates have zeta potentials ranging from -5.8 to -11.2mV. Increased concentrations (up to 184nM, OD 520 =80) of the mixed conjugate (mixture of eight conjugates) did not change the form of fractograms, and the peak areas' dependence on concentration was strongly linear (R 2 values of 0.99919 and 0.99845 for absorption signal and light scattering, respectively). Based on the gyration (R g ) and hydrodynamic (R h ) radii measured during fractionation, we found that the nanoparticles were divided into two populations: (1) those with constant radii (R g =9.9±0.9nm; R h =14.3±0.5nm); and (2) those with increased radii from 9.9 to 24.4nm for R g and from 14.3 to 28.1nm for R h . These results confirm that the aggregate state of the concentrated and mixed conjugates' preparations is the same as that of diluted preparations and that AF4 efficiently characterizes the conjugates' state in a true analytical solution. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Multiplexed Colorimetric Solid-Phase Extraction

    NASA Technical Reports Server (NTRS)

    Gazda, Daniel B.; Fritz, James S.; Porter, Marc D.

    2009-01-01

    Multiplexed colorimetric solid-phase extraction (MC-SPE) is an extension of colorimetric solid-phase extraction (C-SPE) an analytical platform that combines colorimetric reagents, solid phase extraction, and diffuse reflectance spectroscopy to quantify trace analytes in water. In CSPE, analytes are extracted and complexed on the surface of an extraction membrane impregnated with a colorimetric reagent. The analytes are then quantified directly on the membrane surface using a handheld diffuse reflectance spectrophotometer. Importantly, the use of solid-phase extraction membranes as the matrix for impregnation of the colorimetric reagents creates a concentration factor that enables the detection of low concentrations of analytes in small sample volumes. In extending C-SPE to a multiplexed format, a filter holder that incorporates discrete analysis channels and a jig that facilitates the concurrent operation of multiple sample syringes have been designed, enabling the simultaneous determination of multiple analytes. Separate, single analyte membranes, placed in a readout cartridge create unique, analyte-specific addresses at the exit of each channel. Following sample exposure, the diffuse reflectance spectrum of each address is collected serially and the Kubelka-Munk function is used to quantify each water quality parameter via calibration curves. In a demonstration, MC-SPE was used to measure the pH of a sample and quantitate Ag(I) and Ni(II).

  7. Probing mass-transport and binding inhomogeneity in macromolecular interactions by molecular interferometric imaging

    NASA Astrophysics Data System (ADS)

    Zhao, Ming; Wang, Xuefeng; Nolte, David

    2009-02-01

    In solid-support immunoassays, the transport of target analyte in sample solution to capture molecules on the sensor surface controls the detected binding signal. Depletion of the target analyte in the sample solution adjacent to the sensor surface leads to deviations from ideal association, and causes inhomogeneity of surface binding as analyte concentration varies spatially across the sensor surface. In the field of label-free optical biosensing, studies of mass-transport-limited reaction kinetics have focused on the average response on the sensor surface, but have not addressed binding inhomogeneities caused by mass-transport limitations. In this paper, we employ Molecular Interferometric Imaging (MI2) to study mass-transport-induced inhomogeneity of analyte binding within a single protein spot. Rabbit IgG binding to immobilized protein A/G was imaged at various concentrations and under different flow rates. In the mass-transport-limited regime, enhanced binding at the edges of the protein spots was caused by depletion of analyte towards the center of the protein spots. The magnitude of the inhomogeneous response was a function of analyte reaction rate and sample flow rate.

  8. Communication — Modeling polymer-electrolyte fuel-cell agglomerates with double-trap kinetics

    DOE PAGES

    Pant, Lalit M.; Weber, Adam Z.

    2017-04-14

    A new semi-analytical agglomerate model is presented for polymer-electrolyte fuel-cell cathodes. The model uses double-trap kinetics for the oxygen-reduction reaction, which can capture the observed potential-dependent coverage and Tafel-slope changes. An iterative semi-analytical approach is used to obtain reaction rate constants from the double-trap kinetics, oxygen concentration at the agglomerate surface, and overall agglomerate reaction rate. The analytical method can predict reaction rates within 2% of the numerically simulated values for a wide range of oxygen concentrations, overpotentials, and agglomerate sizes, while saving simulation time compared to a fully numerical approach.

  9. Notch Sensitivity of Woven Ceramic Matrix Composites Under Tensile Loading: An Experimental, Analytical, and Finite Element Study

    NASA Technical Reports Server (NTRS)

    Haque, A.; Ahmed, L.; Ware, T.; Jeelani, S.; Verrilli, Michael J. (Technical Monitor)

    2001-01-01

    The stress concentrations associated with circular notches and subjected to uniform tensile loading in woven ceramic matrix composites (CMCs) have been investigated for high-efficient turbine engine applications. The CMC's were composed of Nicalon silicon carbide woven fabric in SiNC matrix manufactured through polymer impregnation process (PIP). Several combinations of hole diameter/plate width ratios and ply orientations were considered in this study. In the first part, the stress concentrations were calculated measuring strain distributions surrounding the hole using strain gages at different locations of the specimens during the initial portion of the stress-strain curve before any microdamage developed. The stress concentration was also calculated analytically using Lekhnitskii's solution for orthotropic plates. A finite-width correction factor for anisotropic and orthotropic composite plate was considered. The stress distributions surrounding the circular hole of a CMC's plate were further studied using finite element analysis. Both solid and shell elements were considered. The experimental results were compared with both the analytical and finite element solutions. Extensive optical and scanning electron microscopic examinations were carried out for identifying the fracture behavior and failure mechanisms of both the notched and notched specimens. The stress concentration factors (SCF) determined by analytical method overpredicted the experimental results. But the numerical solution underpredicted the experimental SCF. Stress concentration factors are shown to increase with enlarged hole size and the effects of ply orientations on stress concentration factors are observed to be negligible. In all the cases, the crack initiated at the notch edge and propagated along the width towards the edge of the specimens.

  10. PLE in the analysis of plant compounds. Part II: One-cycle PLE in determining total amount of analyte in plant material.

    PubMed

    Dawidowicz, Andrzej L; Wianowska, Dorota

    2005-04-29

    Pressurised liquid extraction (PLE) is recognised as one of the most effective sample preparation methods. Despite the enhanced extraction power of PLE, the full recovery of an analyte from plant material may require multiple extractions of the same sample. The presented investigations show the possibility of estimating the true concentration value of an analyte in plant material employing one-cycle PLE in which plant samples of different weight are used. The performed experiments show a linear dependence between the reciprocal value of the analyte amount (E*), extracted in single-step PLE from a plant matrix, and the ratio of plant material mass to extrahent volume (m(p)/V(s)). Hence, time-consuming multi-step PLE can be replaced by a few single-step PLEs performed at different (m(p)/V(s)) ratios. The concentrations of rutin in Sambucus nigra L. and caffeine in tea and coffee estimated by means of the tested procedure are almost the same as their concentrations estimated by multiple PLE.

  11. Sampling hazelnuts for aflatoxin: uncertainty associated with sampling, sample preparation, and analysis.

    PubMed

    Ozay, Guner; Seyhan, Ferda; Yilmaz, Aysun; Whitaker, Thomas B; Slate, Andrew B; Giesbrecht, Francis

    2006-01-01

    The variability associated with the aflatoxin test procedure used to estimate aflatoxin levels in bulk shipments of hazelnuts was investigated. Sixteen 10 kg samples of shelled hazelnuts were taken from each of 20 lots that were suspected of aflatoxin contamination. The total variance associated with testing shelled hazelnuts was estimated and partitioned into sampling, sample preparation, and analytical variance components. Each variance component increased as aflatoxin concentration (either B1 or total) increased. With the use of regression analysis, mathematical expressions were developed to model the relationship between aflatoxin concentration and the total, sampling, sample preparation, and analytical variances. The expressions for these relationships were used to estimate the variance for any sample size, subsample size, and number of analyses for a specific aflatoxin concentration. The sampling, sample preparation, and analytical variances associated with estimating aflatoxin in a hazelnut lot at a total aflatoxin level of 10 ng/g and using a 10 kg sample, a 50 g subsample, dry comminution with a Robot Coupe mill, and a high-performance liquid chromatographic analytical method are 174.40, 0.74, and 0.27, respectively. The sampling, sample preparation, and analytical steps of the aflatoxin test procedure accounted for 99.4, 0.4, and 0.2% of the total variability, respectively.

  12. A simple analytical method to estimate all exit parameters of a cross-flow air dehumidifier using liquid desiccant

    PubMed Central

    Bassuoni, M.M.

    2013-01-01

    The dehumidifier is a key component in liquid desiccant air-conditioning systems. Analytical solutions have more advantages than numerical solutions in studying the dehumidifier performance parameters. This paper presents the performance results of exit parameters from an analytical model of an adiabatic cross-flow liquid desiccant air dehumidifier. Calcium chloride is used as desiccant material in this investigation. A program performing the analytical solution is developed using the engineering equation solver software. Good accuracy has been found between analytical solution and reliable experimental results with a maximum deviation of +6.63% and −5.65% in the moisture removal rate. The method developed here can be used in the quick prediction of the dehumidifier performance. The exit parameters from the dehumidifier are evaluated under the effects of variables such as air temperature and humidity, desiccant temperature and concentration, and air to desiccant flow rates. The results show that hot humid air and desiccant concentration have the greatest impact on the performance of the dehumidifier. The moisture removal rate is decreased with increasing both air inlet temperature and desiccant temperature while increases with increasing air to solution mass ratio, inlet desiccant concentration, and inlet air humidity ratio. PMID:25685485

  13. Optical characterization of nonimaging dish concentrator for the application of dense-array concentrator photovoltaic system.

    PubMed

    Tan, Ming-Hui; Chong, Kok-Keong; Wong, Chee-Woon

    2014-01-20

    Optimization of the design of a nonimaging dish concentrator (NIDC) for a dense-array concentrator photovoltaic system is presented. A new algorithm has been developed to determine configuration of facet mirrors in a NIDC. Analytical formulas were derived to analyze the optical performance of a NIDC and then compared with a simulated result obtained from a numerical method. Comprehensive analysis of optical performance via analytical method has been carried out based on facet dimension and focal distance of the concentrator with a total reflective area of 120 m2. The result shows that a facet dimension of 49.8 cm, focal distance of 8 m, and solar concentration ratio of 411.8 suns is the most optimized design for the lowest cost-per-output power, which is US$1.93 per watt.

  14. What's the Bottom Line

    EPA Science Inventory

    Advances in analytical instrumentation have not only increased the number and types of chemicals measured, but reduced the quantitation limits, allowing these chemicals to be detected at progressively lower concentrations in various environmental matrices. Such analytical advanc...

  15. Filter Membrane Effects on Water-Extractable Phosphorus Concentrations from Soil.

    PubMed

    Norby, Jessica; Strawn, Daniel; Brooks, Erin

    2018-03-01

    To accurately assess P concentrations in soil extracts, standard laboratory practices for monitoring P concentrations are needed. Water-extractable P is a common analytical test to determine P availability for leaching from soils, and it is used to determine best management practices. Most P analytical tests require filtration through a filter membrane with 0.45-μm pore size to distinguish between particulate and dissolved P species. However, filter membrane type is rarely specified in method protocols, and many different types of membranes are available. In this study, three common filter membrane materials (polyether sulfone, nylon, and nitrocellulose), all with 0.45-μm pore sizes, were tested for analytical differences in total P concentrations and dissolved reactive P (DRP) concentrations in water extracts from six soils sampled from two regions. Three of the extracts from the six soil samples had different total P concentrations for all three membrane types. The other three soil extracts had significantly different total P results from at least one filter membrane type. Total P concentration differences were as great as 35%. The DRP concentrations in the extracts were dependent on filter type in five of the six soil types. Results from this research show that filter membrane type is an important parameter that affects concentrations of total P and DRP from soil extracts. Thus, membrane type should be specified in soil extraction protocols. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  16. Tank vapor characterization project. Headspace vapor characterization of Hanford waste tank 241-BY-108: Second comparison study results from samples collected on 3/28/96

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Thomas, B.L.; Pool, K.H.; Evans, J.C.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of waste storage tank 241-BY-108 (Tank BY-108) at the Hanford Site in Washington State. The results described in this report is the second in a series comparing vapor sampling of the tank headspace using the Vapor Sampling System (VSS) and In Situ Vapor Sampling (ISVS) system without high efficiency particulate air (HEPA) prefiltration. The results include air concentrations of water (H{sub 2}O) and ammonia (NH{sub 3}), permanent gases, total non-methane organic compounds (TO-12), and individual organic analytes collected in SUMMA{trademark} canisters and on triple sorbent traps (TSTs).more » Samples were collected by Westinghouse Hanford Company (WHC) and analyzed by Pacific Northwest National Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, sample volume measurements provided by WHC.« less

  17. Chemical clocks, oscillations, and other temporal effects in analytical chemistry: oddity or viable approach?

    PubMed

    Prabhu, Gurpur Rakesh D; Witek, Henryk A; Urban, Pawel L

    2018-05-31

    Most analytical methods are based on "analogue" inputs from sensors of light, electric potentials, or currents. The signals obtained by such sensors are processed using certain calibration functions to determine concentrations of the target analytes. The signal readouts are normally done after an optimised and fixed time period, during which an assay mixture is incubated. This minireview covers another-and somewhat unusual-analytical strategy, which relies on the measurement of time interval between the occurrences of two distinguishable states in the assay reaction. These states manifest themselves via abrupt changes in the properties of the assay mixture (e.g. change of colour, appearance or disappearance of luminescence, change in pH, variations in optical activity or mechanical properties). In some cases, a correlation between the time of appearance/disappearance of a given property and the analyte concentration can be also observed. An example of an assay based on time measurement is an oscillating reaction, in which the period of oscillations is linked to the concentration of the target analyte. A number of chemo-chronometric assays, relying on the existing (bio)transformations or artificially designed reactions, were disclosed in the past few years. They are very attractive from the fundamental point of view but-so far-only few of them have be validated and used to address real-world problems. Then, can chemo-chronometric assays become a practical tool for chemical analysis? Is there a need for further development of such assays? We are aiming to answer these questions.

  18. Monitoring tylosin and sulfamethazine in a tile-drained agricultural watershed using polar organic chemical integrative sampler (POCIS).

    PubMed

    Washington, Maurice T; Moorman, Thomas B; Soupir, Michelle L; Shelley, Mack; Morrow, Amy J

    2018-01-15

    This study evaluated the influence of temporal variation on the occurrence, fate, and transport of tylosin (TYL) and sulfamethazine (SMZ); antibiotics commonly used in swine production. Atrazine (ATZ) was used as a reference analyte to indicate the agricultural origin of the antibiotics. We also assessed the impact of season and hydrology on antibiotic concentrations. A reconnaissance study of the South Fork watershed of the Iowa River (SFIR), was conducted from 2013 to 2015. Tile drain effluent and surface water were monitored using polar organic integrative sampler (POCIS) technology. Approximately 169 animal feeding operations (AFOs) exist in SFIR, with 153 of them being swine facilities. All analytes were detected, and detection frequencies ranged from 69 to 100% showing the persistence in the watershed. Antibiotics were detected at a higher frequency using POCIS compared to grab samples. We observed statistically significant seasonal trends for SMZ and ATZ concentrations during growing and harvest seasons. Time weighted average (TWA) concentrations quantified from the POCIS were 1.87ngL -1 (SMZ), 0.30ngL -1 (TYL), and 754.2ngL -1 (ATZ) in the watershed. SMZ and TYL concentrations were lower than the minimum inhibitory concentrations (MIC) for E. coli. All analytes were detected in tile drain effluent, confirming tile drainage as a pathway for antibiotic transport. Our results identify the episodic occurrence of antibiotics, and highlights the importance identifying seasonal fate and occurrence of these analytes. Published by Elsevier B.V.

  19. Compounds in airborne particulates - Salts and hydrocarbons. [at Cleveland, OH

    NASA Technical Reports Server (NTRS)

    King, R. B.; Antoine, A. C.; Fordyce, J. S.; Neustadter, H. E.; Leibecki, H. F.

    1977-01-01

    Concentrations of 10 polycyclic aromatic hydrocarbons (PAH), the aliphatics as a group, sulfate, nitrate, fluoride, acidity, and carbon in the airborne particulate matter were measured at 16 sites in Cleveland, OH over a 1-year period during 1971 and 1972. Analytical methods used included gas chromatography, colorimetry, and combustion techniques. Uncertainties in the concentrations associated with the sampling procedures, and the analytical methods are evaluated. The data are discussed relative to other studies and source origins. High concentrations downwind of coke ovens for 3,4 benzopyrene are discussed. Hydrocarbon correlation studies indicated no significant relations among compounds studied.

  20. Comparative study of solar optics for paraboloidal concentrators

    NASA Technical Reports Server (NTRS)

    Wen, L.; Poon, P.; Carley, W.; Huang, L.

    1979-01-01

    Different analytical methods for computing the flux distribution on the focal plane of a paraboloidal solar concentrator are reviewed. An analytical solution in algebraic form is also derived for an idealized model. The effects resulting from using different assumptions in the definition of optical parameters used in these methodologies are compared and discussed in detail. These parameters include solar irradiance distribution (limb darkening and circumsolar), reflector surface specular spreading, surface slope error, and concentrator pointing inaccuracy. The type of computational method selected for use depends on the maturity of the design and the data available at the time the analysis is made.

  1. A simple recirculating flow system for the calibration of polar organic chemical integrative samplers (POCIS): effect of flow rate on different water pollutants.

    PubMed

    Di Carro, Marina; Bono, Luca; Magi, Emanuele

    2014-03-01

    A calibration system for POCIS was developed and used to calculate the sampling rates of eight analytes belonging to pesticides, non-steroidal anti-inflammatory drugs and perfluorinated compounds: atrazine, propazine, terbutylazine, diclofenac, ibuprofen, ketoprofen, perfluorooctanoic acid and perfluorooctanesulfonate. Experiments with a linear velocity of 2.0, 5.1, 10.2 and 15.3 cm/s were carried out for 96 h using two different analyte concentrations. POCIS extracts were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS), using multiple reaction monitoring to maximize sensitivity. Results highlighted that the calculated sampling rates are rather constant at the considered concentrations and flow rates. Obtained values of sampling rates were then employed to calculate Time-Weighted Average concentration of the analytes in river and drinking waters. © 2013 Published by Elsevier B.V.

  2. Chitosan as cationic polyelectrolyte for the modification of electroosmotic flow and its utilization for the separation of inorganic anions by capillary zone electrophoresis.

    PubMed

    Takayanagi, Toshio; Motomizu, Shoji

    2006-09-01

    Cationic polyelectrolyte of chitosan was used for the reversal of electroosmotic flow in capillary zone electrophoresis. The chitosan was dissolved in acetic acid solution, and stable electroosmotic flow was obtained at the chitosan concentrations between 50 and 300 microg/mL. Separation of inorganic anions was carried out using the dynamically coated capillary by capillary zone electrophoresis. Nine kinds of anions were separated and detected with the capillary. The electrophoretic mobility of the analyte anions decreased with increasing concentrations of chitosan in the migrating solution through ion-ion interaction, but the migration order of the analyte anions was not changed in the concentration range of the chitosan examined. The signal shape for the analyte anions was developed by using field-enhanced sample stacking with 10 mM sodium sulfate.

  3. Predicting concentrations of trace organic compounds in municipal wastewater treatment plant sludge and biosolids using the PhATE™ model.

    PubMed

    Cunningham, Virginia L; D'Aco, Vincent J; Pfeiffer, Danielle; Anderson, Paul D; Buzby, Mary E; Hannah, Robert E; Jahnke, James; Parke, Neil J

    2012-07-01

    This article presents the capability expansion of the PhATE™ (pharmaceutical assessment and transport evaluation) model to predict concentrations of trace organics in sludges and biosolids from municipal wastewater treatment plants (WWTPs). PhATE was originally developed as an empirical model to estimate potential concentrations of active pharmaceutical ingredients (APIs) in US surface and drinking waters that could result from patient use of medicines. However, many compounds, including pharmaceuticals, are not completely transformed in WWTPs and remain in biosolids that may be applied to land as a soil amendment. This practice leads to concerns about potential exposures of people who may come into contact with amended soils and also about potential effects to plants and animals living in or contacting such soils. The model estimates the mass of API in WWTP influent based on the population served, the API per capita use, and the potential loss of the compound associated with human use (e.g., metabolism). The mass of API on the treated biosolids is then estimated based on partitioning to primary and secondary solids, potential loss due to biodegradation in secondary treatment (e.g., activated sludge), and potential loss during sludge treatment (e.g., aerobic digestion, anaerobic digestion, composting). Simulations using 2 surrogate compounds show that predicted environmental concentrations (PECs) generated by PhATE are in very good agreement with measured concentrations, i.e., well within 1 order of magnitude. Model simulations were then carried out for 18 APIs representing a broad range of chemical and use characteristics. These simulations yielded 4 categories of results: 1) PECs are in good agreement with measured data for 9 compounds with high analytical detection frequencies, 2) PECs are greater than measured data for 3 compounds with high analytical detection frequencies, possibly as a result of as yet unidentified depletion mechanisms, 3) PECs are less than analytical reporting limits for 5 compounds with low analytical detection frequencies, and 4) the PEC is greater than the analytical method reporting limit for 1 compound with a low analytical detection frequency, possibly again as a result of insufficient depletion data. Overall, these results demonstrate that PhATE has the potential to be a very useful tool in the evaluation of APIs in biosolids. Possible applications include: prioritizing APIs for assessment even in the absence of analytical methods; evaluating sludge processing scenarios to explore potential mitigation approaches; using in risk assessments; and developing realistic nationwide concentrations, because PECs can be represented as a cumulative probability distribution. Finally, comparison of PECs to measured concentrations can also be used to identify the need for fate studies of compounds of interest in biosolids. Copyright © 2011 SETAC.

  4. Intrinsic Bioprobes, Inc. (Tempe, AZ)

    DOEpatents

    Nelson, Randall W [Phoenix, AZ; Williams, Peter [Phoenix, AZ; Krone, Jennifer Reeve [Granbury, TX

    2008-07-15

    Rapid mass spectrometric immunoassay methods for detecting and/or quantifying antibody and antigen analytes utilizing affinity capture to isolate the analytes and internal reference species (for quantification) followed by mass spectrometric analysis of the isolated analyte/internal reference species. Quantification is obtained by normalizing and calibrating obtained mass spectrum against the mass spectrum obtained for an antibody/antigen of known concentration.

  5. Determining passive cooling limits in CPV using an analytical thermal model

    NASA Astrophysics Data System (ADS)

    Gualdi, Federico; Arenas, Osvaldo; Vossier, Alexis; Dollet, Alain; Aimez, Vincent; Arès, Richard

    2013-09-01

    We propose an original thermal analytical model aiming to predict the practical limits of passive cooling systems for high concentration photovoltaic modules. The analytical model is described and validated by comparison with a commercial 3D finite element model. The limiting performances of flat plate cooling systems in natural convection are then derived and discussed.

  6. Mass spectrometric immunoassay

    DOEpatents

    Nelson, Randall W; Williams, Peter; Krone, Jennifer Reeve

    2007-12-04

    Rapid mass spectrometric immunoassay methods for detecting and/or quantifying antibody and antigen analytes utilizing affinity capture to isolate the analytes and internal reference species (for quantification) followed by mass spectrometric analysis of the isolated analyte/internal reference species. Quantification is obtained by normalizing and calibrating obtained mass spectrum against the mass spectrum obtained for an antibody/antigen of known concentration.

  7. Mass spectrometric immunoassay

    DOEpatents

    Nelson, Randall W; Williams, Peter; Krone, Jennifer Reeve

    2013-07-16

    Rapid mass spectrometric immunoassay methods for detecting and/or quantifying antibody and antigen analytes utilizing affinity capture to isolate the analytes and internal reference species (for quantification) followed by mass spectrometric analysis of the isolated analyte/internal reference species. Quantification is obtained by normalizing and calibrating obtained mass spectrum against the mass spectrum obtained for an antibody/antigen of known concentration.

  8. Mass spectrometric immunoassay

    DOEpatents

    Nelson, Randall W.; Williams, Peter; Krone, Jennifer Reeve

    2005-12-13

    Rapid mass spectrometric immunoassay methods for detecting and/or quantifying antibody and antigen analytes utilizing affinity capture to isolate the analytes and internal reference species (for quantification) followed by mass spectrometric analysis of the isolated analyte/internal reference species. Quantification is obtained by normalizing and calibrating obtained mass spectrum against the mass spectrum obtained for an antibody/antigen of known concentration.

  9. Exhaled breath condensate – from an analytical point of view

    PubMed Central

    Dodig, Slavica; Čepelak, Ivana

    2013-01-01

    Over the past three decades, the goal of many researchers is analysis of exhaled breath condensate (EBC) as noninvasively obtained sample. A total quality in laboratory diagnostic processes in EBC analysis was investigated: pre-analytical (formation, collection, storage of EBC), analytical (sensitivity of applied methods, standardization) and post-analytical (interpretation of results) phases. EBC analysis is still used as a research tool. Limitations referred to pre-analytical, analytical, and post-analytical phases of EBC analysis are numerous, e.g. low concentrations of EBC constituents, single-analyte methods lack in sensitivity, and multi-analyte has not been fully explored, and reference values are not established. When all, pre-analytical, analytical and post-analytical requirements are met, EBC biomarkers as well as biomarker patterns can be selected and EBC analysis can hopefully be used in clinical practice, in both, the diagnosis and in the longitudinal follow-up of patients, resulting in better outcome of disease. PMID:24266297

  10. A field study of selected U.S. Geological Survey analytical methods for measuring pesticides in filtered stream water, June - September 2012

    USGS Publications Warehouse

    Martin, Jeffrey D.; Norman, Julia E.; Sandstrom, Mark W.; Rose, Claire E.

    2017-09-06

    U.S. Geological Survey monitoring programs extensively used two analytical methods, gas chromatography/mass spectrometry and liquid chromatography/mass spectrometry, to measure pesticides in filtered water samples during 1992–2012. In October 2012, the monitoring programs began using direct aqueous-injection liquid chromatography tandem mass spectrometry as a new analytical method for pesticides. The change in analytical methods, however, has the potential to inadvertently introduce bias in analysis of datasets that span the change.A field study was designed to document performance of the new method in a variety of stream-water matrices and to quantify any potential changes in measurement bias or variability that could be attributed to changes in analytical methods. The goals of the field study were to (1) summarize performance (bias and variability of pesticide recovery) of the new method in a variety of stream-water matrices; (2) compare performance of the new method in laboratory blank water (laboratory reagent spikes) to that in a variety of stream-water matrices; (3) compare performance (analytical recovery) of the new method to that of the old methods in a variety of stream-water matrices; (4) compare pesticide detections and concentrations measured by the new method to those of the old methods in a variety of stream-water matrices; (5) compare contamination measured by field blank water samples in old and new methods; (6) summarize the variability of pesticide detections and concentrations measured by the new method in field duplicate water samples; and (7) identify matrix characteristics of environmental water samples that adversely influence the performance of the new method. Stream-water samples and a variety of field quality-control samples were collected at 48 sites in the U.S. Geological Survey monitoring networks during June–September 2012. Stream sites were located across the United States and included sites in agricultural and urban land-use settings, as well as sites on major rivers.The results of the field study identified several challenges for the analysis and interpretation of data analyzed by both old and new methods, particularly when data span the change in methods and are combined for analysis of temporal trends in water quality. The main challenges identified are large (greater than 30 percent), statistically significant differences in analytical recovery, detection capability, and (or) measured concentrations for selected pesticides. These challenges are documented and discussed, but specific guidance or statistical methods to resolve these differences in methods are beyond the scope of the report. The results of the field study indicate that the implications of the change in analytical methods must be assessed individually for each pesticide and method.Understanding the possible causes of the systematic differences in concentrations between methods that remain after recovery adjustment might be necessary to determine how to account for the differences in data analysis. Because recoveries for each method are independently determined from separate reference standards and spiking solutions, the differences might be due to an error in one of the reference standards or solutions or some other basic aspect of standard procedure in the analytical process. Further investigation of the possible causes is needed, which will lead to specific decisions on how to compensate for these differences in concentrations in data analysis. In the event that further investigations do not provide insight into the causes of systematic differences in concentrations between methods, the authors recommend continuing to collect and analyze paired environmental water samples by both old and new methods. This effort should be targeted to seasons, sites, and expected concentrations to supplement those concentrations already assessed and to compare the ongoing analytical recovery of old and new methods to those observed in the summer and fall of 2012.

  11. UV-Vis as quantification tool for solubilized lignin following a single-shot steam process.

    PubMed

    Lee, Roland A; Bédard, Charles; Berberi, Véronique; Beauchet, Romain; Lavoie, Jean-Michel

    2013-09-01

    In this short communication, UV/Vis was used as an analytical tool for the quantification of lignin concentrations in aqueous mediums. A significant correlation was determined between absorbance and concentration of lignin in solution. For this study, lignin was produced from different types of biomasses (willow, aspen, softwood, canary grass and hemp) using steam processes. Quantification was performed at 212, 225, 237, 270, 280 and 287 nm. UV-Vis quantification of lignin was found suitable for different types of biomass making this a timesaving analytical system that could lead to uses as Process Analytical Tool (PAT) in biorefineries utilizing steam processes or comparable approaches. Copyright © 2013 Elsevier Ltd. All rights reserved.

  12. Liquid chromatographic determination of benzocaine and N-acetylbenzocaine in the edible fillet tissue from rainbow trout

    USGS Publications Warehouse

    Meinertz, J.R.; Stehly, G.R.; Hubert, T.D.; Bernardy, J.A.

    1999-01-01

    A method was developed for determining benzocaine and N-acetylbenzocaine concentrations in fillet tissue of rainbow trout. The method involves extracting the analytes with acetonitrile, removing lipids or hydrophobic compounds from the extract with hexane, and providing additional clean-up with solid-phase extraction techniques. Analyte concentrations are determined using reversed-phase high-performance liquid chromatographic techniques with an isocratic mobile phase and UV detection. The accuracy (range, 92 to 121%), precision (R.S.D., <14%), and sensitivity (method quantitation limit, <24 ng/g) for each analyte indicate the usefulness of this method for studies characterizing the depletion of benzocaine residues from fish exposed to benzocaine. Copyright (C) 1999.

  13. Characterization of highly concentrated antibody solution - A toolbox for the description of protein long-term solution stability

    PubMed Central

    Schermeyer, Marie-Therese; Wöll, Anna K.; Eppink, Michel; Hubbuch, Jürgen

    2017-01-01

    ABSTRACT High protein titers are gaining importance in biopharmaceutical industry. A major challenge in the development of highly concentrated mAb solutions is their long-term stability and often incalculable viscosity. The complexity of the molecule itself, as well as the various molecular interactions, make it difficult to describe their solution behavior. To study the formulation stability, long- and short-range interactions and the formation of complex network structures have to be taken into account. For a better understanding of highly concentrated solutions, we combined established and novel analytical tools to characterize the effect of solution properties on the stability of highly concentrated mAb formulations. In this study, monoclonal antibody solutions in a concentration range of 50–200 mg/ml at pH 5–9 with and without glycine, PEG4000, and Na2SO4 were analyzed. To determine the monomer content, analytical size-exclusion chromatography runs were performed. ζ-potential measurements were conducted to analyze the electrophoretic properties in different solutions. The melting and aggregation temperatures were determined with the help of fluorescence and static light scattering measurements. Additionally, rheological measurements were conducted to study the solution viscosity and viscoelastic behavior of the mAb solutions. The so-determined analytical parameters were scored and merged in an analytical toolbox. The resulting scoring was then successfully correlated with long-term storage (40 d of incubation) experiments. Our results indicate that the sensitivity of complex rheological measurements, in combination with the applied techniques, allows reliable statements to be made with respect to the effect of solution properties, such as protein concentration, ionic strength, and pH shift, on the strength of protein-protein interaction and solution colloidal stability. PMID:28617076

  14. Analytical techniques for steroid estrogens in water samples - A review.

    PubMed

    Fang, Ting Yien; Praveena, Sarva Mangala; deBurbure, Claire; Aris, Ahmad Zaharin; Ismail, Sharifah Norkhadijah Syed; Rasdi, Irniza

    2016-12-01

    In recent years, environmental concerns over ultra-trace levels of steroid estrogens concentrations in water samples have increased because of their adverse effects on human and animal life. Special attention to the analytical techniques used to quantify steroid estrogens in water samples is therefore increasingly important. The objective of this review was to present an overview of both instrumental and non-instrumental analytical techniques available for the determination of steroid estrogens in water samples, evidencing their respective potential advantages and limitations using the Need, Approach, Benefit, and Competition (NABC) approach. The analytical techniques highlighted in this review were instrumental and non-instrumental analytical techniques namely gas chromatography mass spectrometry (GC-MS), liquid chromatography mass spectrometry (LC-MS), enzyme-linked immuno sorbent assay (ELISA), radio immuno assay (RIA), yeast estrogen screen (YES) assay, and human breast cancer cell line proliferation (E-screen) assay. The complexity of water samples and their low estrogenic concentrations necessitates the use of highly sensitive instrumental analytical techniques (GC-MS and LC-MS) and non-instrumental analytical techniques (ELISA, RIA, YES assay and E-screen assay) to quantify steroid estrogens. Both instrumental and non-instrumental analytical techniques have their own advantages and limitations. However, the non-instrumental ELISA analytical techniques, thanks to its lower detection limit and simplicity, its rapidity and cost-effectiveness, currently appears to be the most reliable for determining steroid estrogens in water samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Comparison of the acetyl bromide spectrophotometric method with other analytical lignin methods for determining lignin concentration in forage samples.

    PubMed

    Fukushima, Romualdo S; Hatfield, Ronald D

    2004-06-16

    Present analytical methods to quantify lignin in herbaceous plants are not totally satisfactory. A spectrophotometric method, acetyl bromide soluble lignin (ABSL), has been employed to determine lignin concentration in a range of plant materials. In this work, lignin extracted with acidic dioxane was used to develop standard curves and to calculate the derived linear regression equation (slope equals absorptivity value or extinction coefficient) for determining the lignin concentration of respective cell wall samples. This procedure yielded lignin values that were different from those obtained with Klason lignin, acid detergent acid insoluble lignin, or permanganate lignin procedures. Correlations with in vitro dry matter or cell wall digestibility of samples were highest with data from the spectrophotometric technique. The ABSL method employing as standard lignin extracted with acidic dioxane has the potential to be employed as an analytical method to determine lignin concentration in a range of forage materials. It may be useful in developing a quick and easy method to predict in vitro digestibility on the basis of the total lignin content of a sample.

  16. Some studies related to a new Hexagonal Compound Parabolic Concentrator (HCPC) as a secondary in tandem with a solar tower

    NASA Astrophysics Data System (ADS)

    Suresh, Deivarajan

    Secondary concentrators operate in the focal plane of a point focusing system such as a paraboloidal dish or a tower and, when properly designed, are capable of enhancing the overall concentration ratio of the optical system at least by factor of two to five. The viability of using different shapes was demonstrated both analytically as well as experimentally in recent years, including Compound Parabolic Concentrators (CPCs) of circular cross section and 'trumpets' as secondaries. Current research effort is centered around a HCPC (Hexagonal CPC). Major areas addressed include an overview on the state of development of secondary concentrators, some background information related to the design of a HCPC, the results of an analytical study on the thermal behavior of this HCPC under concentrated flux conditions, and a computer modeling for assessing the possible thermal interactions between the secondary and a high temperature receiver.

  17. A guide for measurement of circulating metabolic hormones in rodents: Pitfalls during the pre-analytical phase

    PubMed Central

    Bielohuby, Maximilian; Popp, Sarah; Bidlingmaier, Martin

    2012-01-01

    Researchers analyse hormones to draw conclusions from changes in hormone concentrations observed under specific physiological conditions and to elucidate mechanisms underlying their biological variability. It is, however, frequently overlooked that also circumstances occurring after collection of biological samples can significantly affect the hormone concentrations measured, owing to analytical and pre-analytical variability. Whereas the awareness for such potential confounders is increasing in human laboratory medicine, there is sometimes limited consensus about the control of these factors in rodent studies. In this guide, we demonstrate how such factors can affect reliability and consequent interpretation of the data from immunoassay measurements of circulating metabolic hormones in rodent studies. We also compare the knowledge about such factors in rodent studies to recent recommendations established for biomarker studies in humans and give specific practical recommendations for the control of pre-analytical conditions in metabolic studies in rodents. PMID:24024118

  18. Numerical and analytical investigation of steel beam subjected to four-point bending

    NASA Astrophysics Data System (ADS)

    Farida, F. M.; Surahman, A.; Sofwan, A.

    2018-03-01

    A One type of bending tests is four-point bending test. The aim of this test is to investigate the properties and behavior of materials with structural applications. This study uses numerical and analytical studies. Results from both of these studies help to improve in experimental works. The purpose of this study is to predict steel beam behavior subjected to four-point bending test. This study intension is to analyze flexural beam subjected to four-point bending prior to experimental work. Main results of this research are location of strain gauge and LVDT on steel beam based on numerical study, manual calculation, and analytical study. Analytical study uses linear elasticity theory of solid objects. This study results is position of strain gauge and LVDT. Strain gauge is located between two concentrated loads at the top beam and bottom beam. LVDT is located between two concentrated loads.

  19. High temperature ion channels and pores

    NASA Technical Reports Server (NTRS)

    Cheley, Stephen (Inventor); Gu, Li Qun (Inventor); Bayley, Hagan (Inventor); Kang, Xiaofeng (Inventor)

    2011-01-01

    The present invention includes an apparatus, system and method for stochastic sensing of an analyte to a protein pore. The protein pore may be an engineer protein pore, such as an ion channel at temperatures above 55.degree. C. and even as high as near 100.degree. C. The analyte may be any reactive analyte, including chemical weapons, environmental toxins and pharmaceuticals. The analyte covalently bonds to the sensor element to produce a detectable electrical current signal. Possible signals include change in electrical current. Detection of the signal allows identification of the analyte and determination of its concentration in a sample solution. Multiple analytes present in the same solution may also be detected.

  20. Accuracy of trace element determinations in alternate fuels

    NASA Technical Reports Server (NTRS)

    Greenbauer-Seng, L. A.

    1980-01-01

    NASA-Lewis Research Center's work on accurate measurement of trace level of metals in various fuels is presented. The differences between laboratories and between analytical techniques especially for concentrations below 10 ppm, are discussed, detailing the Atomic Absorption Spectrometry (AAS) and DC Arc Emission Spectrometry (dc arc) techniques used by NASA-Lewis. Also presented is the design of an Interlaboratory Study which is considering the following factors: laboratory, analytical technique, fuel type, concentration and ashing additive.

  1. A pipette-based calibration system for fast-scan cyclic voltammetry with fast response times.

    PubMed

    Ramsson, Eric S

    2016-01-01

    Fast-scan cyclic voltammetry (FSCV) is an electrochemical technique that utilizes the oxidation and/or reduction of an analyte of interest to infer rapid changes in concentrations. In order to calibrate the resulting oxidative or reductive current, known concentrations of an analyte must be introduced under controlled settings. Here, I describe a simple and cost-effective method, using a Petri dish and pipettes, for the calibration of carbon fiber microelectrodes (CFMs) using FSCV.

  2. Comparison of soil sampling and analytical methods for asbestos at the Sumas Mountain Asbestos Site-Working towards a toolbox for better assessment.

    PubMed

    Wroble, Julie; Frederick, Timothy; Frame, Alicia; Vallero, Daniel

    2017-01-01

    Established soil sampling methods for asbestos are inadequate to support risk assessment and risk-based decision making at Superfund sites due to difficulties in detecting asbestos at low concentrations and difficulty in extrapolating soil concentrations to air concentrations. Environmental Protection Agency (EPA)'s Office of Land and Emergency Management (OLEM) currently recommends the rigorous process of Activity Based Sampling (ABS) to characterize site exposures. The purpose of this study was to compare three soil analytical methods and two soil sampling methods to determine whether one method, or combination of methods, would yield more reliable soil asbestos data than other methods. Samples were collected using both traditional discrete ("grab") samples and incremental sampling methodology (ISM). Analyses were conducted using polarized light microscopy (PLM), transmission electron microscopy (TEM) methods or a combination of these two methods. Data show that the fluidized bed asbestos segregator (FBAS) followed by TEM analysis could detect asbestos at locations that were not detected using other analytical methods; however, this method exhibited high relative standard deviations, indicating the results may be more variable than other soil asbestos methods. The comparison of samples collected using ISM versus discrete techniques for asbestos resulted in no clear conclusions regarding preferred sampling method. However, analytical results for metals clearly showed that measured concentrations in ISM samples were less variable than discrete samples.

  3. Comparison of soil sampling and analytical methods for asbestos at the Sumas Mountain Asbestos Site—Working towards a toolbox for better assessment

    PubMed Central

    2017-01-01

    Established soil sampling methods for asbestos are inadequate to support risk assessment and risk-based decision making at Superfund sites due to difficulties in detecting asbestos at low concentrations and difficulty in extrapolating soil concentrations to air concentrations. Environmental Protection Agency (EPA)’s Office of Land and Emergency Management (OLEM) currently recommends the rigorous process of Activity Based Sampling (ABS) to characterize site exposures. The purpose of this study was to compare three soil analytical methods and two soil sampling methods to determine whether one method, or combination of methods, would yield more reliable soil asbestos data than other methods. Samples were collected using both traditional discrete (“grab”) samples and incremental sampling methodology (ISM). Analyses were conducted using polarized light microscopy (PLM), transmission electron microscopy (TEM) methods or a combination of these two methods. Data show that the fluidized bed asbestos segregator (FBAS) followed by TEM analysis could detect asbestos at locations that were not detected using other analytical methods; however, this method exhibited high relative standard deviations, indicating the results may be more variable than other soil asbestos methods. The comparison of samples collected using ISM versus discrete techniques for asbestos resulted in no clear conclusions regarding preferred sampling method. However, analytical results for metals clearly showed that measured concentrations in ISM samples were less variable than discrete samples. PMID:28759607

  4. 40 CFR Appendix B to Part 136 - Definition and Procedure for the Determination of the Method Detection Limit-Revision 1.11

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... that the analyte concentration is greater than zero and is determined from analysis of a sample in a given matrix containing the analyte. Scope and Application This procedure is designed for applicability to a wide variety of sample types ranging from reagent (blank) water containing analyte to wastewater...

  5. 40 CFR Appendix B to Part 136 - Definition and Procedure for the Determination of the Method Detection Limit-Revision 1.11

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... that the analyte concentration is greater than zero and is determined from analysis of a sample in a given matrix containing the analyte. Scope and Application This procedure is designed for applicability to a wide variety of sample types ranging from reagent (blank) water containing analyte to wastewater...

  6. 40 CFR Appendix B to Part 136 - Definition and Procedure for the Determination of the Method Detection Limit-Revision 1.11

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... that the analyte concentration is greater than zero and is determined from analysis of a sample in a given matrix containing the analyte. Scope and Application This procedure is designed for applicability to a wide variety of sample types ranging from reagent (blank) water containing analyte to wastewater...

  7. An isotope dilution capillary electrophoresis/tandem mass spectrometry (CE-MS/MS) method for the simultaneous measurement of choline, betaine, and dimethylglycine concentrations in human plasma.

    PubMed

    Forteschi, Mauro; Zinellu, Angelo; Assaretti, Stefano; Mangoni, Arduino A; Pintus, Gianfranco; Carru, Ciriaco; Sotgia, Salvatore

    2016-10-01

    Plasma concentrations of choline, betaine, and dimethylglycine provide valuable information on the flow of methyl groups in key biological processes, particularly during folate deficiency states. We developed a new method to simultaneously measure these analytes in human plasma. Following sample deproteinization using acetonitrile, an aliquot was evaporated to dryness under vacuum to be then taken up by water. Finally, analytes were separated by capillary electrophoresis and detected by electrospray ionization triple-quadrupole mass spectrometry, in multiple reaction monitoring mode, using two stable isotope-labeled internal standards. Linearity of the calibration curves of each analyte was good (R(2) > 0.99). Average limits of detection (LODs) and limits of quantification (LOQs) for choline, betaine, and dimethylglycine were, respectively, 0.43, 0.62, and 0.31 μmol/L and 1.52, 2.11, and 0.97 μmol/L. Mean recovery of three replicates of two spiked concentrations levels was close to 100 % for all of the analytes. Repeatability and intermediate precision, expressed as %RSD of measurements, were <9 %. The method, applied to measure analytes in samples from 30 patients with chronic kidney disease and 30 age- and sex-matched healthy controls, was able to detect differences between groups and the sexes.

  8. Single-step transesterification with simultaneous concentration and stable isotope analysis of fatty acid methyl esters by gas chromatography-combustion-isotope ratio mass spectrometry.

    PubMed

    Panetta, Robert J; Jahren, A Hope

    2011-05-30

    Gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is increasingly applied to food and metabolic studies for stable isotope analysis (δ(13) C), with the quantification of analyte concentration often obtained via a second alternative method. We describe a rapid direct transesterification of triacylglycerides (TAGs) for fatty acid methyl ester (FAME) analysis by GC-C-IRMS demonstrating robust simultaneous quantification of amount of analyte (mean r(2) =0.99, accuracy ±2% for 37 FAMEs) and δ(13) C (±0.13‰) in a single analytical run. The maximum FAME yield and optimal δ(13) C values are obtained by derivatizing with 10% (v/v) acetyl chloride in methanol for 1 h, while lower levels of acetyl chloride and shorter reaction times skewed the δ(13) C values by as much as 0.80‰. A Bland-Altman evaluation of the GC-C-IRMS measurements resulted in excellent agreement for pure oils (±0.08‰) and oils extracted from French fries (±0.49‰), demonstrating reliable simultaneous quantification of FAME concentration and δ(13) C values. Thus, we conclude that for studies requiring both the quantification of analyte and δ(13) C data, such as authentication or metabolic flux studies, GC-C-IRMS can be used as the sole analytical method. Copyright © 2011 John Wiley & Sons, Ltd.

  9. Uncertainty Estimation for the Determination of Ni, Pb and Al in Natural Water Samples by SPE-ICP-OES

    NASA Astrophysics Data System (ADS)

    Ghorbani, A.; Farahani, M. Mahmoodi; Rabbani, M.; Aflaki, F.; Waqifhosain, Syed

    2008-01-01

    In this paper we propose uncertainty estimation for the analytical results we obtained from determination of Ni, Pb and Al by solidphase extraction and inductively coupled plasma optical emission spectrometry (SPE-ICP-OES). The procedure is based on the retention of analytes in the form of 8-hydroxyquinoline (8-HQ) complexes on a mini column of XAD-4 resin and subsequent elution with nitric acid. The influence of various analytical parameters including the amount of solid phase, pH, elution factors (concentration and volume of eluting solution), volume of sample solution, and amount of ligand on the extraction efficiency of analytes was investigated. To estimate the uncertainty of analytical result obtained, we propose assessing trueness by employing spiked sample. Two types of bias are calculated in the assessment of trueness: a proportional bias and a constant bias. We applied Nested design for calculating proportional bias and Youden method to calculate the constant bias. The results we obtained for proportional bias are calculated from spiked samples. In this case, the concentration found is plotted against the concentration added and the slop of standard addition curve is an estimate of the method recovery. Estimated method of average recovery in Karaj river water is: (1.004±0.0085) for Ni, (0.999±0.010) for Pb and (0.987±0.008) for Al.

  10. Interference of ascorbic acid with chemical analytes.

    PubMed

    Meng, Qing H; Irwin, William C; Fesser, Jennifer; Massey, K Lorne

    2005-11-01

    Ascorbic acid can interfere with methodologies involving redox reactions, while comprehensive studies on main chemistry analysers have not been reported. We therefore attempted to determine the interference of ascorbic acid with analytes on the Beckman Synchron LX20. Various concentrations of ascorbic acid were added to serum, and the serum analytes were measured on the LX20. With a serum ascorbic acid concentration of 12.0 mmol/L, the values for sodium, potassium, calcium and creatinine increased by 43%, 58%, 103% and 26%, respectively (P<0.01). With a serum ascorbic acid concentration of 12.0 mmol/L, the values for chloride, total bilirubin and uric acid decreased by 33%, 62% and 83%, respectively (P<0.01), and were undetectable for total cholesterol, triglyceride, ammonia and lactate. There was no definite influence of ascorbic acid on analytical values for total CO(2), urea, glucose, phosphate, total protein, albumin, amylase, creatine kinase, creatine kinase-MB, aspartate aminotransferase, alanine aminotransferase, alkaline phosphatase, total iron, unbound iron-binding capacity or magnesium. Ascorbic acid causes a false increase in sodium, potassium, calcium and creatinine results and a false decrease in chloride, total bilirubin, uric acid, total cholesterol, triglyceride, ammonia and lactate results.

  11. Polyglycerol based coatings to reduce non-specific protein adsorption in sample vials and on SPR sensors.

    PubMed

    Becherer, Tobias; Grunewald, Christian; Engelschalt, Vivienne; Multhaup, Gerhard; Risse, Thomas; Haag, Rainer

    2015-03-31

    Coatings based on dendritic polyglycerol (dPG) were investigated for their use to control nonspecific protein adsorption in an assay targeted to analyze concentrations of a specific protein. We demonstrate that coating of the sample vial with dPG can significantly increase the recovery of an antibody after incubation. First, we determine the concentration dependent loss of an antibody due to nonspecific adsorption to glass via quartz crystal microbalance (QCM). Complementary to the QCM measurements, we applied the same antibody as analyte in an surface plasmon resonance (SPR) assay to determine the loss of analyte due to nonspecific adsorption to the sample vial. For this purpose, we used two different coatings based on dPG. For the first coating, which served as a matrix for the SPR sensor, carboxyl groups were incorporated into dPG as well as a dithiolane moiety enabling covalent immobilization to the gold sensor surface. This SPR-matrix exhibited excellent protein resistant properties and allowed the immobilization of amyloid peptides via amide bond formation. The second coating which was intended to prevent nonspecific adsorption to glass vials comprised a silyl moiety that allowed covalent grafting to glass. For demonstrating the impact of the vial coating on the accuracy of an SPR assay, we immobilized amyloid beta (Aβ) 1-40 and used an anti-Aβ 1-40 antibody as analyte. Alternate injection of analyte into the flow cell of the SPR device from uncoated and coated vials, respectively gave us the relative signal loss (1-RUuncoated/RUcoated) caused by the nonspecific adsorption. We found that the relative signal loss increases with decreasing analyte concentration. The SPR data correlate well with concentration dependent non-specific adsorption experiments of the analyte to glass surfaces performed with QCM. Our measurements show that rendering both the sample vial and the sensor surface is crucial for accurate results in protein assays. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. STATISTICAL ANALYSIS OF TANK 18F FLOOR SAMPLE RESULTS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Harris, S.

    2010-09-02

    Representative sampling has been completed for characterization of the residual material on the floor of Tank 18F as per the statistical sampling plan developed by Shine [1]. Samples from eight locations have been obtained from the tank floor and two of the samples were archived as a contingency. Six samples, referred to in this report as the current scrape samples, have been submitted to and analyzed by SRNL [2]. This report contains the statistical analysis of the floor sample analytical results to determine if further data are needed to reduce uncertainty. Included are comparisons with the prior Mantis samples resultsmore » [3] to determine if they can be pooled with the current scrape samples to estimate the upper 95% confidence limits (UCL{sub 95%}) for concentration. Statistical analysis revealed that the Mantis and current scrape sample results are not compatible. Therefore, the Mantis sample results were not used to support the quantification of analytes in the residual material. Significant spatial variability among the current sample results was not found. Constituent concentrations were similar between the North and South hemispheres as well as between the inner and outer regions of the tank floor. The current scrape sample results from all six samples fall within their 3-sigma limits. In view of the results from numerous statistical tests, the data were pooled from all six current scrape samples. As such, an adequate sample size was provided for quantification of the residual material on the floor of Tank 18F. The uncertainty is quantified in this report by an upper 95% confidence limit (UCL{sub 95%}) on each analyte concentration. The uncertainty in analyte concentration was calculated as a function of the number of samples, the average, and the standard deviation of the analytical results. The UCL{sub 95%} was based entirely on the six current scrape sample results (each averaged across three analytical determinations).« less

  13. STATISTICAL ANALYSIS OF TANK 19F FLOOR SAMPLE RESULTS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Harris, S.

    2010-09-02

    Representative sampling has been completed for characterization of the residual material on the floor of Tank 19F as per the statistical sampling plan developed by Harris and Shine. Samples from eight locations have been obtained from the tank floor and two of the samples were archived as a contingency. Six samples, referred to in this report as the current scrape samples, have been submitted to and analyzed by SRNL. This report contains the statistical analysis of the floor sample analytical results to determine if further data are needed to reduce uncertainty. Included are comparisons with the prior Mantis samples resultsmore » to determine if they can be pooled with the current scrape samples to estimate the upper 95% confidence limits (UCL95%) for concentration. Statistical analysis revealed that the Mantis and current scrape sample results are not compatible. Therefore, the Mantis sample results were not used to support the quantification of analytes in the residual material. Significant spatial variability among the current scrape sample results was not found. Constituent concentrations were similar between the North and South hemispheres as well as between the inner and outer regions of the tank floor. The current scrape sample results from all six samples fall within their 3-sigma limits. In view of the results from numerous statistical tests, the data were pooled from all six current scrape samples. As such, an adequate sample size was provided for quantification of the residual material on the floor of Tank 19F. The uncertainty is quantified in this report by an UCL95% on each analyte concentration. The uncertainty in analyte concentration was calculated as a function of the number of samples, the average, and the standard deviation of the analytical results. The UCL95% was based entirely on the six current scrape sample results (each averaged across three analytical determinations).« less

  14. Negative interferences by calcium dobesilate in the detection of five serum analytes involving Trinder reaction-based assays

    PubMed Central

    Wu, Jie; Zhao, Fang; Xia, Liangyu; Cheng, Xinqi; Liu, Qian; Liu, Li; Xu, Ermu; Qiu, Ling

    2018-01-01

    Previously, we reported the strong negative interference of calcium dobesilate, a vasoprotective agent, in creatinine assays involving the Trinder reaction. It is hypothesized that a similar effect occurs in the detection of uric acid (UA), total cholesterol (TC), triglycerides (TG), high-density lipoprotein cholesterol (HDL-C), and low-density lipoprotein cholesterol (LDL-C). The interferences of calcium dobesilate during the detection of the five serum analytes were investigated on automated systems/analysers, and the effects were compared among eight different assay systems for each analyte. A calcium dobesilate standard was added into two sets of the blank serum pools of each analyte at final concentrations of 0, 2, 4, 8, 16, 32, and 64 μg/mL. The percentage deviation of each analyte value was calculated between each drug concentration and the drug-free samples. The clinically acceptable error levels for UA, TC, TG, HDL-C, and LDL-C were defined as ±4.87%, ±4.1%, ±9.57%, ±5.61%, and ±5.46%, respectively. The observed interference was concentration dependent for each analyte. In the presence of 16 μg/mL calcium dobesilate, which was within the therapeutic range, all seven Trinder reaction-based UA assay systems, two TG assay systems, two HDL-C assay systems and one TC assay system exhibited negative drug interferences. Calcium dobesilate negatively interferes with the detection of UA, TG, TC, and HDL-C in assay systems based on the Trinder reaction. The effect was most significant in UA and TG detection. PMID:29432460

  15. Determination of ethane, pentane and isoprene in exhaled air--effects of breath-holding, flow rate and purified air.

    PubMed

    Lärstad, M A E; Torén, K; Bake, B; Olin, A-C

    2007-01-01

    Exhaled ethane, pentane and isoprene have been proposed as biomarkers of oxidative stress. The objectives were to explore whether ethane, pentane and isoprene are produced within the airways and to explore the effect of different sampling parameters on analyte concentrations. The flow dependency of the analyte concentrations, the concentrations in dead-space and alveolar air after breath-holding and the influence of inhaling purified air on analyte concentrations were investigated. The analytical method involved thermal desorption from sorbent tubes and gas chromatography. The studied group comprised 13 subjects with clinically stable asthma and 14 healthy controls. Ethane concentrations decreased slightly, but significantly, at higher flow rates in subjects with asthma (P = 0.0063) but not in healthy controls. Pentane levels were increased at higher flow rates both in healthy and asthmatic subjects (P = 0.022 and 0.0063 respectively). Isoprene levels were increased at higher flow rates, but only significantly in healthy subjects (P = 0.0034). After breath-holding, no significant changes in ethane levels were observed. Pentane and isoprene levels increased significantly after 20 s of breath-holding. Inhalation of purified air before exhalation resulted in a substantial decrease in ethane levels, a moderate decrease in pentane levels and an increase in isoprene levels. The major fractions of exhaled ethane, pentane and isoprene seem to be of systemic origin. There was, however, a tendency for ethane to be flow rate dependent in asthmatic subjects, although to a very limited extent, suggesting that small amounts of ethane may be formed in the airways.

  16. High throughput liquid absorption preconcentrator sampling instrument

    DOEpatents

    Zaromb, Solomon; Bozen, Ralph M.

    1992-01-01

    A system for detecting trace concentrations of an analyte in air includes a preconcentrator for the analyte and an analyte detector. The preconcentrator includes an elongated tubular container comprising a wettable material. The wettable material is continuously wetted with an analyte-sorbing liquid which flows from one part of the container to a lower end. Sampled air flows through the container in contact with the wetted material with a swirling motion which results in efficient transfer of analyte vapors or aerosol particles to the sorbing liquid and preconcentration of traces of analyte in the liquid. The preconcentrated traces of analyte may be either detected within the container or removed therefrom for injection into a separate detection means or for subsequent analysis.

  17. High-throughput liquid-absorption preconcentrator sampling methods

    DOEpatents

    Zaromb, Solomon

    1994-01-01

    A system for detecting trace concentrations of an analyte in air includes a preconcentrator for the analyte and an analyte detector. The preconcentrator includes an elongated tubular container comprising a wettable material. The wettable material is continuously wetted with an analyte-sorbing liquid which flows from one part of the container to a lower end. Sampled air flows through the container in contact with the wetted material with a swirling motion which results in efficient transfer of analyte vapors or aerosol particles to the sorbing liquid and preconcentration of traces of analyte in the liquid. The preconcentrated traces of analyte may be either detected within the container or removed therefrom for injection into a separate detection means or for subsequent analysis.

  18. High throughput liquid absorption preconcentrator sampling instrument

    DOEpatents

    Zaromb, S.; Bozen, R.M.

    1992-12-22

    A system for detecting trace concentrations of an analyte in air includes a preconcentrator for the analyte and an analyte detector. The preconcentrator includes an elongated tubular container comprising a wettable material. The wettable material is continuously wetted with an analyte-sorbing liquid which flows from one part of the container to a lower end. Sampled air flows through the container in contact with the wetted material with a swirling motion which results in efficient transfer of analyte vapors or aerosol particles to the sorbing liquid and preconcentration of traces of analyte in the liquid. The preconcentrated traces of analyte may be either detected within the container or removed therefrom for injection into a separate detection means or for subsequent analysis. 12 figs.

  19. High-throughput liquid-absorption preconcentrator sampling methods

    DOEpatents

    Zaromb, S.

    1994-07-12

    A system for detecting trace concentrations of an analyte in air includes a preconcentrator for the analyte and an analyte detector. The preconcentrator includes an elongated tubular container comprising a wettable material. The wettable material is continuously wetted with an analyte-sorbing liquid which flows from one part of the container to a lower end. Sampled air flows through the container in contact with the wetted material with a swirling motion which results in efficient transfer of analyte vapors or aerosol particles to the sorbing liquid and preconcentration of traces of analyte in the liquid. The preconcentrated traces of analyte may be either detected within the container or removed therefrom for injection into a separate detection means or for subsequent analysis. 12 figs.

  20. Sensors for detecting analytes in fluids

    NASA Technical Reports Server (NTRS)

    Lewis, Nathan S. (Inventor); Severin, Erik (Inventor)

    1998-01-01

    Chemical sensors for detecting analytes in fluids comprise first and second conductive elements (e.g., electrical leads) electrically coupled to and separated by a chemically sensitive resistor which provides an electrical path between the conductive elements. The resistor comprises a plurality of alternating nonconductive regions (comprising a nonconductive organic polymer) and conductive regions (comprising a conductive material) transverse to the electrical path. The resistor provides a difference in resistance between the conductive elements when contacted with a fluid comprising a chemical analyte at a first concentration, than when contacted with a fluid comprising the chemical analyte at a second different concentration. Arrays of such sensors are constructed with at least two sensors having different chemically sensitive resistors providing dissimilar such differences in resistance. Variability in chemical sensitivity from sensor to sensor is provided by qualitatively or quantitatively varying the composition of the conductive and/or nonconductive regions. An electronic nose for detecting an analyte in a fluid may be constructed by using such arrays in conjunction with an electrical measuring device electrically connected to the conductive elements of each sensor.

  1. Sensors for detecting analytes in fluids

    NASA Technical Reports Server (NTRS)

    Severin, Erik (Inventor); Lewis, Nathan S. (Inventor)

    2001-01-01

    Chemical sensors for detecting analytes in fluids comprise first and second conductive elements (e.g., electrical leads) electrically coupled to and separated by a chemically sensitive resistor which provides an electrical path between the conductive elements. The resistor comprises a plurality of alternating nonconductive regions (comprising a nonconductive organic polymer) and conductive regions (comprising a conductive material) transverse to the electrical path. The resistor provides a difference in resistance between the conductive elements when contacted with a fluid comprising a chemical analyte at a first concentration, than when contacted with a fluid comprising the chemical analyte at a second different concentration. Arrays of such sensors are constructed with at least two sensors having different chemically sensitive resistors providing dissimilar such differences in resistance. Variability in chemical sensitivity from sensor to sensor is provided by qualitatively or quantitatively varying the composition of the conductive and/or nonconductive regions. An electronic nose for detecting an analyte in a fluid may be constructed by using such arrays in conjunction with an electrical measuring device electrically connected to the conductive elements of each sensor.

  2. Sensors for detecting analytes in fluids

    NASA Technical Reports Server (NTRS)

    Lewis, Nathan S. (Inventor); Severin, Erik (Inventor)

    1999-01-01

    Chemical sensors for detecting analytes in fluids comprise first and second conductive elements (e.g., electrical leads) electrically coupled to and separated by a chemically sensitive resistor which provides an electrical path between the conductive elements. The resistor comprises a plurality of alternating nonconductive regions (comprising a nonconductive organic polymer) and conductive regions (comprising a conductive material) transverse to the electrical path. The resistor provides a difference in resistance between the conductive elements when contacted with a fluid comprising a chemical analyte at a first concentration, than when contacted with a fluid comprising the chemical analyte at a second different concentration. Arrays of such sensors are constructed with at least two sensors having different chemically sensitive resistors providing dissimilar such differences in resistance. Variability in chemical sensitivity from sensor to sensor is provided by qualitatively or quantitatively varying the composition of the conductive and/or nonconductive regions. An electronic nose for detecting an analyte in a fluid may be constructed by using such arrays in conjunction with an electrical measuring device electrically connected to the conductive elements of each sensor.

  3. Sensor arrays for detecting analytes in fluids

    NASA Technical Reports Server (NTRS)

    Lewis, Nathan S. (Inventor); Freund, Michael S. (Inventor)

    1996-01-01

    Chemical sensors for detecting analytes in fluids comprise first and second conductive elements (e.g. electrical leads) electrically coupled to and separated by a chemically sensitive resistor which provides an electrical path between the conductive elements. The resistor comprises a plurality of alternating nonconductive regions (comprising a nonconductive organic polymer) and conductive regions (comprising a conductive material) transverse to the electrical path. The resistor provides a difference in resistance between the conductive elements when contacted with a fluid comprising a chemical analyte at a first concentration, than when contacted with a fluid comprising the chemical analyte at a second different concentration. Arrays of such sensors are constructed with at least two sensors having different chemically sensitive resistors providing dissimilar such differences in resistance. Variability in chemical sensitivity from sensor to sensor is provided by qualitatively or quantitatively varying the composition of the conductive and/or nonconductive regions. An electronic nose for detecting an analyte in a fluid may be constructed by using such arrays in conjunction with an electrical measuring device electrically connected to the conductive elements of each sensor.

  4. In situ ionic liquid dispersive liquid-liquid microextraction and direct microvial insert thermal desorption for gas chromatographic determination of bisphenol compounds.

    PubMed

    Cacho, Juan Ignacio; Campillo, Natalia; Viñas, Pilar; Hernández-Córdoba, Manuel

    2016-01-01

    A new procedure based on direct insert microvial thermal desorption injection allows the direct analysis of ionic liquid extracts by gas chromatography and mass spectrometry (GC-MS). For this purpose, an in situ ionic liquid dispersive liquid-liquid microextraction (in situ IL DLLME) has been developed for the quantification of bisphenol A (BPA), bisphenol Z (BPZ) and bisphenol F (BPF). Different parameters affecting the extraction efficiency of the microextraction technique and the thermal desorption step were studied. The optimized procedure, determining the analytes as acetyl derivatives, provided detection limits of 26, 18 and 19 ng L(-1) for BPA, BPZ and BPF, respectively. The release of the three analytes from plastic containers was monitored using this newly developed analytical method. Analysis of the migration test solutions for 15 different plastic containers in daily use identified the presence of the analytes at concentrations ranging between 0.07 and 37 μg L(-1) in six of the samples studied, BPA being the most commonly found and at higher concentrations than the other analytes.

  5. Analytical results and sample locality maps of stream-sediment, heavy-mineral-concentrate, and rock samples from the Little Jacks Creek (ID-111-006), Big Jacks Creek (ID-111-007C), Duncan Creek (ID-111-0007B), and Upper Deep Creek (ID-111-044) Wilderness Study Areas, Owyhee County, Idaho

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Erickson, M.S.; Gent, C.A.; Bradley, L.A.

    1989-01-01

    A U.S. Geological Survey report detailing the analytical results and sample locality maps of stream-sediment, heavy-mineral-concentrate, and rock samples from the Little Jacks Creek, Big Jacks Creek, Duncan Creek, and Upper Deep Creek Wilderness Study Areas, Owyhee County, Idaho

  6. Sources and preparation of data for assessing trends in concentrations of pesticides in streams of the United States, 1992–2010

    USGS Publications Warehouse

    Martin, Jeffrey D.; Eberle, Michael; Nakagaki, Naomi

    2011-01-01

    This report updates a previously published water-quality dataset of 44 commonly used pesticides and 8 pesticide degradates suitable for a national assessment of trends in pesticide concentrations in streams of the United States. Water-quality samples collected from January 1992 through September 2010 at stream-water sites of the U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) Program and the National Stream Quality Accounting Network (NASQAN) were compiled, reviewed, selected, and prepared for trend analysis. The principal steps in data review for trend analysis were to (1) identify analytical schedule, (2) verify sample-level coding, (3) exclude inappropriate samples or results, (4) review pesticide detections per sample, (5) review high pesticide concentrations, and (6) review the spatial and temporal extent of NAWQA pesticide data and selection of analytical methods for trend analysis. The principal steps in data preparation for trend analysis were to (1) select stream-water sites for trend analysis, (2) round concentrations to a consistent level of precision for the concentration range, (3) identify routine reporting levels used to report nondetections unaffected by matrix interference, (4) reassign the concentration value for routine nondetections to the maximum value of the long-term method detection level (maxLT-MDL), (5) adjust concentrations to compensate for temporal changes in bias of recovery of the gas chromatography/mass spectrometry (GCMS) analytical method, and (6) identify samples considered inappropriate for trend analysis. Samples analyzed at the USGS National Water Quality Laboratory (NWQL) by the GCMS analytical method were the most extensive in time and space and, consequently, were selected for trend analysis. Stream-water sites with 3 or more water years of data with six or more samples per year were selected for pesticide trend analysis. The selection criteria described in the report produced a dataset of 21,988 pesticide samples at 212 stream-water sites. Only 21,144 pesticide samples, however, are considered appropriate for trend analysis.

  7. Recommended Inorganic Chemicals for Calibration.

    ERIC Educational Resources Information Center

    Moody, John R.; And Others

    1988-01-01

    All analytical techniques depend on the use of calibration chemicals to relate analyte concentration to instrumental parameters. Discusses the preparation of standard solutions and provides a critical evaluation of available materials. Lists elements by group and discusses the purity and uses of each. (MVL)

  8. MEETING DATA QUALITY OBJECTIVES WITH INTERVAL INFORMATION

    EPA Science Inventory

    Immunoassay test kits are promising technologies for measuring analytes under field conditions. Frequently, these field-test kits report the analyte concentrations as falling in an interval between minimum and maximum values. Many project managers use field-test kits only for scr...

  9. Analytical evaluation of BEA zeolite for the pre-concentration of polycyclic aromatic hydrocarbons and their subsequent chromatographic analysis in water samples.

    PubMed

    Wilson, Walter B; Costa, Andréia A; Wang, Huiyong; Dias, José A; Dias, Sílvia C L; Campiglia, Andres D

    2012-07-06

    The analytical performance of BEA - a commercial zeolite - is evaluated for the pre-concentration of fifteen Environmental Protection Agency - polycyclic aromatic hydrocarbons and their subsequent HPLC analysis in tap and lake water samples. The pre-concentration factors obtained with BEA have led to a method with excellent analytical figures of merit. One milliliter aliquots were sufficient to obtain excellent precision of measurements at the parts-per-trillion concentration level with relative standard deviations varying from 4.1% (dibenzo[a,h]anthracene) to 13.4% (pyrene). The limits of detection were excellent as well and varied between 1.1 (anthracene) and 49.9 ng L(-1) (indeno[1,2,3-cd]pyrene). The recovery values of all the studied compounds meet the criterion for regulated polycyclic aromatic hydrocarbons, which mandates relative standard deviations equal or lower than 25%. The small volume of organic solvents (100 μL per sample) and amount of BEA (2 mg per sample) makes sample pre-concentration environmentally friendly and cost effective. The extraction procedure is well suited for numerous samples as the small working volume (1 mL) facilitates the implementation of simultaneous sample extraction. These are attractive features when routine monitoring of numerous samples is contemplated. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. Adjustment of Pesticide Concentrations for Temporal Changes in Analytical Recovery, 1992-2006

    USGS Publications Warehouse

    Martin, Jeffrey D.; Stone, Wesley W.; Wydoski, Duane S.; Sandstrom, Mark W.

    2009-01-01

    Recovery is the proportion of a target analyte that is quantified by an analytical method and is a primary indicator of the analytical bias of a measurement. Recovery is measured by analysis of quality-control (QC) water samples that have known amounts of target analytes added ('spiked' QC samples). For pesticides, recovery is the measured amount of pesticide in the spiked QC sample expressed as percentage of the amount spiked, ideally 100 percent. Temporal changes in recovery have the potential to adversely affect time-trend analysis of pesticide concentrations by introducing trends in environmental concentrations that are caused by trends in performance of the analytical method rather than by trends in pesticide use or other environmental conditions. This report examines temporal changes in the recovery of 44 pesticides and 8 pesticide degradates (hereafter referred to as 'pesticides') that were selected for a national analysis of time trends in pesticide concentrations in streams. Water samples were analyzed for these pesticides from 1992 to 2006 by gas chromatography/mass spectrometry. Recovery was measured by analysis of pesticide-spiked QC water samples. Temporal changes in pesticide recovery were investigated by calculating robust, locally weighted scatterplot smooths (lowess smooths) for the time series of pesticide recoveries in 5,132 laboratory reagent spikes; 1,234 stream-water matrix spikes; and 863 groundwater matrix spikes. A 10-percent smoothing window was selected to show broad, 6- to 12-month time scale changes in recovery for most of the 52 pesticides. Temporal patterns in recovery were similar (in phase) for laboratory reagent spikes and for matrix spikes for most pesticides. In-phase temporal changes among spike types support the hypothesis that temporal change in method performance is the primary cause of temporal change in recovery. Although temporal patterns of recovery were in phase for most pesticides, recovery in matrix spikes was greater than recovery in reagent spikes for nearly every pesticide. Models of recovery based on matrix spikes are deemed more appropriate for adjusting concentrations of pesticides measured in groundwater and stream-water samples than models based on laboratory reagent spikes because (1) matrix spikes are expected to more closely match the matrix of environmental water samples than are reagent spikes and (2) method performance is often matrix dependent, as was shown by higher recovery in matrix spikes for most of the pesticides. Models of recovery, based on lowess smooths of matrix spikes, were developed separately for groundwater and stream-water samples. The models of recovery can be used to adjust concentrations of pesticides measured in groundwater or stream-water samples to 100 percent recovery to compensate for temporal changes in the performance (bias) of the analytical method.

  11. Peak distortion effects in analytical ion chromatography.

    PubMed

    Wahab, M Farooq; Anderson, Jordan K; Abdelrady, Mohamed; Lucy, Charles A

    2014-01-07

    The elution profile of chromatographic peaks provides fundamental understanding of the processes that occur in the mobile phase and the stationary phase. Major advances have been made in the column chemistry and suppressor technology in ion chromatography (IC) to handle a variety of sample matrices and ions. However, if the samples contain high concentrations of matrix ions, the overloaded peak elution profile is distorted. Consequently, the trace peaks shift their positions in the chromatogram in a manner that depends on the peak shape of the overloading analyte. In this work, the peak shapes in IC are examined from a fundamental perspective. Three commercial IC columns AS16, AS18, and AS23 were studied with borate, hydroxide and carbonate as suppressible eluents. Monovalent ions (chloride, bromide, and nitrate) are used as model analytes under analytical (0.1 mM) to overload conditions (10-500 mM). Both peak fronting and tailing are observed. On the basis of competitive Langmuir isotherms, if the eluent anion is more strongly retained than the analyte ion on an ion exchanger, the analyte peak is fronting. If the eluent is more weakly retained on the stationary phase, the analyte peak always tails under overload conditions regardless of the stationary phase capacity. If the charge of the analyte and eluent anions are different (e.g., Br(-) vs CO3(2-)), the analyte peak shapes depend on the eluent concentration in a more complex pattern. It was shown that there are interesting similarities with peak distortions due to strongly retained mobile phase components in other modes of liquid chromatography.

  12. Determination of iodinated X-ray contrast media in sewage by solid-phase extraction and liquid chromatography tandem mass spectrometry.

    PubMed

    Echeverría, S; Borrull, F; Fontanals, N; Pocurull, E

    2013-11-15

    A method for the quantitative determination of five iodinated X-ray contrast media (ICMs) in sewage was developed by solid-phase extraction and high-performance liquid chromatography-tandem mass spectrometry. A fused-core analytical column was successfully applied for the first time for the separation of ICMs. Oasis HLB was selected from the sorbents tested because of its higher recoveries. The optimized method allowed the determination of the ICMs at low ng/L levels in both influent and effluent sewage, with detection limits of 40 ng/L and 10 ng/L for most compounds in influent and effluent sewage, respectively. The five ICMs studied were determined in all samples analysed, with iopromide being the analyte found at the highest concentration (8.9 µg/L), while iopamidol was the analyte found at lowest concentration (1.3 µg/L) in influent sewage. Effluent sewage did not show a significant decrease in ICM concentrations. © 2013 Elsevier B.V. All rights reserved.

  13. Analytical Fingerprint of Wolframite Ore Concentrates.

    PubMed

    Gäbler, Hans-Eike; Schink, Wilhelm; Goldmann, Simon; Bahr, Andreas; Gawronski, Timo

    2017-07-01

    Ongoing violent conflicts in Central Africa are fueled by illegal mining and trading of tantalum, tin, and tungsten ores. The credibility of document-based traceability systems can be improved by an analytical fingerprint applied as an independent method to confirm or doubt the documented origin of ore minerals. Wolframite (Fe,Mn)WO 4 is the most important ore mineral for tungsten and is subject to artisanal mining in Central Africa. Element concentrations of wolframite grains analyzed by laser ablation-inductively coupled plasma-mass spectrometry are used to establish the analytical fingerprint. The data from ore concentrate samples are multivariate, not normal or log-normal distributed. The samples cannot be regarded as representative aliquots of a population. Based on the Kolmogorov-Smirnov distance, a measure of similarity between a sample in question and reference samples from a database is determined. A decision criterion is deduced to recognize samples which do not originate from the declared mine site. © 2017 American Academy of Forensic Sciences.

  14. Extraction of fullerenes from environmental matrices as affected by solvent characteristics and analyte concentration.

    PubMed

    Place, Benjamin J; Kleber, Markus; Field, Jennifer A

    2013-03-01

    Fullerenes possess unique chemical properties that make the isolation of these compounds from heterogeneous environmental matrices difficult. For example, previous reports indicate that toluene-based extraction techniques vary in their ability to extract C60, especially from highly carbonaceous solid matrices. Here, we examined the effects of (i) solvent type (toluene alone versus an 80:20 v/v mixture of toluene and 1-methylnaphthalene) and (ii) analyte concentration on the extraction efficiency of an isotopically labeled surrogate compound, (13)C60. The toluene/1-methylnaphthalene mixture increased fullerene extraction efficiency from carbon lampblack by a factor of five, but was not significantly different from 100% toluene when applied to wood stove soot or montmorillonite. Recovery of the (13)C60 surrogate declined with decreasing analyte concentration. The usefulness of isotopically labeled surrogate is demonstrated and the study provides a quantitative assessment regarding the dependence of fullerene extraction efficiencies on the geochemical characteristics of solid matrices. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Preliminary measurement of gas concentrations of perfluropropane using an analytical weighing balance.

    PubMed

    Clarkson, Douglas McG; Manna, Avinish; Hero, Mark

    2014-02-01

    We describe the use of an analytical weighing balance of measurement accuracy 0.00001g for determination of concentrations of perfluropropane (C3F8) gas used in ophthalmic surgical vitrectomy procedures. A range of test eyes corresponding to an eye volume of 6.1ml were constructed using 27 gauge needle exit ducts and separately 20 gauge (straight) and 23 gauge (angled) entrance ports. This method allowed determination of concentration levels in the sample preparation syringe and also levels in test eyes. It was determined that a key factor influencing gas concentrations accuracy related to the method of gas fill and the value of dead space of the gas preparation/delivery system and with a significant contribution arising from the use of the particle filter. The weighing balance technique was identified as an appropriate technique for estimation of gas concentrations. Copyright © 2013 IPEM. Published by Elsevier Ltd. All rights reserved.

  16. 40 CFR 79.52 - Tier 1.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... methods as presented in current environmental and analytical chemistry literature. Examples of analytical....001 microgram (µg) of compound per milligram of organic extract) of these compounds in the extractable organic matter. The concentration of each individual PAH or NPAH compound identified shall be reported in...

  17. Water Sample Concentrator

    ScienceCinema

    Idaho National Laboratory

    2017-12-09

    Automated portable device that concentrates and packages a sample of suspected contaminated water for safe, efficient transport to a qualified analytical laboratory. This technology will help safeguard against pathogen contamination or chemical and biolog

  18. Assessment of sample preservation techniques for pharmaceuticals, personal care products, and steroids in surface and drinking water.

    PubMed

    Vanderford, Brett J; Mawhinney, Douglas B; Trenholm, Rebecca A; Zeigler-Holady, Janie C; Snyder, Shane A

    2011-02-01

    Proper collection and preservation techniques are necessary to ensure sample integrity and maintain the stability of analytes until analysis. Data from improperly collected and preserved samples could lead to faulty conclusions and misinterpretation of the occurrence and fate of the compounds being studied. Because contaminants of emerging concern, such as pharmaceuticals and personal care products (PPCPs) and steroids, generally occur in surface and drinking water at ng/L levels, these compounds in particular require such protocols to accurately assess their concentrations. In this study, sample bottle types, residual oxidant quenching agents, preservation agents, and hold times were assessed for 21 PPCPs and steroids in surface water and finished drinking water. Amber glass bottles were found to have the least effect on target analyte concentrations, while high-density polyethylene bottles had the most impact. Ascorbic acid, sodium thiosulfate, and sodium sulfite were determined to be acceptable quenching agents and preservation with sodium azide at 4 °C led to the stability of the most target compounds. A combination of amber glass bottles, ascorbic acid, and sodium azide preserved analyte concentrations for 28 days in the tested matrices when held at 4 °C. Samples without a preservation agent were determined to be stable for all but two of the analytes when stored in amber glass bottles at 4 °C for 72 h. Results suggest that if improper protocols are utilized, reported concentrations of target PPCPs and steroids may be inaccurate.

  19. Analytical sensitivity of four commonly used hCG point of care devices.

    PubMed

    Kamer, Sandy M; Foley, Kevin F; Schmidt, Robert L; Greene, Dina N

    2015-04-01

    Point of care (POC) hCG assays are often used to rule-out pregnancy and therefore diagnostic sensitivity, especially at low concentrations of hCG, is important. There are very few studies in the literature that seek to verify the claimed analytical sensitivity of hCG POC devices. The analytical sensitivity of four commonly used hCG POC devices (Alere hCG Combo Cassette, ICON 20 hCG, OSOM hCG Combo Test, and Sure-Vue Serum/Urine hCG-STAT) was challenged using urine samples (n=50) selected based on quantitative hCG concentrations. The majority of these specimens (n=40) had an hCG concentration between 20 and 200 U/L. Each specimen/device combination was reviewed by three individuals. Statistical calculations were performed using Stata 12. The analytical sensitivity of the OSOM was significantly lower inferior than that of the other POC devices. There was no significant difference in the sensitivity of the Alere, ICON 20 and Sure-Vue devices. There was no significant difference in the individual interpretation of the hCG POC results. All hCG POC devices evaluated in this study were susceptible to false negative results at low concentrations of urine hCG. Laboratorians and clinicians should be aware that there are limitations when using urine hCG POC devices to rule out early pregnancy. Copyright © 2014 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

  20. Immunoassay and antibody microarray analysis of the HUPO Plasma Proteome Project reference specimens: Systematic variation between sample types and calibration of mass spectrometry data

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Haab, Brian B.; Geierstanger, Bernhard H.; Michailidis, George

    2005-08-01

    Four different immunoassay and antibody microarray methods performed at four different sites were used to measure the levels of a broad range of proteins (N = 323 assays; 39, 88, 168, and 28 assays at the respective sites; 237 unique analytes) in the human serum and plasma reference specimens distributed by the Plasma Proteome Project (PPP) of the HUPO. The methods provided a means to (1) assess the level of systematic variation in protein abundances associated with blood preparation methods (serum, citrate-anticoagulated-plasma, EDTA-anticoagulated-plasma, or heparin-anticoagulated-plasma) and (2) evaluate the dependence on concentration of MS-based protein identifications from data sets usingmore » the HUPO specimens. Some proteins, particularly cytokines, had highly variable concentrations between the different sample preparations, suggesting specific effects of certain anticoagulants on the stability or availability of these proteins. The linkage of antibody-based measurements from 66 different analytes with the combined MS/MS data from 18 different laboratories showed that protein detection and the quality of MS data increased with analyte concentration. The conclusions from these initial analyses are that the optimal blood preparation method is variable between analytes and that the discovery of blood proteins by MS can be extended to concentrations below the ng/mL range under certain circumstances. Continued developments in antibody-based methods will further advance the scientific goals of the PPP.« less

  1. Simultaneous determination of glucose, triglycerides, urea, cholesterol, albumin and total protein in human plasma by Fourier transform infrared spectroscopy: direct clinical biochemistry without reagents.

    PubMed

    Jessen, Torben E; Höskuldsson, Agnar T; Bjerrum, Poul J; Verder, Henrik; Sørensen, Lars; Bratholm, Palle S; Christensen, Bo; Jensen, Lene S; Jensen, Maria A B

    2014-09-01

    Direct measurement of chemical constituents in complex biologic matrices without the use of analyte specific reagents could be a step forward toward the simplification of clinical biochemistry. Problems related to reagents such as production errors, improper handling, and lot-to-lot variations would be eliminated as well as errors occurring during assay execution. We describe and validate a reagent free method for direct measurement of six analytes in human plasma based on Fourier-transform infrared spectroscopy (FTIR). Blood plasma is analyzed without any sample preparation. FTIR spectrum of the raw plasma is recorded in a sampling cuvette specially designed for measurement of aqueous solutions. For each analyte, a mathematical calibration process is performed by a stepwise selection of wavelengths giving the optimal least-squares correlation between the measured FTIR signal and the analyte concentration measured by conventional clinical reference methods. The developed calibration algorithms are subsequently evaluated for their capability to predict the concentration of the six analytes in blinded patient samples. The correlation between the six FTIR methods and corresponding reference methods were 0.87

  2. A rapid quantitative analysis of bile acids, lysophosphatidylcholines and polyunsaturated fatty acids in biofluids based on ultraperformance liquid chromatography coupled with triple quadrupole tandem massspectrometry.

    PubMed

    Peng, Zhangxiao; Zhang, Qian; Mao, Ziming; Wang, Jie; Liu, Chunying; Lin, Xuejing; Li, Xin; Ji, Weidan; Fan, Jianhui; Wang, Maorong; Su, Changqing

    2017-11-15

    Much evidence suggested that quantitative analysis of bile acids (BAs), lysophosphatidylcholines (LPCs), and polyunsaturated fatty acids (PUFAs) in biofluids may be very useful for diagnosis and prevention of hepatobiliary disease with a non-invasive manner. However, simultaneously fast analysis of these metabolites has been challenging for their huge differences of physicochemical properties and concentration levels in biofluids. In this study, we present a liquid chromatography-mass spectrometry method with a high throughput analytical cycle (10min) to fast and accurately quantify fifteen potential biomarkers (eight BAs, four LPCs and three PUFAs) of hepatobiliary disease. The accuracy for the fifteen analytes in plasma and urine matrices was 80.45%-118.99% and 84.55%-112.66%, respectively. The intra- and inter- precisions for the fifteen analytes in plasma and urine matrices were all less than 20% and the lower limit of quantification (LLOQ) of analytes is up to 0.0283-8.2172nmol/L. Therefore, this method is fast, sensitive and accurate for the quantitative analysis of BAs, LPCs and PUFAs in biofluids. Moreover, the stability and concentration differences of the analytes in plasma and serum were evaluated, and the results demonstrated that LPCs is stable, but PUFAs is very unstable in freeze and thaw cycles, and the concentrations of the analytes in serum were slightly higher than those in plasma. We suggested plasma may be a kind of better bio-sample than serum using for quantitative analysis of metabolites in blood, due to the characteristics of plasma are more close to blood than those of serum. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Preconcentration and separation of analytes in microchannels

    DOEpatents

    Hatch, Anson; Singh, Anup K.; Herr, Amy E.; Throckmorton, Daniel J.

    2010-11-09

    Disclosed herein are methods and devices for preconcentrating and separating analytes such as proteins and polynucleotides in microchannels. As disclosed, at least one size-exclusion polymeric element is adjacent to processing area or an assay area in a microchannel which may be porous polymeric element. The size-exclusion polymeric element may be used to manipulate, e.g. concentrate, analytes in a sample prior to assaying in the assay area.

  4. Method and apparatus for processing a test sample to concentrate an analyte in the sample from a solvent in the sample

    DOEpatents

    Turner, Terry D.; Beller, Laurence S.; Clark, Michael L.; Klingler, Kerry M.

    1997-01-01

    A method of processing a test sample to concentrate an analyte in the sample from a solvent in the sample includes: a) boiling the test sample containing the analyte and solvent in a boiling chamber to a temperature greater than or equal to the solvent boiling temperature and less than the analyte boiling temperature to form a rising sample vapor mixture; b) passing the sample vapor mixture from the boiling chamber to an elongated primary separation tube, the separation tube having internal sidewalls and a longitudinal axis, the longitudinal axis being angled between vertical and horizontal and thus having an upper region and a lower region; c) collecting the physically transported liquid analyte on the internal sidewalls of the separation tube; and d) flowing the collected analyte along the angled internal sidewalls of the separation tube to and pass the separation tube lower region. The invention also includes passing a turbulence inducing wave through a vapor mixture to separate physically transported liquid second material from vaporized first material. Apparatus are also disclosed for effecting separations. Further disclosed is a fluidically powered liquid test sample withdrawal apparatus for withdrawing a liquid test sample from a test sample container and for cleaning the test sample container.

  5. Method and apparatus for processing a test sample to concentrate an analyte in the sample from a solvent in the sample

    DOEpatents

    Turner, T.D.; Beller, L.S.; Clark, M.L.; Klingler, K.M.

    1997-10-14

    A method of processing a test sample to concentrate an analyte in the sample from a solvent in the sample includes: (a) boiling the test sample containing the analyte and solvent in a boiling chamber to a temperature greater than or equal to the solvent boiling temperature and less than the analyte boiling temperature to form a rising sample vapor mixture; (b) passing the sample vapor mixture from the boiling chamber to an elongated primary separation tube, the separation tube having internal sidewalls and a longitudinal axis, the longitudinal axis being angled between vertical and horizontal and thus having an upper region and a lower region; (c) collecting the physically transported liquid analyte on the internal sidewalls of the separation tube; and (d) flowing the collected analyte along the angled internal sidewalls of the separation tube to and pass the separation tube lower region. The invention also includes passing a turbulence inducing wave through a vapor mixture to separate physically transported liquid second material from vaporized first material. Apparatus is also disclosed for effecting separations. Further disclosed is a fluidically powered liquid test sample withdrawal apparatus for withdrawing a liquid test sample from a test sample container and for cleaning the test sample container. 8 figs.

  6. Trace element release from estuarine sediments of South Mosquito Lagoon near Kennedy Space Center

    NASA Technical Reports Server (NTRS)

    Menon, M. P.; Ghuman, G. S.; Emeh, C. O.

    1979-01-01

    Analytical partitioning of four trace metals in estuarine sediments collected from eight sites in South Mosquito Lagoon near Kennedy Space Center, in terms of four different categories was accomplished using four different extraction techniques. The concentrations of the four trace metals, Zn, Mn, Cd, and Cu, released in interstitial water extract, 1 N ammonium acetate extract, conc. HCl extract and fusion extract of sediments as well as their concentrations in water samples collected from the same location were determined using flame atomic absorption technique. From the analytical results the percentages of total amount of each metal distributed among four different categories, interstitial water phase, acetate extractable, acid extractable and detrital crystalline material, were determined. Our results suggest that analytical partitioning of trace metals in estuarine sediments may be used to study the mechanism of incorporation of trace metals with sediments from natural waters. A correlation between the seasonal variation in the concentration of acetate extractable trace metals in the sediment and similar variation in their concentration in water was observed. A mechanism for the release of trace metals from estuarine sediments to natural water is also suggested.

  7. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hoogheem, T.J.; Woods, L.A.

    The Monsanto Analytical Testing (MAT) program was devised and implemented in order to provide analytical standards to Monsanto manufacturing plants involved in the self-monitoring of plant discharges as required by National Pollutant Discharge Elimination System (NPDES) permit conditions. Standards are prepared and supplied at concentration levels normally observed at each individual plant. These levels were established by canvassing all Monsanto plants having NPDES permits and by determining which analyses and concentrations were most appropriate. Standards are prepared by Monsanto's analyses and concentrations were most appropriate. Standards are prepared by Monsanto's Environmental Sciences Center (ESC) using Environmental Protection Agency (EPA) methods.more » Eleven standards are currently available, each in three concentrations. Standards are issued quarterly in a company internal round-robin program or on a per request basis or both. Since initiation of the MAT program in 1981, the internal round-robin program has become an integral part of Monsanto's overall Good Laboratory Practices (GLP) program. Overall, results have shown that the company's plant analytical personnel can accurately analyze and report standard test samples. More importantly, such personnel have gained increased confidence in their ability to report accurate values for compounds regulated in their respective plant NPDES permits. 3 references, 3 tables.« less

  8. Determination of low-molecular-weight amines and ammonium in saline waters by ion chromatography after their extraction by steam distillation.

    PubMed

    Ferreira, Fernanda Nunes; Afonso, Julio Carlos; Pontes, Fernanda Veronesi Marinho; Carneiro, Manuel Castro; Neto, Arnaldo Alcover; Tristão, Maria Luiza Bragança; Monteiro, Maria Inês Couto

    2016-04-01

    A new method was developed for the determination of ammonium ion, monomethylamine and monoethylamine in saline waters by ion chromatography. Steam distillation was used to eliminate matrix interferences. Variables such as distillation time, concentration of sodium hydroxide solution and analyte mass were optimized by using a full two-level factorial (2(3) ) design. The influence of steam distillation on the analytical curves prepared in different matrices was also investigated. Limits of detection of 0.03, 0.05 and 0.05 mg/L were obtained for ammoniumion, monomethylamine and monoethylamine, respectively. Saline water samples from the Brazilian oil industry, containing sodium and potassium concentrations between 2.0-5.2% w/v and 96-928 mg/L, respectively, were analyzed. Satisfactory recoveries (90-105%) of the analytes were obtained for all spiked samples, and the precision was ≤ 7% (n = 3). The proposed method is adequate for analyzing saline waters containing sodium to ammoniumion, monomethylamine and monoethylamine concentration ratios up to 28 000:1 and potassium to ammonium, monomethylamine and monoethylamine concentration ratios up to 12 000:1. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Research highlights: increasing paper possibilities.

    PubMed

    Wu, Chueh-Yu; Adeyiga, Oladunni; Lin, Jonathan; Di Carlo, Dino

    2014-09-07

    In this issue we highlight three recent papers that demonstrate new strategies to extend the capabilities of paper microfluidics. Paper (a mesh of porous fibers) has a long history as a substrate to perform biomolecular assays. Traditional lateral flow immunoassays (LFAs) are widely used for rapid diagnostic tests, and perform well when a yes or no answer is required and the analyte of interest is at relatively high concentrations. High concentrations are required because usually only a small volume of analyte-containing fluid flows past the detection region, leading to a limited signal. Further, the small pores within paper matrices prevent the use of paper to control the flow of larger particles and cells, limiting the use of paper microfluidics for cell-based diagnostics. The work we highlight addresses these important unmet challenges in paper microfluidics: enriching low concentration analytes to a higher concentration in a smaller volume that can be processed effectively, and using paper to pump flows in larger channels amenable to cells. Applying these new approaches may allow diagnosis of disease states currently technically unachievable using current LFA systems, while maintaining many of the "un-instrumented" advantages of an assay on self-wicking paper.

  10. Phenolic compounds in Ross Sea water

    NASA Astrophysics Data System (ADS)

    Zangrando, Roberta; Barbaro, Elena; Gambaro, Andrea; Barbante, Carlo; Corami, Fabiana; Kehrwald, Natalie; Capodaglio, Gabriele

    2016-04-01

    Phenolic compounds are semi-volatile organic compounds produced during biomass burning and lignin degradation in water. In atmospheric and paleoclimatic ice cores studies, these compounds are used as biomarkers of wood combustion and supply information on the type of combusted biomass. Phenolic compounds are therefore indicators of paleoclimatic interest. Recent studies of Antarctic aerosols highlighted that phenolic compounds in Antarctica are not exclusively attributable to biomass burning but also derive from marine sources. In order to study the marine contribution to aerosols we developed an analytical method to determine the concentration of vanillic acid, vanillin, p-coumaric acid, syringic acid, isovanillic acid, homovanillic acid, syringaldehyde, acetosyringone and acetovanillone present in dissolved and particle phases in Sea Ross waters using HPLC-MS/MS. The analytical method was validated and used to quantify phenolic compounds in 28 sea water samples collected during a 2012 Ross Sea R/V cruise. The observed compounds were vanillic acid, vanillin, acetovanillone and p-coumaric acid with concentrations in the ng/L range. Higher concentrations of analytes were present in the dissolved phase than in the particle phase. Sample concentrations were greatest in the coastal, surficial and less saline Ross Sea waters near Victoria Land.

  11. A pilot study evaluating protein abundance in pressure ulcer fluid from people with and without spinal cord injury

    PubMed Central

    Edsberg, Laura E.; Wyffels, Jennifer T.; Ogrin, Rajna; Craven, B. Catharine; Houghton, Pamela

    2015-01-01

    Objective To determine whether the biochemistry of chronic pressure ulcers differs between patients with and without chronic spinal cord injury (SCI) through measurement and comparison of the concentration of wound fluid inflammatory mediators, growth factors, cytokines, acute phase proteins, and proteases. Design Survey. Setting Tertiary spinal cord rehabilitation center and skilled nursing facilities. Participants Twenty-nine subjects with SCI and nine subjects without SCI (>18 years) with at least one chronic pressure ulcer Stage II, III, or IV were enrolled. Outcome measures Total protein and 22 target analyte concentrations including inflammatory mediators, growth factors, cytokines, acute phase proteins, and proteases were quantified in the wound fluid and blood serum samples. Blood samples were tested for complete blood count, albumin, hemoglobin A1c, total iron binding capacity, iron, percent (%) saturation, C-reactive protein, and erythrocyte sedimentation rate. Results Wound fluid concentrations were significantly different between subjects with SCI and subjects without SCI for total protein concentration and nine analytes, MMP-9, S100A12, S100A8, S100A9, FGF2, IL-1b, TIMP-1, TIMP-2, and TGF-b1. Subjects without SCI had higher values for all significantly different analytes measured in wound fluid except FGF2, TGF-b1, and wound fluid total protein. Subject-matched circulating levels of analytes and the standardized local concentration of the same proteins in the wound fluid were weakly or not correlated. Conclusions The biochemical profile of chronic pressure ulcers is different between SCI and non-SCI populations. These differences should be considered when selecting treatment options. Systemic blood serum properties may not represent the local wound environment. PMID:24968005

  12. An analytical model for contaminant transport in landfill composite liners considering coupled effect of consolidation, diffusion, and degradation.

    PubMed

    Xie, Haijian; Yan, Huaxiang; Feng, Shijin; Wang, Qiao; Chen, Peixiong

    2016-10-01

    One-dimensional mathematical model is developed to investigate the behavior of contaminant transport in landfill composite liner system considering coupled effect of consolidation, diffusion, and degradation. The first- and second-type bottom boundary conditions are used to derive the steady-state and quasi-steady-state analytical solutions. The concentration profiles obtained by the proposed analytical solution are in good agreement with those obtained by the laboratory tests. The bottom concentration and flux of the soil liners can be greatly reduced when the degradation effect and porosity changing are considered. For the case under steady-state, the bottom flux and concentration for the case with t 1/2 =10 years can be 2.8 and 5.5 times lower than those of the case with t 1/2 =100 years, respectively. The bottom concentration and flux of the soil liners can be greatly reduced when the coefficient of volume compressibility decreases. For quasi-steady-state and with t 1/2 = 10 years, the bottom flux and concentration for the case with m v  = 0.02/MPa can be 17.4 and 21 times lower than the case with m v  = 0.5/MPa. This may be due to the fact that the true fluid velocity induced by consolidation is greater for the case with high coefficient of volume compressibility. The bottom flux for the case with single compacted clay liner (CCL) can be 1.5 times larger than that for the case with GMB/CCL considering diffusion and consolidation for DCM. The proposed analytical model can be used for verification of more complicated numerical models and assessment of the coupled effect of diffusion, consolidation, and degradation on contaminant transport in landfill liner systems.

  13. Trace detection of analytes using portable raman systems

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Alam, M. Kathleen; Hotchkiss, Peter J.; Martin, Laura E.

    Apparatuses and methods for in situ detection of a trace amount of an analyte are disclosed herein. In a general embodiment, the present disclosure provides a surface-enhanced Raman spectroscopy (SERS) insert including a passageway therethrough, where the passageway has a SERS surface positioned therein. The SERS surface is configured to adsorb molecules of an analyte of interest. A concentrated sample is caused to flow over the SERS surface. The SERS insert is then provided to a portable Raman spectroscopy system, where it is analyzed for the analyte of interest.

  14. Size separation of analytes using monomeric surfactants

    DOEpatents

    Yeung, Edward S.; Wei, Wei

    2005-04-12

    A sieving medium for use in the separation of analytes in a sample containing at least one such analyte comprises a monomeric non-ionic surfactant of the of the general formula, B-A, wherein A is a hydrophilic moiety and B is a hydrophobic moiety, present in a solvent at a concentration forming a self-assembled micelle configuration under selected conditions and having an aggregation number providing an equivalent weight capable of effecting the size separation of the sample solution so as to resolve a target analyte(s) in a solution containing the same, the size separation taking place in a chromatography or electrophoresis separation system.

  15. Simultaneous determination of thirteen different steroid hormones using micro UHPLC-MS/MS with on-line SPE system.

    PubMed

    Márta, Zoltán; Bobály, Balázs; Fekete, Jenő; Magda, Balázs; Imre, Tímea; Mészáros, Katalin Viola; Bálint, Mária; Szabó, Pál Tamás

    2018-02-20

    Ultratrace analysis of sample components requires excellent analytical performance in terms of limits of quantitation (LOQ). Micro UHPLC coupled to sensitive tandem mass spectrometry provides state of the art solution for such analytical problems. Using on-line SPE with column switching on a micro UHPLC-MS/MS system allowed to decrease LOQ without any complex sample preparation protocol. The presented method is capable of reaching satisfactory low LOQ values for analysis of thirteen different steroid molecules from human plasma without the most commonly used off-line SPE or compound derivatization. Steroids were determined by using two simple sample preparation methods, based on lower and higher plasma steroid concentrations. In the first method, higher analyte concentrations were directly determined after protein precipitation with methanol. The organic phase obtained from the precipitation was diluted with water and directly injected into the LC-MS system. In the second method, low steroid levels were determined by concentrating the organic phase after steroid extraction. In this case, analytes were extracted with ethyl acetate and reconstituted in 90/10 water/acetonitrile following evaporation to dryness. This step provided much lower LOQs, outperforming previously published values. The method has been validated and subsequently applied to clinical laboratory measurement. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Quantitative Determination of Fluorinated Alkyl Substances by Large-Volume-Injection LC/MS/MS—Characterization of Municipal Wastewaters

    PubMed Central

    Schultz, Melissa M.; Barofsky, Douglas F.; Field, Jennifer A.

    2008-01-01

    A quantitative method was developed for the determination of fluorinated alkyl substances in municipal wastewater influents and effluents. The method consisted of centrifugation followed by large-volume injection (500 μL) of the supernatant onto a liquid chromatograph with a reverse-phase column and detection by electrospray ionization, and tandem mass spectrometry (LC/MS/MS). The fluorinated analytes studied include perfluoroalkyl sulfonates, fluorotelomer sulfonates, perfluorocarboxylates, and select fluorinated alkyl sulfonamides. Recoveries of the fluorinated analytes from wastewater treatment plant (WWTP) raw influents and final effluent ranged from 77% – 96% and 80% – 99%, respectively. The lower limit of quantitation ranged from 0.5 to 3.0 ng/L depending on the analyte. The method was applied to flow-proportional composites of raw influent and final effluent collected over a 24 hr period from ten WWTPs nationwide. Fluorinated alkyl substances were observed in wastewater at all treatment plants and each plant exhibited unique distributions of fluorinated alkyl substances despite similarities in treatment processes. In nine out of the ten plants sampled, at least one class of fluorinated alkyl substances exhibited increased concentrations in the effluent as compared to the influent concentrations. In some instances, decreases in certain fluorinated analyte concentrations were observed and attributed to sorption to sludge. PMID:16433363

  17. Determination of Residual Chlorine and Turbidity in Drinking Water. Instructor's Manual.

    ERIC Educational Resources Information Center

    Office of Water Program Operations (EPA), Cincinnati, OH. National Training and Operational Technology Center.

    This instructor's guide presents analytical methods for residual chlorine and turbidity. Topics include sample handling, permissable concentration levels, substitution of residual chlorine for bacteriological work, public notification, and the required analytical techniques to determine residual chlorine and turbidity. This publication is intended…

  18. PAVA: Physiological and Anatomical Visual Analytics for Mapping of Tissue-Specific Concentration and Time-Course Data

    EPA Science Inventory

    We describe the development and implementation of a Physiological and Anatomical Visual Analytics tool (PAVA), a web browser-based application, used to visualize experimental/simulated chemical time-course data (dosimetry), epidemiological data and Physiologically-Annotated Data ...

  19. An Experimental Introduction to Interlaboratory Exercises in Analytical Chemistry

    ERIC Educational Resources Information Center

    Puignou, L.; Llaurado, M.

    2005-01-01

    An experimental exercise on analytical proficiency studies in collaborative trials is proposed. This practical provides students in advanced undergraduate courses in chemistry, pharmacy, and biochemistry, with the opportunity to improve their quality assurance skills. It involves an environmental analysis, determining the concentration of a…

  20. Is enzymatic hydrolysis a reliable analytical strategy to quantify glucuronidated and sulfated polyphenol metabolites in human fluids?

    PubMed

    Quifer-Rada, Paola; Martínez-Huélamo, Miriam; Lamuela-Raventos, Rosa M

    2017-07-19

    Phenolic compounds are present in human fluids (plasma and urine) mainly as glucuronidated and sulfated metabolites. Up to now, due to the unavailability of standards, enzymatic hydrolysis has been the method of choice in analytical chemistry to quantify these phase II phenolic metabolites. Enzymatic hydrolysis procedures vary in enzyme concentration, pH and temperature; however, there is a lack of knowledge about the stability of polyphenols in their free form during the process. In this study, we evaluated the stability of 7 phenolic acids, 2 flavonoids and 3 prenylflavanoids in urine during enzymatic hydrolysis to assess the suitability of this analytical procedure, using three different concentrations of β-glucuronidase/sulfatase enzymes from Helix pomatia. The results indicate that enzymatic hydrolysis negatively affected the recovery of the precursor and free-form polyphenols present in the sample. Thus, enzymatic hydrolysis does not seem an ideal analytical strategy to quantify glucuronidated and sulfated polyphenol metabolites.

  1. Determination of linear short chain aliphatic aldehyde and ketone vapors in air using a polystyrene-coated quartz crystal nanobalance sensor.

    PubMed

    Mirmohseni, Abdolreza; Olad, Ali

    2010-01-01

    A polystyrene coated quartz crystal nanobalance (QCN) sensor was developed for use in the determination of a number of linear short-chain aliphatic aldehyde and ketone vapors contained in air. The quartz crystal was modified by a thin-layer coating of a commercial grade general purpose polystyrene (GPPS) from Tabriz petrochemical company using a solution casting method. Determination was based on frequency shifts of the modified quartz crystal due to the adsorption of analytes at the surface of modified electrode in exposure to various concentrations of analytes. The frequency shift was found to have a linear relation to the concentration of analytes. Linear calibration curves were obtained for 7-70 mg l(-1) of analytes with correlation coefficients in the range of 0.9935-0.9989 and sensitivity factors in the range of 2.07-6.74 Hz/mg l(-1). A storage period of over three months showed no loss in the sensitivity and performance of the sensor.

  2. Determination of nonylphenol and short-chained nonylphenol ethoxylates in drain water from an agricultural area.

    PubMed

    Zgoła-Grześkowiak, Agnieszka; Grześkowiak, Tomasz; Rydlichowski, Robert; Łukaszewski, Zenon

    2009-04-01

    Water samples from agricultural drains were tested for the presence of nonylphenol and nonylphenol mono- and diethoxylates. The analytes belong to biodegradation products of long-chained nonylphenol ethoxylates, which are used as additives in pesticide formulations. Quantification of these analytes was performed by HPLC with fluorescence detection after isolation by using multi-capillary polytetrafluoroethylene (PTFE) trap extraction. This newly developed technique allowed obtaining about 90% recovery of these analytes in synthetic samples and several percent lower recovery in real samples. Also, no additional sample cleaning was needed before chromatographic analysis. The limit of quantitation for all the analytes was 0.1 microg L(-1). The nonylphenol, nonylphenol mono- and diethoxylates were detected at the concentrations ranging from 0.5 to 6.0 microg L(-1), from 0.2 to 0.7 microg L(-1) and from below 0.02 to 0.4 microg L(-1), respectively. Concentrations of nonylphenol and its derivatives were higher in samples taken in spring than in summer.

  3. Love Canal Emergency Declaration Area habitability study. Volume 3. Soil assessment: indicator chemicals. Final report

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Not Available

    Environmental studies were conducted to provide data that could be used by the Commissioner of Health for the State of New York in determining whether the Emergency Declaration Area (EDA) surrounding the Love Canal hazardous-waste site is habitable. The soil assessment compared concentrations of the Love Canal Indicator Chemicals found in the EDA to concentrations found in similar western New York communities. An analytical technique was developed to detect the indicator chemicals at very low levels, i.e. 1.0 ppb. The analytical technique utilized a gas chromatograph/mass spectrometer operating in the selected ion monitoring mode. The analytical results were statistically comparedmore » between the EDA and the comparison areas using a modified Wilcoxon rank sum test.« less

  4. Stochastic sensing through covalent interactions

    DOEpatents

    Bayley, Hagan; Shin, Seong-Ho; Luchian, Tudor; Cheley, Stephen

    2013-03-26

    A system and method for stochastic sensing in which the analyte covalently bonds to the sensor element or an adaptor element. If such bonding is irreversible, the bond may be broken by a chemical reagent. The sensor element may be a protein, such as the engineered P.sub.SH type or .alpha.HL protein pore. The analyte may be any reactive analyte, including chemical weapons, environmental toxins and pharmaceuticals. The analyte covalently bonds to the sensor element to produce a detectable signal. Possible signals include change in electrical current, change in force, and change in fluorescence. Detection of the signal allows identification of the analyte and determination of its concentration in a sample solution. Multiple analytes present in the same solution may be detected.

  5. Major- and Trace-Element Concentrations in Rock Samples Collected in 2005 from the Taylor Mountains 1:250,000-scale Quadrangle, Alaska

    USGS Publications Warehouse

    Klimasauskas, Edward P.; Miller, Marti L.; Bradley, Dwight C.; Bundtzen, Tom K.; Hudson, Travis L.

    2006-01-01

    The data consist of major- and minor-element concentrations for rock samples collected during 2005 by the U.S. Geological Survey. Samples were analyzed by fire assay (Au, Pd, Pt), cold vapor atomic absorption spectroscopy (Hg), and the inductively coupled plasma mass spectrometry (ICPMS) 10 and 42 element methods. For details of sample preparation and analytical techniques see USGS Open File Report 02-0223 (Analytical methods for chemical analysis of geologic and other materials, U.S. Geological Survey), available at .

  6. 40 CFR 63.1574 - What notifications must I submit and when?

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... analytical methods you will use to determine the equilibrium catalyst Ni concentration, the equilibrium catalyst Ni concentration monthly rolling average, and the hourly or hourly average Ni operating value. (v...

  7. Systematic investigation of ion suppression and enhancement effects of fourteen stable-isotope-labeled internal standards by their native analogues using atmospheric-pressure chemical ionization and electrospray ionization and the relevance for multi-analyte liquid chromatographic/mass spectrometric procedures.

    PubMed

    Remane, Daniela; Wissenbach, Dirk K; Meyer, Markus R; Maurer, Hans H

    2010-04-15

    In clinical and forensic toxicology, multi-analyte procedures are very useful to quantify drugs and poisons of different classes in one run. For liquid chromatographic/tandem mass spectrometric (LC/MS/MS) multi-analyte procedures, often only a limited number of stable-isotope-labeled internal standards (SIL-ISs) are available. If an SIL-IS is used for quantification of other analytes, it must be excluded that the co-eluting native analyte influences its ionization. Therefore, the effect of ion suppression and enhancement of fourteen SIL-ISs caused by their native analogues has been studied. It could be shown that the native analyte concentration influenced the extent of ion suppression and enhancement effects leading to more suppression with increasing analyte concentration especially when electrospray ionization (ESI) was used. Using atmospheric-pressure chemical ionization (APCI), methanolic solution showed mainly enhancement effects, whereas no ion suppression and enhancement effect, with one exception, occurred when plasma extracts were used under these conditions. Such differences were not observed using ESI. With ESI, eleven SIL-ISs showed relevant suppression effects, but only one analyte showed suppression effects when APCI was used. The presented study showed that ion suppression and enhancement tests using matrix-based samples of different sources are essential for the selection of ISs, particularly if used for several analytes to avoid incorrect quantification. In conclusion, only SIL-ISs should be selected for which no suppression and enhancement effects can be observed. If not enough ISs are free of ionization interferences, a different ionization technique should be considered. 2010 John Wiley & Sons, Ltd.

  8. Diurnal variability of gas phase and surface water ethanol in southeastern North Carolina, USA

    NASA Astrophysics Data System (ADS)

    Kieber, R. J.; Powell, J. P.; Foley, L.; Mead, R. N.; Willey, J. D.; Avery, G. B.

    2017-11-01

    Diurnal variations in gas phase and surface water concentrations of ethanol and acetaldehyde were investigated at five locations in southeastern North Carolina, USA. There were distinct diurnal oscillations observed in gas phase concentrations with maxima occurring in late afternoon suggesting that photochemical production is an important process in the cycling of these analytes in the troposphere. The rapid decrease in concentrations after the mid day maximum suggests that there is also an atmospheric photochemical sink for both analytes most likely involving photo produced hydroxyl radicals with a half-life on the order of hours rather than days at ground level. Ethanol concentrations in the surface microlayer taken at the same time as gas phase samples had a very similar diurnal profile suggesting photochemical processes, in addition to atmospheric deposition, play a role in the aqueous phase cycling of both analytes. The concentration of ethanol and acetaldehyde increased significantly in flasks containing freshwater collected from the Cape Fear River exposed to simulated sunlight for 6 h underscoring the importance of in situ photochemical production. Results of this study are significant because they represent the first simultaneous analyses of the temporal variability of ethanol and acetaldehyde concentrations in the gas and aqueous phases. These measurements are essential in order to better define the processes involved in the global biogeochemical cycling of ethanol both now and in the future as our use of the biofuel continues to grow.

  9. Online measurement of urea concentration in spent dialysate during hemodialysis.

    PubMed

    Olesberg, Jonathon T; Arnold, Mark A; Flanigan, Michael J

    2004-01-01

    We describe online optical measurements of urea in the effluent dialysate line during regular hemodialysis treatment of several patients. Monitoring urea removal can provide valuable information about dialysis efficiency. Spectral measurements were performed with a Fourier-transform infrared spectrometer equipped with a flow-through cell. Spectra were recorded across the 5000-4000 cm(-1) (2.0-2.5 microm) wavelength range at 1-min intervals. Savitzky-Golay filtering was used to remove baseline variations attributable to the temperature dependence of the water absorption spectrum. Urea concentrations were extracted from the filtered spectra by use of partial least-squares regression and the net analyte signal of urea. Urea concentrations predicted by partial least-squares regression matched concentrations obtained from standard chemical assays with a root mean square error of 0.30 mmol/L (0.84 mg/dL urea nitrogen) over an observed concentration range of 0-11 mmol/L. The root mean square error obtained with the net analyte signal of urea was 0.43 mmol/L with a calibration based only on a set of pure-component spectra. The error decreased to 0.23 mmol/L when a slope and offset correction were used. Urea concentrations can be continuously monitored during hemodialysis by near-infrared spectroscopy. Calibrations based on the net analyte signal of urea are particularly appealing because they do not require a training step, as do statistical multivariate calibration procedures such as partial least-squares regression.

  10. Thyroglobulin assay in fluids from lymph node fine needle-aspiration washout: influence of pre-analytical conditions.

    PubMed

    Casson, Florence Boux de; Moal, Valérie; Gauchez, Anne-Sophie; Moineau, Marie-Pierre; Sault, Corinne; Schlageter, Marie-Hélène; Massart, Catherine

    2017-04-01

    The aim of this study was to evaluate the pre-analytical factors contributing to uncertainty in thyroglobulin measurement in fluids from fine-needle aspiration (FNA) washout of cervical lymph nodes. We studied pre-analytical stability, in different conditions, of 41 samples prepared with concentrated solutions of thyroglobulin (FNA washout or certified standard) diluted in physiological saline solution or buffer containing 6% albumin. In this buffer, over time, no changes in thyroglobulin concentrations were observed in all storage conditions tested. In albumin free saline solution, thyroglobulin recovery rates depended on initial sample concentrations and on modalities of their conservation (in conventional storage tubes, recovery mean was 56% after 3 hours-storage at room temperature and 19% after 24 hours-storage for concentrations ranged from 2 to 183 μg/L; recovery was 95%, after 3 hours or 24 hours-storage at room temperature, for a concentration of 5,656 μg/L). We show here that these results are due to non-specific adsorption of thyroglobulin in storage tubes, which depends on sample protein concentrations. We also show that possible contamination of fluids from FNA washout by plasma proteins do not always adequately prevent this adsorption. In conclusion, non-specific adsorption in storage tubes strongly contributes to uncertainty in thyroglobulin measurement in physiological saline solution. It is therefore recommended, for FNA washout, to use a buffer containing proteins provided by the laboratory.

  11. Analogue solution for electrical capacity of membrane covered square cylinders in square array at high concentration.

    PubMed

    Cole, K S

    1975-12-01

    Analytical solutions of Laplace equations have given the electrical characteristics of membranes and interiors of spherical, ellipsoidal, and cylindrical cells in suspensions and tissues from impedance measurements, but the underlying assumptions may be invalid above 50% volume concentrations. However, resistance measurements on several nonconducting, close-packing forms in two and three dimensions closely predicted volume concentrations up to 100% by equations derived from Maxwell and Rayleigh. Calculations of membrane capacities of cells in suspensions and tissues from extensions of theory, as developed by Fricke and by Cole, have been useful but of unknown validity at high concentrations. A resistor analogue has been used to solve the finite difference approximation to the Laplace equation for the resistance and capacity of a square array of square cylindrical cells with surface capacity. An 11 x 11 array of resistors, simulating a quarter of the unit structure, was separated into intra- and extra-cellular regions by rows of capacitors corresponding to surface membrane areas from 3 x 3 to 11 x 11 or 7.5% to 100%. The extended Rayleigh equation predicted the cell concentrations and membrane capacities to within a few percent from boundary resistance and capacity measurements at low frequencies. This single example suggests that analytical solutions for other, similar two- and three-dimensional problems may be approximated up to near 100% concentrations and that there may be analytical justifications for such analogue solutions of Laplace equations.

  12. Sigma metrics used to assess analytical quality of clinical chemistry assays: importance of the allowable total error (TEa) target.

    PubMed

    Hens, Koen; Berth, Mario; Armbruster, Dave; Westgard, Sten

    2014-07-01

    Six Sigma metrics were used to assess the analytical quality of automated clinical chemistry and immunoassay tests in a large Belgian clinical laboratory and to explore the importance of the source used for estimation of the allowable total error. Clinical laboratories are continually challenged to maintain analytical quality. However, it is difficult to measure assay quality objectively and quantitatively. The Sigma metric is a single number that estimates quality based on the traditional parameters used in the clinical laboratory: allowable total error (TEa), precision and bias. In this study, Sigma metrics were calculated for 41 clinical chemistry assays for serum and urine on five ARCHITECT c16000 chemistry analyzers. Controls at two analyte concentrations were tested and Sigma metrics were calculated using three different TEa targets (Ricos biological variability, CLIA, and RiliBÄK). Sigma metrics varied with analyte concentration, the TEa target, and between/among analyzers. Sigma values identified those assays that are analytically robust and require minimal quality control rules and those that exhibit more variability and require more complex rules. The analyzer to analyzer variability was assessed on the basis of Sigma metrics. Six Sigma is a more efficient way to control quality, but the lack of TEa targets for many analytes and the sometimes inconsistent TEa targets from different sources are important variables for the interpretation and the application of Sigma metrics in a routine clinical laboratory. Sigma metrics are a valuable means of comparing the analytical quality of two or more analyzers to ensure the comparability of patient test results.

  13. Assessing the Impact of Analytical Error on Perceived Disease Severity.

    PubMed

    Kroll, Martin H; Garber, Carl C; Bi, Caixia; Suffin, Stephen C

    2015-10-01

    The perception of the severity of disease from laboratory results assumes that the results are free of analytical error; however, analytical error creates a spread of results into a band and thus a range of perceived disease severity. To assess the impact of analytical errors by calculating the change in perceived disease severity, represented by the hazard ratio, using non-high-density lipoprotein (nonHDL) cholesterol as an example. We transformed nonHDL values into ranges using the assumed total allowable errors for total cholesterol (9%) and high-density lipoprotein cholesterol (13%). Using a previously determined relationship between the hazard ratio and nonHDL, we calculated a range of hazard ratios for specified nonHDL concentrations affected by analytical error. Analytical error, within allowable limits, created a band of values of nonHDL, with a width spanning 30 to 70 mg/dL (0.78-1.81 mmol/L), depending on the cholesterol and high-density lipoprotein cholesterol concentrations. Hazard ratios ranged from 1.0 to 2.9, a 16% to 50% error. Increased bias widens this range and decreased bias narrows it. Error-transformed results produce a spread of values that straddle the various cutoffs for nonHDL. The range of the hazard ratio obscures the meaning of results, because the spread of ratios at different cutoffs overlap. The magnitude of the perceived hazard ratio error exceeds that for the allowable analytical error, and significantly impacts the perceived cardiovascular disease risk. Evaluating the error in the perceived severity (eg, hazard ratio) provides a new way to assess the impact of analytical error.

  14. Quality control analytical methods: refractive index.

    PubMed

    Allen, Loyd V

    2015-01-01

    There are numerous analytical methods that can be utilized in a compounding pharmacy for a quality-assurance program. Since the index of refraction of a liquid/solution is a physical constant, it can be used to assist in identification of a substance, establish its purity, and, in some instances, to determine the concentration of an analyte in solution. This article serves as an introduction to refractive index and some applications of its use in a compounding program.

  15. ANALYTICAL METHODS AND QUALITY ASSURANCE CRITERIA FOR LC/ES/MS DETERMINATION OF PFOS IN FISH

    EPA Science Inventory

    PFOS, perfluorooctanesulfonate, has recently received much attention from environmental researchers. Previous analytical methods were based upon complexing with a strong ion-pairing reagent and extraction into MTBE. Detection was done on a concentrate using negative ion LC/ES/MS/...

  16. Quantifying cyanobacterial phycocyanin concentration in turbid productive waters: a quasi-analytical approach

    USDA-ARS?s Scientific Manuscript database

    In this research, we present a novel technique to monitor cyanobacterial algal bloom using remote sensing measurements. We have used a multi-band quasi analytical algorithm that determines phytoplankton absorption coefficients, aF('), from above-surface remote sensing reflectance, Rrs('). In situ da...

  17. Determination of Residual Chlorine and Turbidity in Drinking Water. Student Manual.

    ERIC Educational Resources Information Center

    Office of Water Program Operations (EPA), Cincinnati, OH. National Training and Operational Technology Center.

    This student's manual covers analytical methods for residual chlorine and turbidity. Topics include sample handling, permissable concentration levels, substitution of residual chlorine for bacteriological work, public notification, and the required analytical techniques to determine residual chlorine and turbidity. The publication is intended for…

  18. THE IMPORTANCE OF PROPER INTENSITY CALIBRATION FOR RAMAN ANALYSIS OF LOW-LEVEL ANALYTES IN WATER

    EPA Science Inventory

    Modern dispersive Raman spectroscopy offers unique advantages for the analysis of low-concentration analytes in aqueous solution. However, we have found that proper intensity calibration is critical for obtaining these benefits. This is true not only for producing spectra with ...

  19. ANALYTICAL METHODS NECESSARY TO IMPLEMENT RISK-BASED CRITERIA FOR CHEMICALS IN MUNICIPAL SLUDGE

    EPA Science Inventory

    The Ambient Water Quality Criteria that were promulgated by the U.S. Environmental Protection Agency in 1980 included water concentration levels which, for many pollutants, were so low as to be unmeasurable by standard analytical methods. Criteria for controlling toxics in munici...

  20. Scaling Law for Cross-stream Diffusion in Microchannels under Combined Electroosmotic and Pressure Driven Flow.

    PubMed

    Song, Hongjun; Wang, Yi; Pant, Kapil

    2013-01-01

    This paper presents an analytical study of the cross-stream diffusion of an analyte in a rectangular microchannel under combined electroosmotic flow (EOF) and pressure driven flow to investigate the heterogeneous transport behavior and spatially-dependent diffusion scaling law. An analytical model capable of accurately describing 3D steady-state convection-diffusion in microchannels with arbitrary aspect ratios is developed based on the assumption of the thin Electric Double Layer (EDL). The model is verified against high-fidelity numerical simulation in terms of flow velocity and analyte concentration profiles with excellent agreement (<0.5% relative error). An extensive parametric analysis is then undertaken to interrogate the effect of the combined flow velocity field on the transport behavior in both the positive pressure gradient (PPG) and negative pressure gradient (NPG) cases. For the first time, the evolution from the spindle-shaped concentration profile in the PPG case, via the stripe-shaped profile (pure EOF), and finally to the butterfly-shaped profile in the PPG case is obtained using the analytical model along with a quantitative depiction of the spatially-dependent diffusion layer thickness and scaling law across a wide range of the parameter space.

  1. Scaling Law for Cross-stream Diffusion in Microchannels under Combined Electroosmotic and Pressure Driven Flow

    PubMed Central

    Song, Hongjun; Wang, Yi; Pant, Kapil

    2012-01-01

    This paper presents an analytical study of the cross-stream diffusion of an analyte in a rectangular microchannel under combined electroosmotic flow (EOF) and pressure driven flow to investigate the heterogeneous transport behavior and spatially-dependent diffusion scaling law. An analytical model capable of accurately describing 3D steady-state convection-diffusion in microchannels with arbitrary aspect ratios is developed based on the assumption of the thin Electric Double Layer (EDL). The model is verified against high-fidelity numerical simulation in terms of flow velocity and analyte concentration profiles with excellent agreement (<0.5% relative error). An extensive parametric analysis is then undertaken to interrogate the effect of the combined flow velocity field on the transport behavior in both the positive pressure gradient (PPG) and negative pressure gradient (NPG) cases. For the first time, the evolution from the spindle-shaped concentration profile in the PPG case, via the stripe-shaped profile (pure EOF), and finally to the butterfly-shaped profile in the PPG case is obtained using the analytical model along with a quantitative depiction of the spatially-dependent diffusion layer thickness and scaling law across a wide range of the parameter space. PMID:23554584

  2. Analytical methods for the determination of personal care products in human samples: an overview.

    PubMed

    Jiménez-Díaz, I; Zafra-Gómez, A; Ballesteros, O; Navalón, A

    2014-11-01

    Personal care products (PCPs) are organic chemicals widely used in everyday human life. Nowadays, preservatives, UV-filters, antimicrobials and musk fragrances are widely used PCPs. Different studies have shown that some of these compounds can cause adverse health effects, such as genotoxicity, which could even lead to mutagenic or carcinogenic effects, or estrogenicity because of their endocrine disruption activity. Due to the absence of official monitoring protocols, there is an increasing demand of analytical methods that allow the determination of those compounds in human samples in order to obtain more information regarding their behavior and fate in the human body. The complexity of the biological matrices and the low concentration levels of these compounds make necessary the use of advanced sample treatment procedures that afford both, sample clean-up, to remove potentially interfering matrix components, as well as the concentration of analytes. In the present work, a review of the more recent analytical methods published in the scientific literature for the determination of PCPs in human fluids and tissue samples, is presented. The work focused on sample preparation and the analytical techniques employed. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Quantification of Concentration of Microalgae Anabaena Cylindrica, Coal-bed Methane Water Isolates Nannochloropsis Gaditana and PW-95 in Aquatic Solutions through Hyperspectral Reflectance Measurement and Analytical Model Establishment

    NASA Astrophysics Data System (ADS)

    Zhou, Z.; Zhou, X.; Apple, M. E.; Spangler, L.

    2017-12-01

    Three species of microalgae, Anabaena cylindrica (UTEX # 1611), coal-bed methane water isolates Nannochloropsis gaditana and PW-95 were cultured for the measurements of their hyperspectral profiles in different concentrations. The hyperspectral data were measured by an Analytical Spectral Devices (ASD) spectroradiomter with the spectral resolution of 1 nanometer over the wavelength ranges from 350nm to 1050 nm for samples of microalgae of different concentration. Concentration of microalgae was measured using a Hemocytometer under microscope. The objective of this study is to establish the relation between spectral reflectance and micro-algal concentration so that microalgae concentration can be measured remotely by space- or airborne hyperspectral or multispectral sensors. Two types of analytical models, linear reflectance-concentration model and Lamber-Beer reflectance-concentration model, were established for each species. For linear modeling, the wavelength with the maximum correlation coefficient between the reflectance and concentrations of algae was located and then selected for each species of algae. The results of the linear models for each species are shown in Fig.1(a), in which Refl_1, Refl_2, and Refl_3 represent the reflectance of Anabaena, N. Gaditana, and PW-95 respectively. C1, C2, and C3 represent the Concentrations of Anabaena, N. Gaditana, and PW-95 respectively. The Lamber-Beer models were based on the Lambert-Beer Law, which states that the intensity of light propagating in a substance dissolved in a fully transmitting solvent is directly proportional to the concentration of the substance and the path length of the light through the solution. Thus, for the Lamber-Beer modeling, a wavelength with large absorption in red band was selected for each species. The results of Lambert-Beer models for each species are shown in Fig.1(b). Based on the Lamber-Beer models, the absorption coefficient for the three different species will be quantified.

  4. Concentration history during pumping from a leaky aquifer with stratified initial concentration

    USGS Publications Warehouse

    Goode, Daniel J.; Hsieh, Paul A.; Shapiro, Allen M.; Wood, Warren W.; Kraemer, Thomas F.

    1993-01-01

    Analytical and numerical solutions are employed to examine the concentration history of a dissolved substance in water pumped from a leaky aquifer. Many aquifer systems are characterized by stratification, for example, a sandy layer overlain by a clay layer. To obtain information about separate hydrogeologic units, aquifer pumping tests are often conducted with a well penetrating only one of the layers. When the initial concentration distribution is also stratified (the concentration varies with elevation only), the concentration breakthrough in the pumped well may be interpreted to provide information on aquifer hydraulic and transport properties. To facilitate this interpretation, we present some simple analytical and numerical solutions for limiting cases and illustrate their application to a fractured bedrock/glacial drift aquifer system where the solute of interest is dissolved radon gas. In addition to qualitative information on water source, this method may yield estimates of effective porosity and saturated thickness (or fracture transport aperture) from a single-hole test. Little information about dispersivity is obtained because the measured concentration is not significantly affected by dispersion in the aquifer.

  5. External quality-assurance results for the National Atmospheric Deposition Program/National Trends Network during 1991

    USGS Publications Warehouse

    Nilles, M.A.; Gordon, J.D.; Schroder, L.J.; Paulin, C.E.

    1995-01-01

    The U.S. Geological Survey used four programs in 1991 to provide external quality assurance for the National Atmospheric Deposition Program/National Trends Network (NADP/NTN). An intersite-comparison program was used to evaluate onsite pH and specific-conductance determinations. The effects of routine sample handling, processing, and shipping of wet-deposition samples on analyte determinations and an estimated precision of analyte values and concentrations were evaluated in the blind-audit program. Differences between analytical results and an estimate of the analytical precision of four laboratories routinely measuring wet deposition were determined by an interlaboratory-comparison program. Overall precision estimates for the precipitation-monitoring system were determined for selected sites by a collocated-sampler program. Results of the intersite-comparison program indicated that 93 and 86 percent of the site operators met the NADP/NTN accuracy goal for pH determinations during the two intersite-comparison studies completed during 1991. The results also indicated that 96 and 97 percent of the site operators met the NADP/NTN accuracy goal for specific-conductance determinations during the two 1991 studies. The effects of routine sample handling, processing, and shipping, determined in the blind-audit program indicated significant positive bias (a=.O 1) for calcium, magnesium, sodium, potassium, chloride, nitrate, and sulfate. Significant negative bias (or=.01) was determined for hydrogen ion and specific conductance. Only ammonium determinations were not biased. A Kruskal-Wallis test indicated that there were no significant (*3t=.01) differences in analytical results from the four laboratories participating in the interlaboratory-comparison program. Results from the collocated-sampler program indicated the median relative error for cation concentration and deposition exceeded eight percent at most sites, whereas the median relative error for sample volume, sulfate, and nitrate concentration at all sites was less than four percent. The median relative error for hydrogen ion concentration and deposition ranged from 4.6 to 18.3 percent at the four sites and as indicated in previous years of the study, was inversely proportional to the acidity of the precipitation at a given site. Overall, collocated-sampling error typically was five times that of laboratory error estimates for most analytes.

  6. High speed operation of permanent magnet machines

    NASA Astrophysics Data System (ADS)

    El-Refaie, Ayman M.

    This work proposes methods to extend the high-speed operating capabilities of both the interior PM (IPM) and surface PM (SPM) machines. For interior PM machines, this research has developed and presented the first thorough analysis of how a new bi-state magnetic material can be usefully applied to the design of IPM machines. Key elements of this contribution include identifying how the unique properties of the bi-state magnetic material can be applied most effectively in the rotor design of an IPM machine by "unmagnetizing" the magnet cavity center posts rather than the outer bridges. The importance of elevated rotor speed in making the best use of the bi-state magnetic material while recognizing its limitations has been identified. For surface PM machines, this research has provided, for the first time, a clear explanation of how fractional-slot concentrated windings can be applied to SPM machines in order to achieve the necessary conditions for optimal flux weakening. A closed-form analytical procedure for analyzing SPM machines designed with concentrated windings has been developed. Guidelines for designing SPM machines using concentrated windings in order to achieve optimum flux weakening are provided. Analytical and numerical finite element analysis (FEA) results have provided promising evidence of the scalability of the concentrated winding technique with respect to the number of poles, machine aspect ratio, and output power rating. Useful comparisons between the predicted performance characteristics of SPM machines equipped with concentrated windings and both SPM and IPM machines designed with distributed windings are included. Analytical techniques have been used to evaluate the impact of the high pole number on various converter performance metrics. Both analytical techniques and FEA have been used for evaluating the eddy-current losses in the surface magnets due to the stator winding subharmonics. Techniques for reducing these losses have been investigated. A 6kW, 36slot/30pole prototype SPM machine has been designed and built. Experimental measurements have been used to verify the analytical and FEA results. These test results have demonstrated that wide constant-power speed range can be achieved. Other important machine features such as the near-sinusoidal back-emf, high efficiency, and low cogging torque have also been demonstrated.

  7. Novel Flourescent Sensors for the Detection of Organic Molecules in Extraterrestrial Samples

    NASA Astrophysics Data System (ADS)

    Adkin, Roy C.; Bruce, James I.; Pearson, Victoria K.

    2015-04-01

    Organic compounds in extraterrestrial samples have mostly been elucidated by destructive analytical techniques therefore information regarding spatial relationships between minerals and organic species is lost. Minerals form under specific chemical and physical conditions so organic compounds associated with these minerals are likely to have formed under the same conditions. It is therefore possible to infer in which cosmological provinces their chemical evolution took place. We will describe progress towards developing fluorescent sensors that may resolve spatial discrimination. Lanthanide elements such as europium and terbium produce well defined line-like, high intensity and long lived fluorescent emissions. Interactions with organic molecules may alter the luminescent emission characteristics. The lanthanide atom needs to be rendered chemically inert but must remain susceptible to these organic molecule interactions. An organic ligand must be employed to attain this. DOTA (1,4,7,10-tetraazacyclododecanetetracetic acid) was chosen as a plausible organic ligand because its structure, a tetra-substituted cyclen ring, and ability to chelate are well characterized. It is also commercially available. Fluorescent lanthanide-DOTA complexes are used in many biological and analytical imaging applications so it is logical to investigate their applicability to fluorimetric analysis of extraterrestrial organics. Lanthanide-DOTA complexes are very stable because the lanthanide metal atom is enveloped within the DOTA structure. Experimental procedures were designed to investigate lanthanide/analyte interactions and their effect upon fluorescent emissions. A range of compounds were chosen giving a good representation of the organics identified in extraterrestrial samples and whether they may to interact with the lanthanide metal ion. An Europium-DOTA baseline fluorescent spectrum was obtained and compared against Europium-DOTA/analyte mixtures of a range of concentrations resembling those present in extraterrestrial samples. Upon collation and analysis of results a much reduced set of analytes were chosen for experimentation with Terbium-DOTA. Results showed no change in fluorescent intensity or emission spectrum for any of the analytes at the concentrations found in extraterrestrial samples (μM to nM). This could be due to no interaction at any concentration of analyte or there is an intrinsic limit of detection. Experiments were carried out at equimolar concentration with fewer analytes. It was found that here was an increase in fluorescent intensity for some analytes and decrease for others (e.g. adenine and ornithine, respectively). There was no discernible trend in behaviour according to analyte structure or how they might interact as a result. Attention has now turned to the tris-substituted cyclen ring, DO3A, which could afford improved scope for interaction. DOTA is an unsuitable ligand to use for the sensor. Experimentation has shown that neither lanthanide-DOTA complexes exhibited a change in fluorescent spectrum; the ligand requires modification not the choice of lanthanide. We will present results from the development and preliminary testing of the DO3A sensor.

  8. The Unanticipated Explosion: Private Higher Education's Global Surge

    ERIC Educational Resources Information Center

    Levy, Daniel C.

    2006-01-01

    This article provides a broad and analytical overview of the private higher education explosion. It concentrates on a crucial yet generally ignored characteristic: the largely unanticipated emergence, not following a broad preconception or systemic design. The article's main conceptual thrust is to identify and provide analytical perspectives on…

  9. Transport of a decay chain in homogenous porous media: analytical solutions.

    PubMed

    Bauer, P; Attinger, S; Kinzelbach, W

    2001-06-01

    With the aid of integral transforms, analytical solutions for the transport of a decay chain in homogenous porous media are derived. Unidirectional steady-state flow and radial steady-state flow in single and multiple porosity media are considered. At least in Laplace domain, all solutions can be written in closed analytical formulae. Partly, the solutions can also be inverted analytically. If not, analytical calculation of the steady-state concentration distributions, evaluation of temporal moments and numerical inversion are still possible. Formulae for several simple boundary conditions are given and visualized in this paper. The derived novel solutions are widely applicable and are very useful for the validation of numerical transport codes.

  10. Evaluation of analytical methodology for hydrocarbons in high pressure air and nitrogen systems. [evaluation of methodology

    NASA Technical Reports Server (NTRS)

    1977-01-01

    Samples of liquid oxygen, high pressure nitrogen, low pressure nitrogen, and missile grade air were studied to determine the hydrocarbon concentrations. Concentration of the samples was achieved by adsorption on a molecular sieve and activated charcoal. The trapped hydrocarbons were then desorbed and transferred to an analytical column in a gas chromatograph. The sensitivity of the method depends on the volume of gas passed through the adsorbent tubes. The value of the method was verified through recoverability and reproducibility studies. The use of this method enables LOX, GN2, and missile grade air systems to be routinely monitored to determine low level increases in specific hydrocarbon concentration that could lead to potentially hazardous conditions.

  11. Determination of finasteride and its metabolite in urine by dispersive liquid-liquid microextraction combined with field-enhanced sample stacking and sweeping.

    PubMed

    Chen, Chun-Hsien; Chao, Yu-Ying; Lin, Yi-Hui; Chen, Yen-Ling

    2018-04-27

    The on-line preconcentration technique of field-enhanced sample stacking and sweeping (FESS-sweeping) are combined with dispersive liquid-liquid microextraction (DLLME) to monitor the concentrations of finasteride, which is used in the treatment of androgenetic alopecia, and its metabolite, finasteride carboxylic acid (M3), in urine samples. DLLME is used to concentrate and eliminate the interferences of urine samples and uses chloroform as an extracting solvent and acetonitrile as a disperser solvent. A high conductivity buffer (HCB) was introduced into capillary and then sample plug (90.7% capillary length) was injected into capillary. After applying voltage, the sodium dodecyl sulfate (SDS) swept the analytes from the low conductivity sample solution into HCB. The analytes were concentrated on the field-enhanced sample stacking boundary. The limit of detection for the analytes is 20 ng mL -1 . The sensitivity enrichment of finasteride and M3 are 362-fold and 480-fold, respectively, compared with the conventional MEKC method. The on-line preconcentration technique of field-enhanced sample stacking and sweeping possess good selectivity because the endogenous steroid did not interfere the detection of finasteride and M3. The analytical technique is applied to investigate the concentrations in urine samples from patients who have been administered finasteride for the treatment of androgenetic alopecia; the amount of M3 detected in 12 h was 72.69 ± 4.18 μg. Copyright © 2018 Elsevier B.V. All rights reserved.

  12. Rapid, specific determination of iodine and iodide by combined solid-phase extraction/diffuse reflectance spectroscopy

    NASA Technical Reports Server (NTRS)

    Arena, Matteo P.; Porter, Marc D.; Fritz, James S.

    2002-01-01

    A new, rapid methodology for trace analysis using solid-phase extraction is described. The two-step methodology is based on the concentration of an analyte onto a membrane disk and on the determination by diffuse reflectance spectroscopy of the amount of analyte extracted on the disk surface. This method, which is adaptable to a wide range of analytes, has been used for monitoring ppm levels of iodine and iodide in spacecraft water. Iodine is used as a biocide in spacecraft water. For these determinations, a water sample is passed through a membrane disk by means of a 10-mL syringe that is attached to a disk holder assembly. The disk, which is a polystyrene-divinylbenzene composite, is impregnated with poly(vinylpyrrolidone) (PVP), which exhaustively concentrates iodine as a yellow iodine-PVP complex. The amount of concentrated iodine is then determined in only 2 s by using a hand-held diffuse reflectance spectrometer by comparing the result with a calibration curve based on the Kubelka-Munk function. The same general procedure can be used to determine iodide levels after its facile and exhaustive oxidation to iodine by peroxymonosulfate (i.e., Oxone reagent). For samples containing both analytes, a two-step procedure can be used in which the iodide concentration is calculated from the difference in iodine levels before and after treatment of the sample with peroxymonosulfate. With this methodology, iodine and iodide levels in the 0.1-5.0 ppm range can be determined with a total workup time of approximately 60 s with a RSD of approximately 6%.

  13. Analyte preconcentration in nanofluidic channels with nonuniform zeta potential

    NASA Astrophysics Data System (ADS)

    Eden, A.; McCallum, C.; Storey, B. D.; Pennathur, S.; Meinhart, C. D.

    2017-12-01

    It is well known that charged analytes in the presence of nonuniform electric fields concentrate at locations where the relevant driving forces balance, and a wide range of ionic stacking and focusing methods are commonly employed to leverage these physical mechanisms in order to improve signal levels in biosensing applications. In particular, nanofluidic channels with spatially varying conductivity distributions have been shown to provide increased preconcentration of charged analytes due to the existence of a finite electric double layer (EDL), in which electrostatic attraction and repulsion from charged surfaces produce nonuniform transverse ion distributions. In this work, we use numerical simulations to show that one can achieve greater levels of sample accumulation by using field-effect control via wall-embedded electrodes to tailor the surface potential heterogeneity in a nanochannel with overlapped EDLs. In addition to previously demonstrated stacking and focusing mechanisms, we find that the coupling between two-dimensional ion distributions and the axial electric field under overlapped EDL conditions can generate an ion concentration polarization interface in the middle of the channel. Under an applied electric field, this interface can be used to concentrate sample ions between two stationary regions of different surface potential and charge density. Our numerical model uses the Poisson-Nernst-Planck system of equations coupled with the Stokes equation to demonstrate the phenomenon, and we discuss in detail the driving forces behind the predicted sample enhancement. The numerical velocity and salt concentration profiles exhibit good agreement with analytical results from a simplified one-dimensional area-averaged model for several limiting cases, and we show predicted amplification ratios of up to 105.

  14. Analytical characterization and clinical evaluation of an enzyme-linked immunosorbent assay for measurement of afamin in human plasma.

    PubMed

    Dieplinger, Benjamin; Egger, Margot; Gabriel, Christian; Poelz, Werner; Morandell, Elisabeth; Seeber, Beata; Kronenberg, Florian; Haltmayer, Meinhard; Mueller, Thomas; Dieplinger, Hans

    2013-10-21

    Comparative proteomics has recently identified afamin, the newest member of the albumin gene family, as a potential biomarker for ovarian cancer. The aim of this study was the analytical and clinical evaluation of a sandwich enzyme-linked immunosorbent assay for the determination of afamin in human plasma. We evaluated precision, linearity, and detection limit of the assay, analyte stability and biological variability, determined reference values and quantified afamin concentrations in various diseases. Within-run and total coefficients of variation were <10%. The method was linear across the tested measurement range. Detection limit was 7 mg/L for the assay. The analyte was stable for 24 h at room temperature, for 48 h at 4°C, and for at least one year at -20°C and -80°C. The reference change value for healthy individuals was 24%. Age- and sex-independent reference values in healthy blood donors were 45-99 mg/L (median 68 mg/L). In the clinical assay evaluation afamin plasma concentrations were modestly decreased in patients with heart failure. Patients with pneumonia or sepsis exhibited markedly decreased afamin plasma concentrations. However, patients with chronic renal disease or chronic obstructive pulmonary disease showed no difference in afamin plasma concentrations as compared to healthy individuals. Correlation analyses revealed an inverse association between afamin and inflammatory biomarkers. The afamin assay meets quality specifications for laboratory medicine. The results of the clinical assay evaluation revealed novel insights with respect to afamin as a potential negative acute phase protein and should encourage further studies. © 2013.

  15. Accuracy of travel time distribution (TTD) models as affected by TTD complexity, observation errors, and model and tracer selection

    USGS Publications Warehouse

    Green, Christopher T.; Zhang, Yong; Jurgens, Bryant C.; Starn, J. Jeffrey; Landon, Matthew K.

    2014-01-01

    Analytical models of the travel time distribution (TTD) from a source area to a sample location are often used to estimate groundwater ages and solute concentration trends. The accuracies of these models are not well known for geologically complex aquifers. In this study, synthetic datasets were used to quantify the accuracy of four analytical TTD models as affected by TTD complexity, observation errors, model selection, and tracer selection. Synthetic TTDs and tracer data were generated from existing numerical models with complex hydrofacies distributions for one public-supply well and 14 monitoring wells in the Central Valley, California. Analytical TTD models were calibrated to synthetic tracer data, and prediction errors were determined for estimates of TTDs and conservative tracer (NO3−) concentrations. Analytical models included a new, scale-dependent dispersivity model (SDM) for two-dimensional transport from the watertable to a well, and three other established analytical models. The relative influence of the error sources (TTD complexity, observation error, model selection, and tracer selection) depended on the type of prediction. Geological complexity gave rise to complex TTDs in monitoring wells that strongly affected errors of the estimated TTDs. However, prediction errors for NO3− and median age depended more on tracer concentration errors. The SDM tended to give the most accurate estimates of the vertical velocity and other predictions, although TTD model selection had minor effects overall. Adding tracers improved predictions if the new tracers had different input histories. Studies using TTD models should focus on the factors that most strongly affect the desired predictions.

  16. Nondestructive quantification of analyte diffusion in cornea and sclera using optical coherence tomography.

    PubMed

    Ghosn, Mohamad G; Tuchin, Valery V; Larin, Kirill V

    2007-06-01

    Noninvasive functional imaging, monitoring, and quantification of analytes transport in epithelial ocular tissues are extremely important for therapy and diagnostics of many eye diseases. In this study the authors investigated the capability of optical coherence tomography (OCT) for noninvasive monitoring and quantification of diffusion of different analytes in sclera and cornea of rabbit eyes. A portable time-domain OCT system with wavelength of 1310 +/- 15 nm, output power of 3.5 mW, and resolution of 25 mum was used in this study. Diffusion of different analytes was monitored and quantified in rabbit cornea and sclera of whole eyeballs. Diffusion of water, metronidazole (0.5%), dexamethasone (0.2%), ciprofloxacin (0.3%), mannitol (20%), and glucose solution (20%) were examined, and their permeability coefficients were calculated by using OCT signal slope and depth-resolved amplitude methods. Permeability coefficients were calculated as a function of time and tissue depth. For instance, mannitol was found to have a permeability coefficient of (8.99 +/- 1.43) x 10(-6) cm/s in cornea and (6.18 +/- 1.08) x 10(-6) cm/s in sclera. The permeability coefficient of drugs with small concentrations (where water was the major solvent) was found to be in the range of that of water in the same tissue type, whereas permeability coefficients of higher concentrated solutions varied significantly. Results suggest that the OCT technique might be a powerful tool for noninvasive diffusion studies of different analytes in ocular tissues. However, additional methods of OCT signal acquisition and processing are required to study the diffusion of agents of small concentrations.

  17. A highly sensitive method for the simultaneous UHPLC-MS/MS analysis of clonidine, morphine, midazolam and their metabolites in blood plasma using HFIP as the eluent additive.

    PubMed

    Veigure, Rūta; Aro, Rudolf; Metsvaht, Tuuli; Standing, Joseph F; Lutsar, Irja; Herodes, Koit; Kipper, Karin

    2017-05-01

    In intensive care units, the precise administration of sedatives and analgesics is crucial in order to avoid under- or over sedation and for appropriate pain control. Both can be harmful to the patient, causing side effects or pain and suffering. This is especially important in the case of pediatric patients, and dose-response relationships require studies using pharmacokinetic-pharmacodynamic modeling. The aim of this work was to develop and validate a rapid ultra-high performance liquid chromatographic-tandem mass spectrometric method for the analysis of three common sedative and analgesic agents: morphine, clonidine and midazolam, and their metabolites (morphine-3-glucuronide, morphine-6-glucuronide and 1'-hydroxymidazolam) in blood plasma at trace level concentrations. Low concentrations and low sampling volumes may be expected in pediatric patients; we report the lowest limit of quantification for all analytes as 0.05ng/mL using only 100μL of blood plasma. The analytes were separated chromatographically using the C18 column with the weak ion-pairing additive 1,1,1,3,3,3-hexafluoro-2-propanol and methanol. The method was fully validated and a matrix matched calibration range of 0.05-250ng/mL was attained for all analytes In addition, between-day accuracy for all analytes remained within 93-108%, and precision remained within 1.5-9.6% for all analytes at all concentration levels over the calibration range. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

  18. Analytical solutions to compartmental indoor air quality models with application to environmental tobacco smoke concentrations measured in a house.

    PubMed

    Ott, Wayne R; Klepeis, Neil E; Switzer, Paul

    2003-08-01

    This paper derives the analytical solutions to multi-compartment indoor air quality models for predicting indoor air pollutant concentrations in the home and evaluates the solutions using experimental measurements in the rooms of a single-story residence. The model uses Laplace transform methods to solve the mass balance equations for two interconnected compartments, obtaining analytical solutions that can be applied without a computer. Environmental tobacco smoke (ETS) sources such as the cigarette typically emit pollutants for relatively short times (7-11 min) and are represented mathematically by a "rectangular" source emission time function, or approximated by a short-duration source called an "impulse" time function. Other time-varying indoor sources also can be represented by Laplace transforms. The two-compartment model is more complicated than the single-compartment model and has more parameters, including the cigarette or combustion source emission rate as a function of time, room volumes, compartmental air change rates, and interzonal air flow factors expressed as dimensionless ratios. This paper provides analytical solutions for the impulse, step (Heaviside), and rectangular source emission time functions. It evaluates the indoor model in an unoccupied two-bedroom home using cigars and cigarettes as sources with continuous measurements of carbon monoxide (CO), respirable suspended particles (RSP), and particulate polycyclic aromatic hydrocarbons (PPAH). Fine particle mass concentrations (RSP or PM3.5) are measured using real-time monitors. In our experiments, simultaneous measurements of concentrations at three heights in a bedroom confirm an important assumption of the model-spatial uniformity of mixing. The parameter values of the two-compartment model were obtained using a "grid search" optimization method, and the predicted solutions agreed well with the measured concentration time series in the rooms of the home. The door and window positions in each room had considerable effect on the pollutant concentrations observed in the home. Because of the small volumes and low air change rates of most homes, indoor pollutant concentrations from smoking activity in a home can be very high and can persist at measurable levels indoors for many hours.

  19. All-organic microelectromechanical systems integrating specific molecular recognition--a new generation of chemical sensors.

    PubMed

    Ayela, Cédric; Dubourg, Georges; Pellet, Claude; Haupt, Karsten

    2014-09-03

    Cantilever-type all-organic microelectromechanical systems based on molecularly imprinted polymers for specific analyte recognition are used as chemical sensors. They are produced by a simple spray-coating-shadow-masking process. Analyte binding to the cantilever generates a measurable change in its resonance frequency. This allows label-free detection by direct mass sensing of low-molecular-weight analytes at nanomolar concentrations. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Modeling systematic errors: polychromatic sources of Beer-Lambert deviations in HPLC/UV and nonchromatographic spectrophotometric assays.

    PubMed

    Galli, C

    2001-07-01

    It is well established that the use of polychromatic radiation in spectrophotometric assays leads to excursions from the Beer-Lambert limit. This Note models the resulting systematic error as a function of assay spectral width, slope of molecular extinction coefficient, and analyte concentration. The theoretical calculations are compared with recent experimental results; a parameter is introduced which can be used to estimate the magnitude of the systematic error in both chromatographic and nonchromatographic spectrophotometric assays. It is important to realize that the polychromatic radiation employed in common laboratory equipment can yield assay errors up to approximately 4%, even at absorption levels generally considered 'safe' (i.e. absorption <1). Thus careful consideration of instrumental spectral width, analyte concentration, and slope of molecular extinction coefficient is required to ensure robust analytical methods.

  1. Analytical methods involving separation techniques for determination of low-molecular-weight biothiols in human plasma and blood.

    PubMed

    Isokawa, Muneki; Kanamori, Takahiro; Funatsu, Takashi; Tsunoda, Makoto

    2014-08-01

    Low-molecular-weight biothiols such as homocysteine, cysteine, and glutathione are metabolites of the sulfur cycle and play important roles in biological processes such as the antioxidant defense network, methionine cycle, and protein synthesis. Thiol concentrations in human plasma and blood are related to diseases such as cardiovascular disease, neurodegenerative disease, and cancer. The concentrations of homocysteine, cysteine, and glutathione in plasma samples from healthy human subjects are approximately in the range of 5-15, 200-300, and 1-5 μM, respectively. Glutathione concentration in the whole blood is in the millimolar range. Measurement of biothiol levels in plasma and blood is thought to be important for understanding the physiological roles and biomarkers for certain diseases. This review summarizes the relationship of biothiols with certain disease as well as pre-analytical treatment and analytical methods for determination of biothiols in human plasma and blood by using high-performance liquid chromatography and capillary electrophoresis coupled with ultraviolet, fluorescence, or chemiluminescence detection; or mass spectrometry. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. The precision of wet atmospheric deposition data from national atmospheric deposition program/national trends network sites determined with collocated samplers

    USGS Publications Warehouse

    Nilles, M.A.; Gordon, J.D.; Schroder, L.J.

    1994-01-01

    A collocated, wet-deposition sampler program has been operated since October 1988 by the U.S. Geological Survey to estimate the overall sampling precision of wet atmospheric deposition data collected at selected sites in the National Atmospheric Deposition Program and National Trends Network (NADP/NTN). A duplicate set of wet-deposition sampling instruments was installed adjacent to existing sampling instruments at four different NADP/NTN sites for each year of the study. Wet-deposition samples from collocated sites were collected and analysed using standard NADP/NTN procedures. Laboratory analyses included determinations of pH, specific conductance, and concentrations of major cations and anions. The estimates of precision included all variability in the data-collection system, from the point of sample collection through storage in the NADP/NTN database. Sampling precision was determined from the absolute value of differences in the analytical results for the paired samples in terms of median relative and absolute difference. The median relative difference for Mg2+, Na+, K+ and NH4+ concentration and deposition was quite variable between sites and exceeded 10% at most sites. Relative error for analytes whose concentrations typically approached laboratory method detection limits were greater than for analytes that did not typically approach detection limits. The median relative difference for SO42- and NO3- concentration, specific conductance, and sample volume at all sites was less than 7%. Precision for H+ concentration and deposition ranged from less than 10% at sites with typically high levels of H+ concentration to greater than 30% at sites with low H+ concentration. Median difference for analyte concentration and deposition was typically 1.5-2-times greater for samples collected during the winter than during other seasons at two northern sites. Likewise, the median relative difference in sample volume for winter samples was more than double the annual median relative difference at the two northern sites. Bias accounted for less than 25% of the collocated variability in analyte concentration and deposition from weekly collocated precipitation samples at most sites.A collocated, wet-deposition sampler program has been operated since OCtober 1988 by the U.S Geological Survey to estimate the overall sampling precision of wet atmospheric deposition data collected at selected sites in the National Atmospheric Deposition Program and National Trends Network (NADP/NTN). A duplicate set of wet-deposition sampling instruments was installed adjacent to existing sampling instruments four different NADP/NTN sites for each year of the study. Wet-deposition samples from collocated sites were collected and analysed using standard NADP/NTN procedures. Laboratory analyses included determinations of pH, specific conductance, and concentrations of major cations and anions. The estimates of precision included all variability in the data-collection system, from the point of sample collection through storage in the NADP/NTN database.

  3. Effects of small-scale vertical variations in well-screen inflow rates and concentrations of organic compounds on the collection of representative ground-water-quality samples

    USGS Publications Warehouse

    Gibs, Jacob; Brown, G. Allan; Turner, Kenneth S.; MacLeod, Cecilia L.; Jelinski, James; Koehnlein, Susan A.

    1993-01-01

    Because a water sample collected from a well is an integration of water from different depths along the well screen, measured concentrations can be biased if analyte concentrations are not uniform along the length of the well screen. The resulting concentration in the sample, therefore, is a function of variations in well-screen inflow rate and analyte concentration with depth. A multiport sampler with seven short screened intervals was designed and used to investigate small-scale vertical variations in water chemistry and aquifer hydraulic conductivity in ground water contaminated by leaded gasoline at Galloway Township, Atlantic County, New Jersey. The multiport samplers were used to collect independent samples from seven intervals within the screened zone that were flow-rate weighted and integrated to simulate a 5-foot-long, 2.375-inch- outside-diameter conventional wire-wound screen. The integration of the results of analyses of samples collected from two multiport samplers showed that a conventional 5-foot-long well screen would integrate contaminant concentrations over its length and resulted in an apparent contaminant concentration that was a little as 28 percent of the maximum concentration observed in the multiport sampler.

  4. Rapid analytical determination of glutaraldehyde concentrations

    NASA Technical Reports Server (NTRS)

    Frigerio, N. A.; Shaw, M. H.

    1971-01-01

    Technique utilizes the iodimetric procedure which adds unknown excess of bisulfite to glutaraldehyde /GA/ then titrates unreacted bisulfite with standard iodine isotope to determine GA concentrations. Technique may interest microscopists, food researchers, biochemical or medical laboratories, and drug manufacturers.

  5. Quantitative imaging for discovery and assembly of the metabo-regulome

    PubMed Central

    Okumoto, Sakiko; Takanaga, Hitomi; Frommer, Wolf B.

    2009-01-01

    Summary Little is known about regulatory networks that control metabolic flux in plant cells. Detailed understanding of regulation is crucial for synthetic biology. The difficulty of measuring metabolites with cellular and subcellular precision is a major roadblock. New tools have been developed for monitoring extracellular, cytosolic, organellar and vacuolar ion and metabolite concentrations with a time resolution of milliseconds to hours. Genetically encoded sensors allow quantitative measurement of steady-state concentrations of ions, signaling molecules and metabolites and their respective changes over time. Fluorescence resonance energy transfer (FRET) sensors exploit conformational changes in polypeptides as a proxy for analyte concentrations. Subtle effects of analyte binding on the conformation of the recognition element are translated into a FRET change between two fused green fluorescent protein (GFP) variants, enabling simple monitoring of analyte concentrations using fluorimetry or fluorescence microscopy. Fluorimetry provides information averaged over cell populations, while microscopy detects differences between cells or populations of cells. The genetically encoded sensors can be targeted to subcellular compartments or the cell surface. Confocal microscopy ultimately permits observation of gradients or local differences within a compartment. The FRET assays can be adapted to high-throughput analysis to screen mutant populations in order to systematically identify signaling networks that control individual steps in metabolic flux. PMID:19138219

  6. Practical deviations from Henry`s law for water/air partitioning of volatile organic compounds

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Schabron, J.F.; Rovani, J.F. Jr.

    A study was conducted to define parameters relating to the use of a down hole submersible photoionization detector (PID) probe to measure volatile organic compounds (VOCs) in an artificial headspace. The partitioning of toluene and trichloroethylene between water and air was studied as a function of analyte concentration and water temperature. The Henry`s law constant governing this partitioning represents an ideal condition at infinite dilution for a particular temperature. The results show that in practice. this partitioning is far from ideal. Conditions resulting in apparent, practical deviations from Henry`s law include temperature and VOC concentration. Thus, a single value ofmore » Henry`s law constant for a particular VOC such as toluene can provide only an approximation of concentration in the field. Detector response in saturated humidity environments as a function of water temperature and analyte concentration was studied also.« less

  7. Evaluation of lipid-containing semipermeable membrane devices for monitoring organochlorine contaminants in the Upper Mississippi river

    USGS Publications Warehouse

    Ellis, Geoffrey S.; Rostad, Colleen E.; Huckins, James N.; Schmitt, Christopher J.; MacCarthy, Patrick

    1995-01-01

    Organochlorine contaminants sequestered in lipid-containing semipermeable membrane devices (SPMDs) were compared to those found in tangential-flow ultrafilter permeates as part of a pilot study at 10 sites in the Upper Mississippi River system. Caged and feral fish from three primary sites were also analyzed for comparison. Concentrated organochlorine (OC) compounds were readily extracted from the SPMDs by dialysis into hexane, and samples were analyzed by gas chromatography-negative chemical ionization-mass spectrometry. Fish and water samples were processed by conventional methods. Reasonable agreement was found between analyte SPMD-derived water concentrations and measured values of ultrafilter permeates; however, concentrations of the same analytes in caged fish did not appear to be proportional to water concentrations derived from SPMDs and ultrafilter permeates. The greatest number of OC compounds was detected in SPMDs; fewer were detected in caged fish and feral fish.

  8. Determination of nanomolar chromate in drinking water with solid phase extraction and a portable spectrophotometer.

    PubMed

    Ma, Jian; Yang, Bo; Byrne, Robert H

    2012-06-15

    Determination of chromate at low concentration levels in drinking water is an important analytical objective for both human health and environmental science. Here we report the use of solid phase extraction (SPE) in combination with a custom-made portable light-emitting diode (LED) spectrophotometer to achieve detection of chromate in the field at nanomolar levels. The measurement chemistry is based on a highly selective reaction between 1,5-diphenylcarbazide (DPC) and chromate under acidic conditions. The Cr-DPC complex formed in the reaction can be extracted on a commercial C18 SPE cartridge. Concentrated Cr-DPC is subsequently eluted with methanol and detected by spectrophotometry. Optimization of analytical conditions involved investigation of reagent compositions and concentrations, eluent type, flow rate (sample loading), sample volume, and stability of the SPE cartridge. Under optimized conditions, detection limits are on the order of 3 nM. Only 50 mL of sample is required for an analysis, and total analysis time is around 10 min. The targeted analytical range of 0-500 nM can be easily extended by changing the sample volume. Compared to previous SPE-based spectrophotometric methods, this analytical procedure offers the benefits of improved sensitivity, reduced sample consumption, shorter analysis time, greater operational convenience, and lower cost. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Tank Vapor Characterization Project: Tank 241-S-102 fourth temporal study: Headspace gas and vapor characterization results from samples collected on December 19, 1996

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pool, K.H.; Evans, J.C.; Olsen, K.B.

    1997-08-01

    This report presents the results from analyses of samples taken from the headspace of waste storage tank 241-S-102 (Tank S-102) at the Hanford Site in Washington State. Tank headspace samples collected by SGN Eurisys Service Corporation (SESC) were analyzed by Pacific Northwest National Laboratory (PNNL) to determine headspace concentrations of selected non-radioactive analytes. Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Vapor concentrations from sorbent trap samples are based on measured sample volumes provided by SESC. Ammonia was determined to be above the immediate notification limit of 150 ppm as specified by the sampling and analysis planmore » (SAP). Hydrogen was the principal flammable constituent of the Tank S-102 headspace, determined to be present at approximately 2.410% of its lower flammability limit (LFL). Total headspace flammability was estimated to be <2.973% of its lower flammability limit (LFL). Total headspace flammability was estimated to be <2.973% of the LFL. Average measured concentrations of targeted gases, inorganic vapors, and selected organic vapors are provided in Table S.1. A summary of experimental methods, including sampling methodology, analytical procedures, and quality assurance and control methods are presented in Section 2.0. Detailed descriptions of the analytical results are provided in Section 3.0.« less

  10. Can neutral analytes be concentrated by transient isotachophoresis in micellar electrokinetic chromatography and how much?

    PubMed

    Matczuk, Magdalena; Foteeva, Lidia S; Jarosz, Maciej; Galanski, Markus; Keppler, Bernhard K; Hirokawa, Takeshi; Timerbaev, Andrei R

    2014-06-06

    Transient isotachophoresis (tITP) is a versatile sample preconcentration technique that uses ITP to focus electrically charged analytes at the initial stage of CE analysis. However, according to the ruling principle of tITP, uncharged analytes are beyond its capacity while being separated and detected by micellar electrokinetic chromatography (MEKC). On the other hand, when these are charged micelles that undergo the tITP focusing, one can anticipate the concentration effect, resulting from the formation of transient micellar stack at moving sample/background electrolyte (BGE) boundary, which increasingly accumulates the analytes. This work expands the enrichment potential of tITP for MEKC by demonstrating the quantitative analysis of uncharged metal-based drugs from highly saline samples and introducing to the BGE solution anionic surfactants and buffer (terminating) co-ions of different mobility and concentration to optimize performance. Metallodrugs of assorted lipophilicity were chosen so as to explore whether their varying affinity toward micelles plays the role. In addition to altering the sample and BGE composition, optimization of the detection capability was achieved due to fine-tuning operational variables such as sample volume, separation voltage and pressure, etc. The results of optimization trials shed light on the mechanism of micellar tITP and render effective determination of selected drugs in human urine, with practical limits of detection using conventional UV detector. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Pre-analytical effects of blood sampling and handling in quantitative immunoassays for rheumatoid arthritis.

    PubMed

    Zhao, Xiaoyan; Qureshi, Ferhan; Eastman, P Scott; Manning, William C; Alexander, Claire; Robinson, William H; Hesterberg, Lyndal K

    2012-04-30

    Variability in pre-analytical blood sampling and handling can significantly impact results obtained in quantitative immunoassays. Understanding the impact of these variables is critical for accurate quantification and validation of biomarker measurements. Particularly, in the design and execution of large clinical trials, even small differences in sample processing and handling can have dramatic effects in analytical reliability, results interpretation, trial management and outcome. The effects of two common blood sampling methods (serum vs. plasma) and two widely-used serum handling methods (on the clot with ambient temperature shipping, "traditional", vs. centrifuged with cold chain shipping, "protocol") on protein and autoantibody concentrations were examined. Matched serum and plasma samples were collected from 32 rheumatoid arthritis (RA) patients representing a wide range of disease activity status. Additionally, a set of matched serum samples with two sample handling methods was collected. One tube was processed per manufacturer's instructions and shipped overnight on cold packs (protocol). The matched tube, without prior centrifugation, was simultaneously shipped overnight at ambient temperatures (traditional). Upon delivery, the traditional tube was centrifuged. All samples were subsequently aliquoted and frozen prior to analysis of protein and autoantibody biomarkers. Median correlation between paired serum and plasma across all autoantibody assays was 0.99 (0.98-1.00) with a median % difference of -3.3 (-7.5 to 6.0). In contrast, observed protein biomarker concentrations were significantly affected by sample types, with median correlation of 0.99 (0.33-1.00) and a median % difference of -10 (-55 to 23). When the two serum collection/handling methods were compared, the median correlation between paired samples for autoantibodies was 0.99 (0.91-1.00) with a median difference of 4%. In contrast, significant increases were observed in protein biomarker concentrations among certain biomarkers in samples processed with the 'traditional' method. Autoantibody quantification appears robust to both sample type (plasma vs. serum) and pre-analytical sample collection/handling methods (protocol vs. traditional). In contrast, for non-antibody protein biomarker concentrations, sample type had a significant impact; plasma samples generally exhibit decreased protein biomarker concentrations relative to serum. Similarly, sample handling significantly impacted the variability of protein biomarker concentrations. When biomarker concentrations are combined algorithmically into a single test score such as a multi-biomarker disease activity test for rheumatoid arthritis (MBDA), changes in protein biomarker concentrations may result in a bias of the score. These results illustrate the importance of characterizing pre-analytical methodology, sample type, sample processing and handling procedures for clinical testing in order to ensure test accuracy. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. 40 CFR 1065.750 - Analytical gases.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... O2 concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen... concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen. (3) Use the....41) mol/mol, balance He, and a stated total hydrocarbon concentration of 0.05 µmol/mol or less. (ii...

  13. 40 CFR 1065.750 - Analytical gases.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... O2 concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen... concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen. (3) Use the....41) mol/mol, balance He, and a stated total hydrocarbon concentration of 0.05 µmol/mol or less. (ii...

  14. 40 CFR 1065.750 - Analytical gases.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... O2 concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen... concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen. (3) Use the....41) mol/mol, balance He, and a stated total hydrocarbon concentration of 0.05 µmol/mol or less. (ii...

  15. 40 CFR 1065.750 - Analytical gases.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... O2 concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen... concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen. (3) Use the....41) mol/mol, balance He, and a stated total hydrocarbon concentration of 0.05 µmol/mol or less. (ii...

  16. Comparison of soil sampling and analytical methods for asbestos at the Sumas Mountain Asbestos Site—Working towards a toolbox for better assessment

    EPA Science Inventory

    Established soil sampling methods for asbestos are inadequate to support risk assessment and risk-based decision making at Superfund sites due to difficulties in detecting asbestos at low concentrations and difficulty in extrapolating soil concentrations to air concentrations. En...

  17. [Concentrations and influencing factors of gaseous polycyclic aromatic hydrocarbons in residential air in Beijing].

    PubMed

    Wei, Zhi-cheng; Chang, Biao; Qiu, Wei-xun; Wang, Yi; Wu, Shi-min; Xing, Bao-shan; Liu, Wen-xin; Tao, Shu

    2007-09-01

    7 gas phase PAHs components in indoor air collected from 38 families were investigated by modified passive air samplers in Beijing areas during the local heating and non-heating seasons, and the influencing factors were discussed as well. The analytical results indicate that the gasous PAHs in local indoor air are dominated by 2 and 3 rings compounds, the mean concentrations for the 7 individual gaseous components range from 1 to 40 ng/m3, and the average concentration of total gaseous PAHs is about 100 ng/m3. There is no significant difference in total gaseous PAHs concentrations between the heating and the non-heating seasons, while some apparent seasonal changes occur in ACY and FLA concentrations. Compared with heating season, contribution of 2 rings compounds decreases while the proportions of 3 and 4 rings species increase during the non-heating season. Based on household activity questionnaires and actual analytical concentrations, the main influencing factors accounted for gaseous PAHs in indoor air, identified by multifactor analysis of variance, include cigarette smoking, use of moth ball, intensity of draft, cuisine frequency and built age.

  18. STATISTICAL EVALUATION OF AN ANALYTICAL GC/MS METHOD FOR THE DETERMINATION OF LONG CHAIN FATTY ACIDS

    EPA Science Inventory

    In-depth evaluation of an analytical method to detect and quantify long chain fatty acids (C8 - C16) at trace level concentrations (25-1000 µg/l) is presented. The method requires derivatization of the acids with methanolic boron trifluoride, separation, and...

  19. Liquid-Liquid Extraction of Insecticides from Juice: An Analytical Chemistry Laboratory Experiment

    ERIC Educational Resources Information Center

    Radford, Samantha A.; Hunter, Ronald E., Jr.; Barr, Dana Boyd; Ryan, P. Barry

    2013-01-01

    A laboratory experiment was developed to target analytical chemistry students and to teach them about insecticides in food, sample extraction, and cleanup. Micro concentrations (sub-microgram/mL levels) of 12 insecticides spiked into apple juice samples are extracted using liquid-liquid extraction and cleaned up using either a primary-secondary…

  20. Different analytical approaches in assessing antibacterial activity and the purity of commercial lysozyme preparations for dairy application.

    PubMed

    Brasca, Milena; Morandi, Stefano; Silvetti, Tiziana; Rosi, Veronica; Cattaneo, Stefano; Pellegrino, Luisa

    2013-05-21

    Hen egg-white lysozyme (LSZ) is currently used in the food industry to limit the proliferation of lactic acid bacteria spoilage in the production of wine and beer, and to inhibit butyric acid fermentation in hard and extra hard cheeses (late blowing) caused by the outgrowth of clostridial spores. The aim of this work was to evaluate how the enzyme activity in commercial preparations correlates to the enzyme concentration and can be affected by the presence of process-related impurities. Different analytical approaches, including turbidimetric assay, SDS-PAGE and HPLC were used to analyse 17 commercial preparations of LSZ marketed in different countries. The HPLC method adopted by ISO allowed the true LSZ concentration to be determined with accuracy. The turbidimetric assay was the most suitable method to evaluate LSZ activity, whereas SDS-PAGE allowed the presence of other egg proteins, which are potential allergens, to be detected. The analytical results showed that the purity of commercially available enzyme preparations can vary significantly, and evidenced the effectiveness of combining different analytical approaches in this type of control.

  1. Electrospun polyvinyl alcohol ultra-thin layer chromatography of amino acids.

    PubMed

    Lu, Tian; Olesik, Susan V

    2013-01-01

    Electrospun polyvinyl alcohol (PVA) ultrathin layer chromatographic (UTLC) plates were fabricated using in situ crosslinking electrospinning technique. The value of these ULTC plates were characterized using the separation of fluorescein isothiocyanate (FITC) labeled amino acids and the separation of amino acids followed visualization using ninhydrin. The in situ crosslinked electrospun PVA plates showed enhanced stability in water and were stable when used for the UTLC study. The selectivity of FITC labeled amino acids on PVA plate was compared with that on commercial Si-Gel plate. The efficiency of the separation varied with analyte concentration, size of capillary analyte applicator, analyte volume, and mat thickness. The concentration of 7mM or less, 50μm i.d. capillary applicator, minimum volume of analyte solution and three-layered mat provides the best efficiency of FITC-labeled amino acids on PVA UTLC plate. The efficiency on PVA plate was greatly improved compared to the efficiency on Si-Gel HPTLC plate. The hydrolysis products of aspartame in diet coke, aspartic acid and phenylalanine, were also successfully analyzed using PVA-UTLC plate. Copyright © 2012 Elsevier B.V. All rights reserved.

  2. Software Compensates Electronic-Nose Readings for Humidity

    NASA Technical Reports Server (NTRS)

    Zhou, Hanying

    2007-01-01

    A computer program corrects for the effects of humidity on the readouts of an array of chemical sensors (an "electronic nose"). To enable the use of this program, the array must incorporate an independent humidity sensor in addition to sensors designed to detect analytes other than water vapor. The basic principle of the program was described in "Compensating for Effects of Humidity on Electronic Noses" (NPO-30615), NASA Tech Briefs, Vol. 28, No. 6 (June 2004), page 63. To recapitulate: The output of the humidity sensor is used to generate values that are subtracted from the outputs of the other sensors to correct for contributions of humidity to those readings. Hence, in principle, what remains after corrections are the contributions of the analytes only. The outputs of the non-humidity sensors are then deconvolved to obtain the concentrations of the analytes. In addition, the humidity reading is retained as an analyte reading in its own right. This subtraction of the humidity background increases the ability of the software to identify such events as spills in which contaminants may be present in small concentrations and accompanied by large changes in humidity.

  3. Analytical Modeling of a Double-Sided Flux Concentrating E-Core Transverse Flux Machine with Pole Windings

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Muljadi, Eduard; Hasan, Iftekhar; Husain, Tausif

    In this paper, a nonlinear analytical model based on the Magnetic Equivalent Circuit (MEC) method is developed for a double-sided E-Core Transverse Flux Machine (TFM). The proposed TFM has a cylindrical rotor, sandwiched between E-core stators on both sides. Ferrite magnets are used in the rotor with flux concentrating design to attain high airgap flux density, better magnet utilization, and higher torque density. The MEC model was developed using a series-parallel combination of flux tubes to estimate the reluctance network for different parts of the machine including air gaps, permanent magnets, and the stator and rotor ferromagnetic materials, in amore » two-dimensional (2-D) frame. An iterative Gauss-Siedel method is integrated with the MEC model to capture the effects of magnetic saturation. A single phase, 1 kW, 400 rpm E-Core TFM is analytically modeled and its results for flux linkage, no-load EMF, and generated torque, are verified with Finite Element Analysis (FEA). The analytical model significantly reduces the computation time while estimating results with less than 10 percent error.« less

  4. Insulator-based DEP with impedance measurements for analyte detection

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Davalos, Rafael V.; Simmons, Blake A.; Crocker, Robert W.

    2010-03-16

    Disclosed herein are microfluidic devices for assaying at least one analyte specie in a sample comprising at least one analyte concentration area in a microchannel having insulating structures on or in at least one wall of the microchannel which provide a nonuniform electric field in the presence of an electric field provided by off-chip electrodes; and a pair of passivated sensing electrodes for impedance detection in a detection area. Also disclosed are assay methods and methods of making.

  5. EPA Region 6 Laboratory Method Specific Analytical Capabilities with Sample Concentration Range

    EPA Pesticide Factsheets

    EPA Region 6 Environmental Services Branch (ESB) Laboratory is capable of analyzing a wide range of samples with concentrations ranging for low part-per trillion (ppt) to low percent () levels, depending on the sample matrix.

  6. Analytical solutions of one-dimensional multispecies reactive transport in a permeable reactive barrier-aquifer system

    NASA Astrophysics Data System (ADS)

    Mieles, John; Zhan, Hongbin

    2012-06-01

    The permeable reactive barrier (PRB) remediation technology has proven to be more cost-effective than conventional pump-and-treat systems, and has demonstrated the ability to rapidly reduce the concentrations of specific chemicals of concern (COCs) by up to several orders of magnitude in some scenarios. This study derives new steady-state analytical solutions to multispecies reactive transport in a PRB-aquifer (dual domain) system. The advantage of the dual domain model is that it can account for the potential existence of natural degradation in the aquifer, when designing the required PRB thickness. The study focuses primarily on the steady-state analytical solutions of the tetrachloroethene (PCE) serial degradation pathway and secondly on the analytical solutions of the parallel degradation pathway. The solutions in this study can also be applied to other types of dual domain systems with distinct flow and transport properties. The steady-state analytical solutions are shown to be accurate and the numerical program RT3D is selected for comparison. The results of this study are novel in that the solutions provide improved modeling flexibility including: 1) every species can have unique first-order reaction rates and unique retardation factors, and 2) daughter species can be modeled with their individual input concentrations or solely as byproducts of the parent species. The steady-state analytical solutions exhibit a limitation that occurs when interspecies reaction rate factors equal each other, which result in undefined solutions. Excel spreadsheet programs were created to facilitate prompt application of the steady-state analytical solutions, for both the serial and parallel degradation pathways.

  7. Quantitative interference by cysteine and N-acetylcysteine metabolites during the LC-MS/MS bioanalysis of a small molecule.

    PubMed

    Barricklow, Jason; Ryder, Tim F; Furlong, Michael T

    2009-08-01

    During LC-MS/MS quantification of a small molecule in human urine samples from a clinical study, an unexpected peak was observed to nearly co-elute with the analyte of interest in many study samples. Improved chromatographic resolution revealed the presence of at least 3 non-analyte peaks, which were identified as cysteine metabolites and N-acetyl (mercapturic acid) derivatives thereof. These metabolites produced artifact responses in the parent compound MRM channel due to decomposition in the ionization source of the mass spectrometer. Quantitative comparison of the analyte concentrations in study samples using the original chromatographic method and the improved chromatographic separation method demonstrated that the original method substantially over-estimated the analyte concentration in many cases. The substitution of electrospray ionization (ESI) for atmospheric pressure chemical ionization (APCI) nearly eliminated the source instability of these metabolites, which would have mitigated their interference in the quantification of the analyte, even without chromatographic separation. These results 1) demonstrate the potential for thiol metabolite interferences during the quantification of small molecules in pharmacokinetic samples, and 2) underscore the need to carefully evaluate LC-MS/MS methods for molecules that can undergo metabolism to thiol adducts to ensure that they are not susceptible to such interferences during quantification.

  8. Capillary waveguide optrodes: an approach to optical sensing in medical diagnostics

    NASA Astrophysics Data System (ADS)

    Lippitsch, Max E.; Draxler, Sonja; Kieslinger, Dietmar; Lehmann, Hartmut; Weigl, Bernhard H.

    1996-07-01

    Glass capillaries with a chemically sensitive coating on the inner surface are used as optical sensors for medical diagnostics. A capillary simultaneously serves as a sample compartment, a sensor element, and an inhomogeneous optical waveguide. Various detection schemes based on absorption, fluorescence intensity, or fluorescence lifetime are described. In absorption-based capillary waveguide optrodes the absorption in the sensor layer is analyte dependent; hence light transmission along the inhomogeneous waveguiding structure formed by the capillary wall and the sensing layer is a function of the analyte concentration. Similarly, in fluorescence-based capillary optrodes the fluorescence intensity or the fluorescence lifetime of an indicator dye fixed in the sensing layer is analyte dependent; thus the specific property of fluorescent light excited in the sensing layer and thereafter guided along the inhomogeneous waveguiding structure is a function of the analyte concentration. Both schemes are experimentally demonstrated, one with carbon dioxide as the analyte and the other one with oxygen. The device combines optical sensors with the standard glass capillaries usually applied to gather blood drops from fingertips, to yield a versatile diagnostic instrument, integrating the sample compartment, the optical sensor, and the light-collecting optics into a single piece. This ensures enhanced sensor performance as well as improved handling compared with other sensors. waveguide, blood gases, medical diagnostics.

  9. Thickness dependences of solar cell performance

    NASA Technical Reports Server (NTRS)

    Sah, C. T.

    1982-01-01

    The significance of including factors such as the base resistivity loss for solar cells thicker than 100 microns and emitter and BSF layer recombination for thin cells in predicting the fill factor and efficiency of solar cells is demonstrated analytically. A model for a solar cell is devised with the inclusion of the dopant impurity concentration profile, variation of the electron and hole mobility with dopant concentration, the concentration and thermal capture and emission rates of the recombination center, device temperature, the AM1 spectra and the Si absorption coefficient. Device equations were solved by means of the transmission line technique. The analytical results were compared with those of low-level theory for cell performance. Significant differences in predictions of the fill factor resulted, and inaccuracies in the low-level approximations are discussed.

  10. Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York--July 1999 through June 2001

    USGS Publications Warehouse

    Lincoln, Tricia A.; Horan-Ross, Debra A.; McHale, Michael R.; Lawrence, Gregory B.

    2006-01-01

    The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's LabMaster data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality-control samples analyzed from July 1999 through June 2001. Results for the quality-control samples for 18 analytical procedures were evaluated for bias and precision. Control charts indicate that data for eight of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, total aluminum, calcium, chloride and nitrate (ion chromatography and colormetric method) and sulfate. The total aluminum and dissolved organic carbon procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits. The calcium and specific conductance procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The magnesium procedure was biased for the high-concentration and low concentration samples, but was within control limits. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 14 of 15 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 17 of the 18 analytes. At least 90 percent of the samples met data-quality objectives for all analytes except ammonium (81 percent of samples met objectives), chloride (75 percent of samples met objectives), and sodium (86 percent of samples met objectives). Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated good data quality over the time period, with most ratings for each sample in the good to excellent range. The P-sample (low-ionic-strength constituents) analysis had one satisfactory rating for the specific conductance procedure in one study. The T-sample (trace constituents) analysis had one satisfactory rating for the aluminum procedure in one study and one unsatisfactory rating for the sodium procedure in another. The remainder of the samples had good or excellent ratings for each study. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 89 percent of the samples met data-quality objectives for 10 of the 14 analytes; the exceptions were ammonium, total aluminum, dissolved organic carbon, and sodium. Results indicate a positive bias for the ammonium procedure in all studies. Data-quality objectives were not met in 50 percent of samples analyzed for total aluminum, 38 percent of samples analyzed for dissolved organic carbon, and 27 percent of samples analyzed for sodium. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 91 percent of the samples analyzed for calcium, chloride, fluoride, magnesium, pH, potassium, and sulfate. Data-quality objectives were met by 75 percent of the samples analyzed for sodium and 58 percent of the samples analyzed for specific conductance.

  11. Identifying or measuring selected substances or toxins in a subject using resonant raman signals

    NASA Technical Reports Server (NTRS)

    Borchert, Mark S. (Inventor); Lambert, James L. (Inventor)

    2005-01-01

    Methods and systems of the present invention identify the presence of and/or the concentration of a selected analyte in a subject by: (a) illuminating a selected region of the eye of a subject with an optical excitation beam, wherein the excitation beam wavelength is selected to generate a resonant Raman spectrum of the selected analyte with a signal strength that is at least 100 times greater than Raman spectrums generated by non-resonant wavelengths and/or relative to signals of normal constituents present in the selected region of the eye; (b) detecting a resonant Raman spectrum corresponding to the selected illuminated region of the eye; and (c) identifying the presence, absence and/or the concentration of the selected analyte in the subject based on said detecting step. The apparatus may also be configured to be able to obtain biometric data of the eye to identify (confirm the identity of) the subject.

  12. Analysis of Mathematical Modelling on Potentiometric Biosensors

    PubMed Central

    Mehala, N.; Rajendran, L.

    2014-01-01

    A mathematical model of potentiometric enzyme electrodes for a nonsteady condition has been developed. The model is based on the system of two coupled nonlinear time-dependent reaction diffusion equations for Michaelis-Menten formalism that describes the concentrations of substrate and product within the enzymatic layer. Analytical expressions for the concentration of substrate and product and the corresponding flux response have been derived for all values of parameters using the new homotopy perturbation method. Furthermore, the complex inversion formula is employed in this work to solve the boundary value problem. The analytical solutions obtained allow a full description of the response curves for only two kinetic parameters (unsaturation/saturation parameter and reaction/diffusion parameter). Theoretical descriptions are given for the two limiting cases (zero and first order kinetics) and relatively simple approaches for general cases are presented. All the analytical results are compared with simulation results using Scilab/Matlab program. The numerical results agree with the appropriate theories. PMID:25969765

  13. Analysis of mathematical modelling on potentiometric biosensors.

    PubMed

    Mehala, N; Rajendran, L

    2014-01-01

    A mathematical model of potentiometric enzyme electrodes for a nonsteady condition has been developed. The model is based on the system of two coupled nonlinear time-dependent reaction diffusion equations for Michaelis-Menten formalism that describes the concentrations of substrate and product within the enzymatic layer. Analytical expressions for the concentration of substrate and product and the corresponding flux response have been derived for all values of parameters using the new homotopy perturbation method. Furthermore, the complex inversion formula is employed in this work to solve the boundary value problem. The analytical solutions obtained allow a full description of the response curves for only two kinetic parameters (unsaturation/saturation parameter and reaction/diffusion parameter). Theoretical descriptions are given for the two limiting cases (zero and first order kinetics) and relatively simple approaches for general cases are presented. All the analytical results are compared with simulation results using Scilab/Matlab program. The numerical results agree with the appropriate theories.

  14. Smart phone: a popular device supports amylase activity assay in fisheries research.

    PubMed

    Thongprajukaew, Karun; Choodum, Aree; Sa-E, Barunee; Hayee, Ummah

    2014-11-15

    Colourimetric determinations of amylase activity were developed based on a standard dinitrosalicylic acid (DNS) staining method, using maltose as the analyte. Intensities and absorbances of red, green and blue (RGB) were obtained with iPhone imaging and Adobe Photoshop image analysis. Correlation of green and analyte concentrations was highly significant, and the accuracy of the developed method was excellent in analytical performance. The common iPhone has sufficient imaging ability for accurate quantification of maltose concentrations. Detection limits, sensitivity and linearity were comparable to a spectrophotometric method, but provided better inter-day precision. In quantifying amylase specific activity from a commercial source (P>0.02) and fish samples (P>0.05), differences compared with spectrophotometric measurements were not significant. We have demonstrated that iPhone imaging with image analysis in Adobe Photoshop has potential for field and laboratory studies of amylase. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. METHOD 544. DETERMINATION OF MICROCYSTINS AND ...

    EPA Pesticide Factsheets

    Method 544 is an accurate and precise analytical method to determine six microcystins (including MC-LR) and nodularin in drinking water using solid phase extraction and liquid chromatography tandem mass spectrometry (SPE-LC/MS/MS). The advantage of this SPE-LC/MS/MS is its sensitivity and ability to speciate the microcystins. This method development task establishes sample preservation techniques, sample concentration and analytical procedures, aqueous and extract holding time criteria and quality control procedures. Draft Method 544 undergone a multi-laboratory verification to ensure other laboratories can implement the method and achieve the quality control measures specified in the method. It is anticipated that Method 544 may be used in UCMR 4 to collect nationwide occurrence data for selected microcystins in drinking water. The purpose of this research project is to develop an accurate and precise analytical method to concentrate and determine selected MCs and nodularin in drinking water.

  16. In Vitro and In Vivo SERS Biosensing for Disease Diagnosis.

    PubMed

    Moore, T Joshua; Moody, Amber S; Payne, Taylor D; Sarabia, Grace M; Daniel, Alyssa R; Sharma, Bhavya

    2018-05-11

    For many disease states, positive outcomes are directly linked to early diagnosis, where therapeutic intervention would be most effective. Recently, trends in disease diagnosis have focused on the development of label-free sensing techniques that are sensitive to low analyte concentrations found in the physiological environment. Surface-enhanced Raman spectroscopy (SERS) is a powerful vibrational spectroscopy that allows for label-free, highly sensitive, and selective detection of analytes through the amplification of localized electric fields on the surface of a plasmonic material when excited with monochromatic light. This results in enhancement of the Raman scattering signal, which allows for the detection of low concentration analytes, giving rise to the use of SERS as a diagnostic tool for disease. Here, we present a review of recent developments in the field of in vivo and in vitro SERS biosensing for a range of disease states including neurological disease, diabetes, cardiovascular disease, cancer, and viral disease.

  17. Ratio-based vs. model-based methods to correct for urinary creatinine concentrations.

    PubMed

    Jain, Ram B

    2016-08-01

    Creatinine-corrected urinary analyte concentration is usually computed as the ratio of the observed level of analyte concentration divided by the observed level of the urinary creatinine concentration (UCR). This ratio-based method is flawed since it implicitly assumes that hydration is the only factor that affects urinary creatinine concentrations. On the contrary, it has been shown in the literature, that age, gender, race/ethnicity, and other factors also affect UCR. Consequently, an optimal method to correct for UCR should correct for hydration as well as other factors like age, gender, and race/ethnicity that affect UCR. Model-based creatinine correction in which observed UCRs are used as an independent variable in regression models has been proposed. This study was conducted to evaluate the performance of ratio-based and model-based creatinine correction methods when the effects of gender, age, and race/ethnicity are evaluated one factor at a time for selected urinary analytes and metabolites. It was observed that ratio-based method leads to statistically significant pairwise differences, for example, between males and females or between non-Hispanic whites (NHW) and non-Hispanic blacks (NHB), more often than the model-based method. However, depending upon the analyte of interest, the reverse is also possible. The estimated ratios of geometric means (GM), for example, male to female or NHW to NHB, were also compared for the two methods. When estimated UCRs were higher for the group (for example, males) in the numerator of this ratio, these ratios were higher for the model-based method, for example, male to female ratio of GMs. When estimated UCR were lower for the group (for example, NHW) in the numerator of this ratio, these ratios were higher for the ratio-based method, for example, NHW to NHB ratio of GMs. Model-based method is the method of choice if all factors that affect UCR are to be accounted for.

  18. Authentication of Kalix (N.E. Sweden) vendace caviar using inductively coupled plasma-based analytical techniques: evaluation of different approaches.

    PubMed

    Rodushkin, I; Bergman, T; Douglas, G; Engström, E; Sörlin, D; Baxter, D C

    2007-02-05

    Different analytical approaches for origin differentiation between vendace and whitefish caviars from brackish- and freshwaters were tested using inductively coupled plasma double focusing sector field mass spectrometry (ICP-SFMS) and multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). These approaches involve identifying differences in elemental concentrations or sample-specific isotopic composition (Sr and Os) variations. Concentrations of 72 elements were determined by ICP-SFMS following microwave-assisted digestion in vendace and whitefish caviar samples from Sweden (from both brackish and freshwater), Finland and USA, as well as in unprocessed vendace roe and salt used in caviar production. This data set allows identification of elements whose contents in caviar can be affected by salt addition as well as by contamination during production and packaging. Long-term method reproducibility was assessed for all analytes based on replicate caviar preparations/analyses and variations in element concentrations in caviar from different harvests were evaluated. The greatest utility for differentiation was demonstrated for elements with varying concentrations between brackish and freshwaters (e.g. As, Br, Sr). Elemental ratios, specifically Sr/Ca, Sr/Mg and Sr/Ba, are especially useful for authentication of vendace caviar processed from brackish water roe, due to the significant differences between caviar from different sources, limited between-harvest variations and relatively high concentrations in samples, allowing precise determination by modern analytical instrumentation. Variations in the 87Sr/86Sr ratio for vendace caviar from different harvests (on the order of 0.05-0.1%) is at least 10-fold less than differences between caviar processed from brackish and freshwater roe. Hence, Sr isotope ratio measurements (either by ICP-SFMS or by MC-ICP-MS) have great potential for origin differentiation. On the contrary, it was impossible to differentiate between Swedish caviar processed from brackish water roe and Finnish freshwater caviar based solely on 187Os/188Os ratios.

  19. Biological Variation of Chloride and Sodium in Sweat Obtained by Pilocarpine Iontophoresis in Adults: How Sure are You About Sweat Test Results?

    PubMed

    Willems, Philippe; Weekx, Steven; Meskal, Anissa; Schouwers, Sofie

    2017-04-01

    The measurement of chloride and sodium concentrations in sweat is an important test for the diagnosis of cystic fibrosis (CF). The aim of this study was to assess the analytical variation (CV A ) and within-subject (CV I ) and between-subject (CV G ) biological variation of chloride and sodium concentrations in sweat, collected by pilocarpine iontophoresis and to determine their effect on the clinical interpretation of sweat test results. Twelve Caucasian adults (six male and six female) without symptoms suggestive for CF and with a mean age of 41 years (range 28-59) were included in the study. At least eight samples of sweat were collected from each individual by pilocarpine iontophoresis. Chloride and sodium concentrations were measured in duplicate for each sample using ion selective electrodes. After the removal of outliers, the CV A , CV I , and CV G of chloride and sodium were determined, and their impact on measurement uncertainty and reference change value were calculated. The CV A , CV I , and CV G of chloride in sweat samples were 6.5, 17.7, and 47.2%, respectively. The CV A , CV I , and CV G of sodium sweat samples were 6.0, 17.5, and 42.6%, respectively. Our study indicates that sweat chloride and sodium concentration results must be interpreted with great care. Different components of variation, particularly the biological variations, have a considerable impact on the interpretation of these results. If no pre-analytical, analytical, or post-analytical errors are suspected, repeated sweat testing to confirm first-measurement results might not be desirable.

  20. A large-scale superhydrophobic surface-enhanced Raman scattering (SERS) platform fabricated via capillary force lithography and assembly of Ag nanocubes for ultratrace molecular sensing.

    PubMed

    Tan, Joel Ming Rui; Ruan, Justina Jiexin; Lee, Hiang Kwee; Phang, In Yee; Ling, Xing Yi

    2014-12-28

    An analytical platform with an ultratrace detection limit in the atto-molar (aM) concentration range is vital for forensic, industrial and environmental sectors that handle scarce/highly toxic samples. Superhydrophobic surface-enhanced Raman scattering (SERS) platforms serve as ideal platforms to enhance detection sensitivity by reducing the random spreading of aqueous solution. However, the fabrication of superhydrophobic SERS platforms is generally limited due to the use of sophisticated and expensive protocols and/or suffers structural and signal inconsistency. Herein, we demonstrate a high-throughput fabrication of a stable and uniform superhydrophobic SERS platform for ultratrace molecular sensing. Large-area box-like micropatterns of the polymeric surface are first fabricated using capillary force lithography (CFL). Subsequently, plasmonic properties are incorporated into the patterned surfaces by decorating with Ag nanocubes using the Langmuir-Schaefer technique. To create a stable superhydrophobic SERS platform, an additional 25 nm Ag film is coated over the Ag nanocube-decorated patterned template followed by chemical functionalization with perfluorodecanethiol. Our resulting superhydrophobic SERS platform demonstrates excellent water-repellency with a static contact angle of 165° ± 9° and a consequent analyte concentration factor of 59-fold, as compared to its hydrophilic counterpart. By combining the analyte concentration effect of superhydrophobic surfaces with the intense electromagnetic "hot spots" of Ag nanocubes, our superhydrophobic SERS platform achieves an ultra-low detection limit of 10(-17) M (10 aM) for rhodamine 6G using just 4 μL of analyte solutions, corresponding to an analytical SERS enhancement factor of 10(13). Our fabrication protocol demonstrates a simple, cost- and time-effective approach for the large-scale fabrication of a superhydrophobic SERS platform for ultratrace molecular detection.

  1. Stability of Routine Biochemical Analytes in Whole Blood and Plasma From Lithium Heparin Gel Tubes During 6-hr Storage.

    PubMed

    Monneret, Denis; Godmer, Alexandre; Le Guen, Ronan; Bravetti, Clotilde; Emeraud, Cecile; Marteau, Anthony; Alkouri, Rana; Mestari, Fouzi; Dever, Sylvie; Imbert-Bismut, Françoise; Bonnefont-Rousselot, Dominique

    2016-09-01

    The stability of biochemical analytes has already been investigated, but results strongly differ depending on parameters, methodologies, and sample storage times. We investigated the stability for many biochemical parameters after different storage times of both whole blood and plasma, in order to define acceptable pre- and postcentrifugation delays in hospital laboratories. Twenty-four analytes were measured (Modular® Roche analyzer) in plasma obtained from blood collected into lithium heparin gel tubes, after 2-6 hr of storage at room temperature either before (n = 28: stability in whole blood) or after (n = 21: stability in plasma) centrifugation. Variations in concentrations were expressed as mean bias from baseline, using the analytical change limit (ACL%) or the reference change value (RCV%) as acceptance limit. In tubes stored before centrifugation, mean plasma concentrations significantly decreased after 3 hr for phosphorus (-6.1% [95% CI: -7.4 to -4.7%]; ACL 4.62%) and lactate dehydrogenase (LDH; -5.7% [95% CI: -7.4 to -4.1%]; ACL 5.17%), and slightly decreased after 6 hr for potassium (-2.9% [95% CI: -5.3 to -0.5%]; ACL 4.13%). In plasma stored after centrifugation, mean concentrations decreased after 6 hr for bicarbonates (-19.7% [95% CI: -22.9 to -16.5%]; ACL 15.4%), and moderately increased after 4 hr for LDH (+6.0% [95% CI: +4.3 to +7.6%]; ACL 5.17%). Based on RCV, all the analytes can be considered stable up to 6 hr, whether before or after centrifugation. This study proposes acceptable delays for most biochemical tests on lithium heparin gel tubes arriving at the laboratory or needing to be reanalyzed. © 2016 Wiley Periodicals, Inc.

  2. Effects of freezer storage time on levels of complement biomarkers.

    PubMed

    Morgan, Angharad R; O'Hagan, Caroline; Touchard, Samuel; Lovestone, Simon; Morgan, B Paul

    2017-11-06

    There is uncertainty regarding how stable complement analytes are during long-term storage at - 80 °C. As part of our work program we have measured 17 complement biomarkers (C1q, C1 inhibitor, C3, C3a, iC3b, C4, C5, C9, FB, FD, FH, FI, TCC, Bb, sCR1, sCR2, Clusterin) and the benchmark inflammatory marker C-reactive protein (CRP) in a large set of plasma samples (n = 720) that had been collected, processed and subsequently stored at - 80 °C over a period of 6.6-10.6 years, prior to laboratory analysis. The biomarkers were measured using solid-phase enzyme immunoassays with a combination of multiplex assays using the MesoScale Discovery Platform and single-plex enzyme-linked immunosorbent assays (ELISAs). As part of a post hoc analysis of extrinsic factors (co-variables) affecting the analyses we investigated the impact of freezer storage time on the values obtained for each complement analyte. With the exception of five analytes (C4, C9, sCR2, clusterin and CRP), storage time was significantly correlated with measured plasma concentrations. For ten analytes: C3, FI, FB, FD, C5, sCR1, C3a, iC3b, Bb and TCC, storage time was positively correlated with concentration and for three analytes: FH, C1q, and C1 inhibitor, storage time was negatively correlated with concentration. The results suggest that information on storage time should be regarded as an important co-variable and taken into consideration when analysing data to look for associations of complement biomarker levels and disease or other outcomes.

  3. Ground-water and soil contamination near two pesticide-burial sites in Minnesota

    USGS Publications Warehouse

    Stark, J.R.; Strudell, J.D.; Bloomgren, P.A.; Eger, P.

    1987-01-01

    In general, concentrations of lead and arsenic in soil and groundwater were below background concentrations for the areas. Concentrations of organic pesticides generally were below analytical-detection limits. The limited solubility of the chemicals and the tendency of the contaminants to be sorbed on soil particles probably combined to restrict mobilization of the chemicals.

  4. Determination of Mercury in Milk by Cold Vapor Atomic Fluorescence: A Green Analytical Chemistry Laboratory Experiment

    ERIC Educational Resources Information Center

    Armenta, Sergio; de la Guardia, Miguel

    2011-01-01

    Green analytical chemistry principles were introduced to undergraduate students in a laboratory experiment focused on determining the mercury concentration in cow and goat milk. In addition to traditional goals, such as accuracy, precision, sensitivity, and limits of detection in method selection and development, attention was paid to the…

  5. Mercury concentrations in estuarine sediments, Lavaca and Matagorda bays, Texas, 1992

    USGS Publications Warehouse

    Brown, David S.; Snyder, Grant L.; Taylor, R. Lynn

    1998-01-01

    U.S. Environmental Protection Agency Method 7471 (Cold Vapor Atomic Absorption) was an acceptable analytical method for determining the total mercury concentrations in the Lavaca-Matagorda Bays estuarine sediment samples. Measurement of additional trace metals would aid in the characterization of total mercury concentrations and in the identification of concentrator/collector relations that are principally responsible for the adsorption of mercurous compounds to particulates in the bottom sediments.

  6. Prioritizing pesticide compounds for analytical methods development

    USGS Publications Warehouse

    Norman, Julia E.; Kuivila, Kathryn; Nowell, Lisa H.

    2012-01-01

    The U.S. Geological Survey (USGS) has a periodic need to re-evaluate pesticide compounds in terms of priorities for inclusion in monitoring and studies and, thus, must also assess the current analytical capabilities for pesticide detection. To meet this need, a strategy has been developed to prioritize pesticides and degradates for analytical methods development. Screening procedures were developed to separately prioritize pesticide compounds in water and sediment. The procedures evaluate pesticide compounds in existing USGS analytical methods for water and sediment and compounds for which recent agricultural-use information was available. Measured occurrence (detection frequency and concentrations) in water and sediment, predicted concentrations in water and predicted likelihood of occurrence in sediment, potential toxicity to aquatic life or humans, and priorities of other agencies or organizations, regulatory or otherwise, were considered. Several existing strategies for prioritizing chemicals for various purposes were reviewed, including those that identify and prioritize persistent, bioaccumulative, and toxic compounds, and those that determine candidates for future regulation of drinking-water contaminants. The systematic procedures developed and used in this study rely on concepts common to many previously established strategies. The evaluation of pesticide compounds resulted in the classification of compounds into three groups: Tier 1 for high priority compounds, Tier 2 for moderate priority compounds, and Tier 3 for low priority compounds. For water, a total of 247 pesticide compounds were classified as Tier 1 and, thus, are high priority for inclusion in analytical methods for monitoring and studies. Of these, about three-quarters are included in some USGS analytical method; however, many of these compounds are included on research methods that are expensive and for which there are few data on environmental samples. The remaining quarter of Tier 1 compounds are high priority as new analytes. The objective for analytical methods development is to design an integrated analytical strategy that includes as many of the Tier 1 pesticide compounds as possible in a relatively few, cost-effective methods. More than 60 percent of the Tier 1 compounds are high priority because they are anticipated to be present at concentrations approaching levels that could be of concern to human health or aquatic life in surface water or groundwater. An additional 17 percent of Tier 1 compounds were frequently detected in monitoring studies, but either were not measured at levels potentially relevant to humans or aquatic organisms, or do not have benchmarks available with which to compare concentrations. The remaining 21 percent are pesticide degradates that were included because their parent pesticides were in Tier 1. Tier 1 pesticide compounds for water span all major pesticide use groups and a diverse range of chemical classes, with herbicides and their degradates composing half of compounds. Many of the high priority pesticide compounds also are in several national regulatory programs for water, including those that are regulated in drinking water by the U.S. Environmental Protection Agency under the Safe Drinking Water Act and those that are on the latest Contaminant Candidate List. For sediment, a total of 175 pesticide compounds were classified as Tier 1 and, thus, are high priority for inclusion in analytical methods available for monitoring and studies. More than 60 percent of these compounds are included in some USGS analytical method; however, some are spread across several research methods that are expensive to perform, and monitoring data are not extensive for many compounds. The remaining Tier 1 compounds for sediment are high priority as new analytes. The objective for analytical methods development for sediment is to enhance an existing analytical method that currently includes nearly half of the pesticide compounds in Tier 1 by adding as many additional Tier 1 compounds as are analytically compatible. About 35 percent of the Tier 1 compounds for sediment are high priority on the basis of measured occurrence. A total of 74 compounds, or 42 percent, are high priority on the basis of predicted likelihood of occurrence according to physical-chemical properties, and either have potential toxicity to aquatic life, high pesticide useage, or both. The remaining 22 percent of Tier 1 pesticide compounds were either degradates of Tier 1 parent compounds or included for other reasons. As with water, the Tier 1 pesticide compounds for sediment are distributed across the major pesticide-use groups; insecticides and their degradates are the largest fraction, making up 45 percent of Tier 1. In contrast to water, organochlorines, at 17 percent, are the largest chemical class for Tier 1 in sediment, which is to be expected because there is continued widespread detection in sediments of persistent organochlorine pesticides and their degradates at concentrations high enough for potential effects on aquatic life. Compared to water, there are fewer available benchmarks with which to compare contaminant concentrations in sediment, but a total of 19 Tier 1 compounds have at least one sediment benchmark or screening value for aquatic organisms. Of the 175 compounds in Tier 1, 77 percent have high aquatic-life toxicity, as defined for this process. This evaluation of pesticides and degradates resulted in two lists of compounds that are priorities for USGS analytical methods development, one for water and one for sediment. These lists will be used as the basis for redesigning and enhancing USGS analytical capabilities for pesticides in order to capture as many high-priority pesticide compounds as possible using an economically feasible approach.

  7. Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York - July 2005 through June 2007

    USGS Publications Warehouse

    Lincoln, Tricia A.; Horan-Ross, Debra A.; McHale, Michael R.; Lawrence, Gregory B.

    2009-01-01

    The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's Lab Master data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality control samples analyzed from July 2005 through June 2007. Results for the quality-control samples for 19 analytical procedures were evaluated for bias and precision. Control charts indicate that data for eight of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: total aluminum, calcium, magnesium, nitrate (colorimetric method), potassium, silicon, sodium, and sulfate. Eight of the analytical procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits; these procedures were: total aluminum, calcium, dissolved organic carbon, chloride, nitrate (ion chromatograph), potassium, silicon, and sulfate. The magnesium and pH procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The acid-neutralizing capacity, total monomeric aluminum, nitrite, and specific conductance procedures were biased for the high-concentration and low-concentration samples, but were within control limits. Results from the filter-blank and analytical-blank analyses indicated that the procedures for 16 of 17 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 18 of the 21 analytes. At least 93 percent of the samples met data-quality objectives for all analytes except acid-neutralizing capacity (85 percent of samples met objectives), total monomeric aluminum (83 percent of samples met objectives), total aluminum (85 percent of samples met objectives), and chloride (85 percent of samples met objectives). The ammonium and total dissolved nitrogen did not meet the data-quality objectives. Results of the USGS interlaboratory Standard Reference Sample (SRS) Project met the Troy Laboratory data-quality objectives for 87 percent of the samples analyzed. The P-sample (low-ionic-strength constituents) analysis had two outliers each in two studies. The T-sample (trace constituents) analysis and the N-sample (nutrient constituents) analysis had one outlier each in two studies. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 85 percent of the samples met data-quality objectives for 11 of the 14 analytes; the exceptions were acid-neutralizing capacity, total aluminum and ammonium. Data-quality objectives were not met in 41 percent of samples analyzed for acid-neutralizing capacity, 50 percent of samples analyzed for total aluminum, and 44 percent of samples analyzed for ammonium. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 86 percent of the samples analyzed for calcium, magnesium, pH, potassium, and sodium. Data-quality objectives were met by 76 percent of the samples analyzed for chloride, 80 percent of the samples analyzed for specific conductance, and 77 percent of the samples analyzed for sulfate.

  8. Quality-assurance data for routine water analyses by the U.S. Geological Survey laboratory in Troy, New York - July 2003 through June 2005

    USGS Publications Warehouse

    Lincoln, Tricia A.; Horan-Ross, Debra A.; McHale, Michael R.; Lawrence, Gregory B.

    2009-01-01

    The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's Lab Master data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality control samples analyzed from July 2003 through June 2005. Results for the quality-control samples for 20 analytical procedures were evaluated for bias and precision. Control charts indicate that data for five of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, pH, silicon, and sodium. Seven of the analytical procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits; these procedures were: dissolved organic carbon, chloride, nitrate (ion chromatograph), nitrite, silicon, sodium, and sulfate. The calcium and magnesium procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The total aluminum and specific conductance procedures were biased for the high-concentration and low-concentration samples, but were within control limits. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 17 of 18 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 18 of the 22 analytes. At least 85 percent of the samples met data-quality objectives for all analytes except total monomeric aluminum (82 percent of samples met objectives), total aluminum (77 percent of samples met objectives), chloride (80 percent of samples met objectives), fluoride (76 percent of samples met objectives), and nitrate (ion chromatograph) (79 percent of samples met objectives). The ammonium and total dissolved nitrogen did not meet the data-quality objectives. Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated good data quality over the time period, with ratings for each sample in the satisfactory, good, and excellent ranges or less than 10 percent error. The P-sample (low-ionic-strength constituents) analysis had one marginal and two unsatisfactory ratings for the chloride procedure. The T-sample (trace constituents)analysis had two unsatisfactory ratings and one high range percent error for the aluminum procedure. The N-sample (nutrient constituents) analysis had one marginal rating for the nitrate procedure. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 84 percent of the samples met data-quality objectives for 11 of the 14 analytes; the exceptions were ammonium, total aluminum, and acid-neutralizing capacity. The ammonium procedure did not meet data quality objectives in all studies. Data-quality objectives were not met in 23 percent of samples analyzed for total aluminum and 45 percent of samples analyzed acid-neutralizing capacity. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 86 percent of the samples analyzed for calcium, chloride, fluoride, magnesium, pH, potassium, sodium, and sulfate. Data-quality objectives were not met by samples analyzed for fluoride. 

  9. Comparative study of inorganic elements determined in whole blood from Dmd(mdx)/J mice strain by EDXRF and NAA analytical techniques.

    PubMed

    Redígolo, M M; Sato, I M; Metairon, S; Zamboni, C B

    2016-04-01

    Several diseases can be diagnosed observing the variation of specific elements concentration in body fluids. In this study the concentration of inorganic elements in blood samples of dystrophic (Dmd(mdx)/J) and C57BL/6J (control group) mice strain were determined. The results obtained from Energy Dispersive X-ray Fluorescence (EDXRF) were compared with Neutron Activation Analysis (NAA) technique. Both analytical techniques showed to be appropriate and complementary offering a new contribution for veterinary medicine as well as detailed knowledge of this pathology. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Assessment of Polycyclic Aromatic Hydrocarbon Contamination of Breeding Pools Utilized by the Puerto Rican Crested Toad, Peltophryne lemur

    PubMed Central

    Gjeltema, Jenessa; Stoskopf, Michael; Shea, Damian; De Voe, Ryan

    2012-01-01

    Habitat preservation and management may play an important role in the conservation of the Puerto Rican crested toad, Peltophryne lemur, due to this species' small geographic range and declining native wild population. Bioavailable water concentrations of Polycyclic Aromatic Hydrocarbon (PAH) contaminants within breeding pools at 3 sites were established using Passive Sampling Devices (PSDs) and gas chromatography-mass spectrometry (GC/MS). A more diverse population of PAH analytes were found in higher concentrations at the breeding site that allowed direct vehicular access, but calculated risk quotients indicated low risk to toad reproduction associated with the current PAH analyte levels. PMID:23762634

  11. Protein associations and analytical ultracentrifugation

    NASA Astrophysics Data System (ADS)

    Laue, Tom

    2010-03-01

    Analytical ultracentrifugation (AUC) is a first principle method for characterizing the thermodynamics of macromolecules in solution. Since AUC directly assesses mass, it is particularly useful for characterizing both reversible and irreversible binding interactions between macromolecules. The principle measurement in AUC is the concentration as a function of radial position, which may be provided by either absorbance, interference or fluorescence detection. Each of these three different detectors may be used to characterize protein associations using either sedimentation equilibrium or sedimentation velocity analysis. Examples will be shown for characterizing irreversible (aggregate) formation, high-accuracy reversible association analysis, and the detection of protein interactions in complex and concentrated fluids (e.g. serum, cell cytosol).

  12. Combined effects of heat and mass transfer to magneto hydrodynamics oscillatory dusty fluid flow in a porous channel

    NASA Astrophysics Data System (ADS)

    Govindarajan, A.; Vijayalakshmi, R.; Ramamurthy, V.

    2018-04-01

    The main aim of this article is to study the combined effects of heat and mass transfer to radiative Magneto Hydro Dynamics (MHD) oscillatory optically thin dusty fluid in a saturated porous medium channel. Based on certain assumptions, the momentum, energy, concentration equations are obtained.The governing equations are non-dimensionalised, simplified and solved analytically. The closed analytical form solutions for velocity, temperature, concentration profiles are obtained. Numerical computations are presented graphically to show the salient features of various physical parameters. The shear stress, the rate of heat transfer and the rate of mass transfer are also presented graphically.

  13. An analytical/numerical correlation study of the multiple concentric cylinder model for the thermoplastic response of metal matrix composites

    NASA Technical Reports Server (NTRS)

    Pindera, Marek-Jerzy; Salzar, Robert S.; Williams, Todd O.

    1993-01-01

    The utility of a recently developed analytical micromechanics model for the response of metal matrix composites under thermal loading is illustrated by comparison with the results generated using the finite-element approach. The model is based on the concentric cylinder assemblage consisting of an arbitrary number of elastic or elastoplastic sublayers with isotropic or orthotropic, temperature-dependent properties. The elastoplastic boundary-value problem of an arbitrarily layered concentric cylinder is solved using the local/global stiffness matrix formulation (originally developed for elastic layered media) and Mendelson's iterative technique of successive elastic solutions. These features of the model facilitate efficient investigation of the effects of various microstructural details, such as functionally graded architectures of interfacial layers, on the evolution of residual stresses during cool down. The available closed-form expressions for the field variables can readily be incorporated into an optimization algorithm in order to efficiently identify optimal configurations of graded interfaces for given applications. Comparison of residual stress distributions after cool down generated using finite-element analysis and the present micromechanics model for four composite systems with substantially different temperature-dependent elastic, plastic, and thermal properties illustrates the efficacy of the developed analytical scheme.

  14. Development of a temperature gradient focusing method for in situ extraterrestrial biomarker analysis.

    PubMed

    Danger, Grégoire; Ross, David

    2008-08-01

    Scanning temperature gradient focusing (TGF) is a recently described technique for the simultaneous concentration and separation of charged analytes. It allows for high analyte peak capacities and low LODs in microcolumn electrophoretic separations. In this paper, we present the application of scanning TGF for chiral separations of amino acids. Using a mixture of seven carboxyfluorescein succinimidyl ester-labeled amino acids (including five chiral amino acids) which constitute the Mars7 standard, we show that scanning TGF is a very simple and efficient method for chiral separations. The modulation of TGF separation parameters (temperature window, pressure scan rate, temperature range, and chiral selector concentration) allows optimization of peak efficiencies and analyte resolutions. The use of hydroxypropyl-beta-CD at low concentration (1-5 mmol/L) as a chiral selector, with an appropriate pressure scan rate ( -0.25 Pa/s) and with a low temperature range (3-25 degrees C over 1 cm) provided high resolution between enantiomers (Rs >1.5 for each pair of enantiomers) using a short, 4 cm long capillary. With these new results, the scanning TGF method appears to be a viable method for in situ trace biomarker analysis for future missions to Mars or other solar system bodies.

  15. Metabolomic analysis of urine samples by UHPLC-QTOF-MS: Impact of normalization strategies.

    PubMed

    Gagnebin, Yoric; Tonoli, David; Lescuyer, Pierre; Ponte, Belen; de Seigneux, Sophie; Martin, Pierre-Yves; Schappler, Julie; Boccard, Julien; Rudaz, Serge

    2017-02-22

    Among the various biological matrices used in metabolomics, urine is a biofluid of major interest because of its non-invasive collection and its availability in large quantities. However, significant sources of variability in urine metabolomics based on UHPLC-MS are related to the analytical drift and variation of the sample concentration, thus requiring normalization. A sequential normalization strategy was developed to remove these detrimental effects, including: (i) pre-acquisition sample normalization by individual dilution factors to narrow the concentration range and to standardize the analytical conditions, (ii) post-acquisition data normalization by quality control-based robust LOESS signal correction (QC-RLSC) to correct for potential analytical drift, and (iii) post-acquisition data normalization by MS total useful signal (MSTUS) or probabilistic quotient normalization (PQN) to prevent the impact of concentration variability. This generic strategy was performed with urine samples from healthy individuals and was further implemented in the context of a clinical study to detect alterations in urine metabolomic profiles due to kidney failure. In the case of kidney failure, the relation between creatinine/osmolality and the sample concentration is modified, and relying only on these measurements for normalization could be highly detrimental. The sequential normalization strategy was demonstrated to significantly improve patient stratification by decreasing the unwanted variability and thus enhancing data quality. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Picoelectrospray Ionization Mass Spectrometry Using Narrow-bore Chemically Etched Emitters

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Marginean, Ioan; Tang, Keqi; Smith, Richard D.

    2014-01-01

    Electrospray ionization mass spectrometry (ESI-MS) at flow rates below ~10 nL/min has been only sporadically explored due to difficulty in reproducibly fabricating emitters that can operate at lower flow rates. Here we demonstrate narrow orifice chemically etched emitters for stable electrospray at flow rates as low as 400 pL/min. Depending on the analyte concentration, we observe two types of MS signal response as a function of flow rate. At low concentrations, an optimum flow rate is observed slightly above 1 nL/min, while the signal decreases monotonically with decreasing flow rates at higher concentrations. In spite of lower MS signal, themore » ion utilization efficiency increases exponentially with decreasing flow rate in all cases. No unimolecular response was observed within this flow rate range during the analysis of an equimolar mixture of peptides, indicating that ionization efficiency is an analyte-dependent characteristic in given experimental conditions. While little to no gain in signal-to-noise was achieved at ultralow flow rates for concentration-limited analyses, experiments consuming the same amount of analyte suggest that mass-limited analyses will benefit strongly from the use of low flow rates and avoiding unnecessary sample dilution. By operating under optimal conditions, consumption of just 500 zmol of sample yielded signal-to-noise ratios ~10 for some peptides. These findings have important implications for the analysis of trace biological samples.« less

  17. Analytical validation of a new point-of-care assay for serum amyloid A in horses.

    PubMed

    Schwartz, D; Pusterla, N; Jacobsen, S; Christopher, M M

    2018-01-17

    Serum amyloid A (SAA) is a major acute phase protein in horses. A new point-of-care (POC) test for SAA (Stablelab) is available, but studies evaluating its analytical accuracy are lacking. To evaluate the analytical performance of the SAA POC test by 1) determining linearity and precision, 2) comparing results in whole blood with those in serum or plasma, and 3) comparing POC results with those obtained using a previously validated turbidimetric immunoassay (TIA). Assay validation. Analytical validation of the POC test was done in accordance with American Society of Veterinary Clinical Pathology guidelines using residual equine serum/plasma and whole blood samples from the Clinical Pathology Laboratory at the University of California-Davis. A TIA was used as the reference method. We also evaluated the effect of haematocrit (HCT). The POC test was linear for SAA concentrations of up to at least 1000 μg/mL (r = 0.991). Intra-assay CVs were 13, 18 and 15% at high (782 μg/mL), intermediate (116 μg/mL) and low (64 μg/mL) concentrations. Inter-assay (inter-batch) CVs were 45, 14 and 15% at high (1372 μg/mL), intermediate (140 μg/mL) and low (56 μg/mL) concentrations. SAA results in whole blood were significantly lower than those in serum/plasma (P = 0.0002), but were positively correlated (r = 0.908) and not affected by HCT (P = 0.261); proportional negative bias was observed in samples with SAA>500 μg/mL. The difference between methods exceeded the 95% confidence interval of the combined imprecision of both methods (15%). Analytical validation could not be performed in whole blood, the sample most likely to be used stall side. The POC test has acceptable accuracy and precision in equine serum/plasma with SAA concentrations of up to at least 1000 μg/mL. Low inter-batch precision at high concentrations may affect serial measurements, and the use of the same test batch and sample type (serum/plasma or whole blood) is recommended. Comparison of results between the POC test and the TIA is not recommended. © 2018 EVJ Ltd.

  18. Method For Chemical Sensing Using A Microfabricated Teeter-Totter Resonator

    DOEpatents

    Adkins, Douglas Ray; Heller, Edwin J.; Shul, Randy J.

    2004-11-30

    A method for sensing a chemical analyte in a fluid stream comprises providing a microfabricated teeter-totter resonator that relies upon a Lorentz force to cause oscillation in a paddle, applying a static magnetic field substantially aligned in-plane with the paddle, energizing a current conductor line on a surface of the paddle with an alternating electrical current to generate the Lorentz force, exposing the resonator to the analyte, and detecting the response of the oscillatory motion of the paddle to the chemical analyte. Preferably, a chemically sensitive coating is disposed on at least one surface of the paddle to enhance the sorption of the analyte by the paddle. The concentration of the analyte in a fluid stream can be determined by measuring the change in the resonant frequency or phase of the teeter-totter resonator as the chemical analyte is added to or removed from the paddle.

  19. Dielectrokinetic chromatography devices

    DOEpatents

    Chirica, Gabriela S; Fiechtner, Gregory J; Singh, Anup K

    2014-12-16

    Disclosed herein are methods and devices for dielectrokinetic chromatography. As disclosed, the devices comprise microchannels having at least one perturber which produces a non-uniformity in a field spanning the width of the microchannel. The interaction of the field non-uniformity with a perturber produces a secondary flow which competes with a primary flow. By decreasing the size of the perturber the secondary flow becomes significant for particles/analytes in the nanometer-size range. Depending on the nature of a particle/analyte present in the fluid and its interaction with the primary flow and the secondary flow, the analyte may be retained or redirected. The composition of the primary flow can be varied to affect the magnitude of primary and/or secondary flows on the particles/analytes and thereby separate and concentrate it from other particles/analytes.

  20. Dielectrokinetic chromatography and devices thereof

    DOEpatents

    Chirica, Gabriela S; Fiechtner, Gregory J; Singh, Anup K

    2014-04-22

    Disclosed herein are methods and devices for dielectrokinetic chromatography. As disclosed, the devices comprise microchannels having at least one perturber which produces a non-uniformity in a field spanning the width of the microchannel. The interaction of the field non-uniformity with a perturber produces a secondary flow which competes with a primary flow. By decreasing the size of the perturber the secondary flow becomes significant for particles/analytes in the nanometer-size range. Depending on the nature of a particle/analyte present in the fluid and its interaction with the primary flow and the secondary flow, the analyte may be retained or redirected. The composition of the primary flow can be varied to affect the magnitude of primary and/or secondary flows on the particles/analytes and thereby separate and concentrate it from other particles/analytes.

  1. A Paper-Based Electrochromic Array for Visualized Electrochemical Sensing.

    PubMed

    Zhang, Fengling; Cai, Tianyi; Ma, Liang; Zhan, Liyuan; Liu, Hong

    2017-01-31

    We report a battery-powered, paper-based electrochromic array for visualized electrochemical sensing. The paper-based sensing system consists of six parallel electrochemical cells, which are powered by an aluminum-air battery. Each single electrochemical cell uses a Prussian Blue spot electrodeposited on an indium-doped tin oxide thin film as the electrochromic indicator. Each electrochemical cell is preloaded with increasing amounts of analyte. The sample activates the battery for the sensing. Both the preloaded analyte and the analyte in the sample initiate the color change of Prussian Blue to Prussian White. With a reaction time of 60 s, the number of electrochemical cells with complete color changes is correlated to the concentration of analyte in the sample. As a proof-of-concept analyte, lactic acid was detected semi-quantitatively using the naked eye.

  2. Sequential Multiplex Analyte Capturing for Phosphoprotein Profiling*

    PubMed Central

    Poetz, Oliver; Henzler, Tanja; Hartmann, Michael; Kazmaier, Cornelia; Templin, Markus F.; Herget, Thomas; Joos, Thomas O.

    2010-01-01

    Microarray-based sandwich immunoassays can simultaneously detect dozens of proteins. However, their use in quantifying large numbers of proteins is hampered by cross-reactivity and incompatibilities caused by the immunoassays themselves. Sequential multiplex analyte capturing addresses these problems by repeatedly probing the same sample with different sets of antibody-coated, magnetic suspension bead arrays. As a miniaturized immunoassay format, suspension bead array-based assays fulfill the criteria of the ambient analyte theory, and our experiments reveal that the analyte concentrations are not significantly changed. The value of sequential multiplex analyte capturing was demonstrated by probing tumor cell line lysates for the abundance of seven different receptor tyrosine kinases and their degree of phosphorylation and by measuring the complex phosphorylation pattern of the epidermal growth factor receptor in the same sample from the same cavity. PMID:20682761

  3. An analytical model for solute transport through a GCL-based two-layered liner considering biodegradation.

    PubMed

    Guan, C; Xie, H J; Wang, Y Z; Chen, Y M; Jiang, Y S; Tang, X W

    2014-01-01

    An analytical model for solute advection and dispersion in a two-layered liner consisting of a geosynthetic clay liner (GCL) and a soil liner (SL) considering the effect of biodegradation was proposed. The analytical solution was derived by Laplace transformation and was validated over a range of parameters using the finite-layer method based software Pollute v7.0. Results show that if the half-life of the solute in GCL is larger than 1 year, the degradation in GCL can be neglected for solute transport in GCL/SL. When the half-life of GCL is less than 1 year, neglecting the effect of degradation in GCL on solute migration will result in a large difference of relative base concentration of GCL/SL (e.g., 32% for the case with half-life of 0.01 year). The 100-year solute base concentration can be reduced by a factor of 2.2 when the hydraulic conductivity of the SL was reduced by an order of magnitude. The 100-year base concentration was reduced by a factor of 155 when the half life of the contaminant in the SL was reduced by an order of magnitude. The effect of degradation is more important in approving the groundwater protection level than the hydraulic conductivity. The analytical solution can be used for experimental data fitting, verification of complicated numerical models and preliminary design of landfill liner systems. © 2013.

  4. Effect of injection matrix concentration on peak shape and separation efficiency in ion chromatography.

    PubMed

    Zhang, Ya; Lucy, Charles A

    2014-12-05

    In HPLC, injection of solvents that differ from the eluent can result in peak broadening due to solvent strength mismatch or viscous fingering. Broadened, distorted or even split analyte peaks may result. Past studies of this injection-induced peak distortion in reversed phase (RPLC) and hydrophilic interaction (HILIC) liquid chromatography have led to the conclusion that the sample should be injected in the eluent or a weaker solvent. However, there have been no studies of injection-induced peak distortion in ion chromatography (IC). To address this, injection-induced effects were studied for six inorganic anions (F-, Cl-, NO2-, Br-, NO3- and SO4(2-)) on a Dionex AS23 IC column using a HCO3-/CO3(2-) eluent. The VanMiddlesworth-Dorsey injection sensitivity parameter (s) showed that IC of anions has much greater tolerance to the injection matrix (HCO3-/CO3(2-) herein) mismatch than RPLC or HILIC. Even when the injection contained a ten-fold greater concentration of HCO3-/CO3(2-) than the eluent, the peak shapes and separation efficiencies of six analyte ions did not change significantly. At more than ten-fold greater matrix concentrations, analyte anions that elute near the system peak of the matrix were distorted, and in the extreme cases exhibited a small secondary peak on the analyte peak front. These studies better guide the degree of dilution needed prior to IC analysis of anions. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. A critical evaluation of liquid chromatography with hybrid linear ion trap-Orbitrap mass spectrometry for the determination of acidic contaminants in wastewater effluents.

    PubMed

    Cahill, Michael G; Dineen, Brian A; Stack, Mary A; James, Kevin J

    2012-12-28

    Acidic pesticide and pharmaceutical contaminants were pre-concentrated and extracted from wastewater samples (500 mL) using solid-phase extraction. Analyte recoveries were 79-96%, with % RSD values in the range, 1.7-7.4%. Analyte identification and quantification were carried out using liquid chromatography-mass spectrometry (LC-MS) with hybrid linear ion trap (LIT) Orbitrap instrumentation. Using a resolution setting of 30,000 FWHM, full-scan MS analysis was performed using heated electrospray ionization (HESI) in negative mode. The high mass resolution capabilities of the Orbitrap MS were exploited for the determination of trace contaminants allowing facile discrimination between analytes and matrix. The dependant scan functions of the Orbitrap MS using higher collisional dissociation (HCD) and LIT MS were evaluated for the confirmation of analytes at trace concentration levels. Mass accuracy for target contaminants using this method was less than 2 ppm. The limits of quantitation (LOQs) were in the range, 2.1-27 ng/L. The inter-day accuracy and precision were measured over a five-day period at two concentrations. The % relative errors were in the range, 0.30-7.7%, and the % RSD values were in the range, 1.5-5.5%. Using this method, 2,4-D, mecoprop, ibuprofen, naproxene and gemfibrozil were identified in several wastewater treatment plants in Ireland. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. Monitoring of emerging pollutants in Guadiamar River basin (South of Spain): analytical method, spatial distribution and environmental risk assessment.

    PubMed

    Garrido, Eva; Camacho-Muñoz, Dolores; Martín, Julia; Santos, Antonio; Santos, Juan Luis; Aparicio, Irene; Alonso, Esteban

    2016-12-01

    Guadiamar River is located in the southwest of the Iberian Peninsula and connects two protected areas in the South of Spain: Sierra Morena and Doñana National Park. It is sited in an area affected by urban, industrial and agriculture sewage pollution and with tradition on intensive mining activities. Most of the studies performed in this area have been mainly focused on the presence of heavy metals and, until now, little is known about the occurrence of other contaminants such as emerging organic pollutants (EOPs). In this work, an analytical method has been optimized and validated for monitoring of forty-seven EOPs in surface water. The analytical method has been applied to study the distribution and environmental risk of these pollutants in Guadiamar River basin. The analytical method was based on solid-phase extraction and determination by liquid chromatography-triple quadrupole-tandem mass spectrometry. The 60 % of the target compounds were found in the analyzed samples. The highest concentrations were found for two plasticizers (bisphenol A and di(2-ethyhexyl)phthalate, mean concentration up to 930 ng/L) and two pharmaceutical compounds (caffeine (up to 623 ng/L) and salicylic acid (up to 318 ng/L)). This study allowed to evaluate the potential sources (industrial or urban) of the studied compounds and the spatial distribution of their concentrations along the river. Environmental risk assessment showed a major risk on the south of the river, mainly due to discharges of wastewater effluents.

  7. Concentration Gradient Immunoassay I. A Rapid Immunoassay Based on Interdiffusion and Surface Binding in a Microchannel

    PubMed Central

    Nelson, Kjell E.; Foley, Jennifer O.; Yager, Paul

    2008-01-01

    We describe a novel microfluidic immunoassay method based on the diffusion of a small molecule analyte into a parallel-flowing stream containing cognate antibody. This interdiffusion results in a steady-state gradient of antibody binding site occupancy transverse to convective flow. In contrast to the diffusion immunoassay (Hatch et al. Nature Biotechnology,19:461−465 (2001)), this antibody occupancy gradient is interrogated by a sensor surface coated with a functional analog of the analyte. Antibodies with at least one unoccupied binding site may specifically bind to this functionalized surface, leading to a quantifiable change in surface coverage by the antibody. SPR imaging is used to probe the spatial distribution of antibody binding to the surface and, therefore, the outcome of the assay. We show that the pattern of antibody binding to the SPR sensing surface correlates with the concentration of a model analyte (phenytoin) in the sample stream. Using an inexpensive disposable microfluidic device, we demonstrate assays for phenytoin ranging in concentration from 75 to 1000 nM in phosphate buffer. At a total volumetric flow rate of 90 nL/sec, the assays are complete within 10 minutes. Inclusion of an additional flow stream on the side of the antibody stream opposite to that of the sample enables simultaneous calibration of the assay. This assay method is suitable for rapid quantitative detection of low-molecular weight analytes for point-of-care diagnostic instrumentation. PMID:17437332

  8. Pair mobility functions for rigid spheres in concentrated colloidal dispersions: Stresslet and straining motion couplings

    NASA Astrophysics Data System (ADS)

    Su, Yu; Swan, James W.; Zia, Roseanna N.

    2017-03-01

    Accurate modeling of particle interactions arising from hydrodynamic, entropic, and other microscopic forces is essential to understanding and predicting particle motion and suspension behavior in complex and biological fluids. The long-range nature of hydrodynamic interactions can be particularly challenging to capture. In dilute dispersions, pair-level interactions are sufficient and can be modeled in detail by analytical relations derived by Jeffrey and Onishi [J. Fluid Mech. 139, 261-290 (1984)] and Jeffrey [Phys. Fluids A 4, 16-29 (1992)]. In more concentrated dispersions, analytical modeling of many-body hydrodynamic interactions quickly becomes intractable, leading to the development of simplified models. These include mean-field approaches that smear out particle-scale structure and essentially assume that long-range hydrodynamic interactions are screened by crowding, as particle mobility decays at high concentrations. Toward the development of an accurate and simplified model for the hydrodynamic interactions in concentrated suspensions, we recently computed a set of effective pair of hydrodynamic functions coupling particle motion to a hydrodynamic force and torque at volume fractions up to 50% utilizing accelerated Stokesian dynamics and a fast stochastic sampling technique [Zia et al., J. Chem. Phys. 143, 224901 (2015)]. We showed that the hydrodynamic mobility in suspensions of colloidal spheres is not screened, and the power law decay of the hydrodynamic functions persists at all concentrations studied. In the present work, we extend these mobility functions to include the couplings of particle motion and straining flow to the hydrodynamic stresslet. The couplings computed in these two articles constitute a set of orthogonal coupling functions that can be utilized to compute equilibrium properties in suspensions at arbitrary concentration and are readily applied to solve many-body hydrodynamic interactions analytically.

  9. Developing a semi-analytical algorithm to estimate particulate organic carbon (POC) levels in inland eutrophic turbid water based on MERIS images: A case study of Lake Taihu

    NASA Astrophysics Data System (ADS)

    Lyu, Heng; Wang, Yannan; Jin, Qi; Shi, Lei; Li, Yunmei; Wang, Qiao

    2017-10-01

    Particulate organic carbon (POC) plays an important role in the carbon cycle in water due to its biological pump process. In the open ocean, algorithms can accurately estimate the surface POC concentration. However, no suitable POC-estimation algorithm based on MERIS bands is available for inland turbid eutrophic water. A total of 228 field samples were collected from Lake Taihu in different seasons between 2013 and 2015. At each site, the optical parameters and water quality were analyzed. Using in situ data, it was found that POC-estimation algorithms developed for the open ocean and coastal waters using remote sensing reflectance were not suitable for inland turbid eutrophic water. The organic suspended matter (OSM) concentration was found to be the best indicator of the POC concentration, and POC has an exponential relationship with the OSM concentration. Through an analysis of the POC concentration and optical parameters, it was found that the absorption peak of total suspended matter (TSM) at 665 nm was the optimum parameter to estimate POC. As a result, MERIS band 7, MERIS band 10 and MERIS band 12 were used to derive the absorption coefficient of TSM at 665 nm, and then, a semi-analytical algorithm was used to estimate the POC concentration for inland turbid eutrophic water. An accuracy assessment showed that the developed semi-analytical algorithm could be successfully applied with a MAPE of 31.82% and RMSE of 2.68 mg/L. The developed algorithm was successfully applied to a MERIS image, and two full-resolution MERIS images, acquired on August 13, 2010, and December 7, 2010, were used to map the POC spatial distribution in Lake Taihu in summer and winter.

  10. Major to ultra trace element bulk rock analysis of nanoparticulate pressed powder pellets by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Peters, Daniel; Pettke, Thomas

    2016-04-01

    An efficient, clean procedure for bulk rock major to trace element analysis by 193 nm Excimer LA-ICP-MS analysis of nanoparticulate pressed powder pellets (PPPs) employing a binder is presented. Sample powders are milled in water suspension in a planetary ball mill, reducing average grain size by about one order of magnitude compared to common dry milling protocols. Microcrystalline cellulose (MCC) is employed as a binder, improving the mechanical strength of the PPP and the ablation behaviour, because MCC absorbs 193 nm laser light well. Use of MCC binder allows for producing cohesive pellets of materials that cannot be pelletized in their pure forms, such as quartz powder. Rigorous blank quantification was performed on synthetic quartz treated like rock samples, demonstrating that procedural blanks are irrelevant except for a few elements at the 10 ng g-1 concentration level. The LA-ICP-MS PPP analytical procedure was optimised and evaluated using six different SRM powders (JP-1, UB-N, BCR-2, GSP-2, OKUM, and MUH-1). Calibration based on external standardization using SRM 610, SRM 612, BCR-2G, and GSD-1G glasses allows for evaluation of possible matrix effects during LA-ICP-MS analysis. The data accuracy of the PPP LA-ICP-MS analytical procedure compares well to that achieved for liquid ICP-MS and LA-ICP-MS glass analysis, except for element concentrations below ˜30 ng g-1, where liquid ICP-MS offers more precise data and in part lower limits of detection. Uncertainties on the external reproducibility of LA-ICP-MS PPP element concentrations are of the order of 0.5 to 2 % (1σ standard deviation) for concentrations exceeding ˜1 μg g-1. For lower element concentrations these uncertainties increase to 5-10% or higher when analyte-depending limits of detection (LOD) are approached, and LODs do not significantly differ from glass analysis. Sample homogeneity is demonstrated by the high analytical precision, except for very few elements where grain size effects can rarely still be resolved analytically. Matrix effects are demonstrated for PPP analysis of diverse rock compositions and basalt glass analysis when externally calibrated based on SRM 610 and SRM 612 glasses; employing basalt glass GSD-1G or BCR-2G for external standardisation basically eliminates these problems. Perhaps the most prominent progress of the LA-ICP-MS PPP analytical procedure presented here is the fact that trace elements not commonly analysed, i.e. new, unconventional geochemical tracers, can be measured straightforwardly, including volatile elements, the flux elements Li and B, the chalcophile elements As, Sb, Tl, Bi, and elements that alloy with metal containers employed in conventional glass production approaches. The method presented here thus overcomes many common problems and limitations in analytical geochemistry and is shown to be an efficient alternative for bulk rock trace elements analysis.

  11. Mitigating the Hook Effect in Lateral Flow Sandwich Immunoassays Using Real-Time Reaction Kinetics.

    PubMed

    Rey, Elizabeth G; O'Dell, Dakota; Mehta, Saurabh; Erickson, David

    2017-05-02

    The quantification of analyte concentrations using lateral flow assays is a low-cost and user-friendly alternative to traditional lab-based assays. However, sandwich-type immunoassays are often limited by the high-dose hook effect, which causes falsely low results when analytes are present at very high concentrations. In this paper, we present a reaction kinetics-based technique that solves this problem, significantly increasing the dynamic range of these devices. With the use of a traditional sandwich lateral flow immunoassay, a portable imaging device, and a mobile interface, we demonstrate the technique by quantifying C-reactive protein concentrations in human serum over a large portion of the physiological range. The technique could be applied to any hook effect-limited sandwich lateral flow assay and has a high level of accuracy even in the hook effect range.

  12. Interlaboratory comparability, bias, and precision for four laboratories measuring analytes in wet deposition, October 1983-December 1984

    USGS Publications Warehouse

    Brooks, Myron H.; Schroder, LeRoy J.; Willoughby, Timothy C.

    1987-01-01

    Four laboratories involved in the routine analysis of wet-deposition samples participated in an interlaboratory comparison program managed by the U.S. Geological Survey. The four participants were: Illinois State Water Survey central analytical laboratory in Champaign, Illinois; U.S. Geological Survey national water-quality laboratories in Atlanta, Georgia, and Denver, Colorado; and Inland Waters Directorate national water-quality laboratory in Burlington, Ontario, Canada. Analyses of interlaboratory samples performed by the four laboratories from October 1983 through December 1984 were compared.Participating laboratories analyzed three types of interlaboratory samples--natural wet deposition, simulated wet deposition, and deionized water--for pH and specific conductance, and for dissolved calcium, magnesium, sodium, sodium, potassium, chloride, sulfate, nitrate, ammonium, and orthophosphate. Natural wet-deposition samples were aliquots of actual wet-deposition samples. Analyses of these samples by the four laboratories were compared using analysis of variance. Test results indicated that pH, calcium, nitrate, and ammonium results were not directly comparable among the four laboratories. Statistically significant differences between laboratory results probably only were meaningful for analyses of dissolved calcium. Simulated wet-deposition samples with known analyte concentrations were used to test each laboratory for analyte bias. Laboratory analyses of calcium, magnesium, sodium, potassium, chloride, sulfate, and nitrate were not significantly different from the known concentrations of these analytes when tested using analysis of variance. Deionized-water samples were used to test each laboratory for reporting of false positive values. The Illinois State Water Survey Laboratory reported the smallest percentage of false positive values for most analytes. Analyte precision was estimated for each laboratory from results of replicate measurements. In general, the Illinois State Water Survey laboratory achieved the greatest precision, whereas the U.S. Geological Survey laboratories achieved the least precision.

  13. Inorganic chemical analysis of environmental materials—A lecture series

    USGS Publications Warehouse

    Crock, J.G.; Lamothe, P.J.

    2011-01-01

    At the request of the faculty of the Colorado School of Mines, Golden, Colorado, the authors prepared and presented a lecture series to the students of a graduate level advanced instrumental analysis class. The slides and text presented in this report are a compilation and condensation of this series of lectures. The purpose of this report is to present the slides and notes and to emphasize the thought processes that should be used by a scientist submitting samples for analyses in order to procure analytical data to answer a research question. First and foremost, the analytical data generated can be no better than the samples submitted. The questions to be answered must first be well defined and the appropriate samples collected from the population that will answer the question. The proper methods of analysis, including proper sample preparation and digestion techniques, must then be applied. Care must be taken to achieve the required limits of detection of the critical analytes to yield detectable analyte concentration (above "action" levels) for the majority of the study's samples and to address what portion of those analytes answer the research question-total or partial concentrations. To guarantee a robust analytical result that answers the research question(s), a well-defined quality assurance and quality control (QA/QC) plan must be employed. This QA/QC plan must include the collection and analysis of field and laboratory blanks, sample duplicates, and matrix-matched standard reference materials (SRMs). The proper SRMs may include in-house materials and/or a selection of widely available commercial materials. A discussion of the preparation and applicability of in-house reference materials is also presented. Only when all these analytical issues are sufficiently addressed can the research questions be answered with known certainty.

  14. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Koester, C J; Moulik, A

    This article discusses developments in environmental analytical chemistry that occurred in the years of 2003 and 2004. References were found by searching the ''Science Citation Index and Current Contents''. As in our review of two years ago (A1), techniques are highlighted that represent current trends and state-of-the-art technologies in the sampling, extraction, separation, and detection of trace concentrations, low-part-per-billion and less, of organic, inorganic, and organometallic contaminants in environmental samples. New analytes of interest are also reviewed, the detections of which are made possible by recently developed analytical instruments and methods.

  15. Detection of biological molecules using chemical amplification and optical sensors

    DOEpatents

    Van Antwerp, William Peter; Mastrototaro, John Joseph

    2001-01-01

    Methods are provided for the determination of the concentration of biological levels of polyhydroxylated compounds, particularly glucose. The methods utilize an amplification system that is an analyte transducer immobilized in a polymeric matrix, where the system is implantable and biocompatible. Upon interrogation by an optical system, the amplification system produces a signal capable of detection external to the skin of the patient. Quantitation of the analyte of interest is achieved by measurement of the emitted signal. Specifically, the analyte transducer immobilized in a polymeric matrix can be a boronic acid moiety.

  16. Determination of stoichiometry and concentration of trace elements in thin BaxSr1-xTiO3 perovskite layers.

    PubMed

    Becker, J S; Boulyga, S F

    2001-07-01

    This paper describes an analytical procedure for determining the stoichiometry of BaxSr1-xTiO3 perovskite layers using inductively coupled plasma mass spectrometry (ICP-MS). The analytical results of mass spectrometry measurements are compared to those of X-ray fluorescence analysis (XRF). The performance and the limits of solid-state mass spectrometry analytical methods for the surface analysis of thin BaxSr1-xTiO3 perovskite layers sputtered neutral mass spectrometry (SNMS)--are investigated and discussed.

  17. [The uncertainty evaluation of analytical results of 27 elements in geological samples by X-ray fluorescence spectrometry].

    PubMed

    Wang, Yi-Ya; Zhan, Xiu-Chun

    2014-04-01

    Evaluating uncertainty of analytical results with 165 geological samples by polarized dispersive X-ray fluorescence spectrometry (P-EDXRF) has been reported according to the internationally accepted guidelines. One hundred sixty five pressed pellets of similar matrix geological samples with reliable values were analyzed by P-EDXRF. These samples were divided into several different concentration sections in the concentration ranges of every component. The relative uncertainties caused by precision and accuracy of 27 components were evaluated respectively. For one element in one concentration, the relative uncertainty caused by precision can be calculated according to the average value of relative standard deviation with different concentration level in one concentration section, n = 6 stands for the 6 results of one concentration level. The relative uncertainty caused by accuracy in one concentration section can be evaluated by the relative standard deviation of relative deviation with different concentration level in one concentration section. According to the error propagation theory, combining the precision uncertainty and the accuracy uncertainty into a global uncertainty, this global uncertainty acted as method uncertainty. This model of evaluating uncertainty can solve a series of difficult questions in the process of evaluating uncertainty, such as uncertainties caused by complex matrix of geological samples, calibration procedure, standard samples, unknown samples, matrix correction, overlap correction, sample preparation, instrument condition and mathematics model. The uncertainty of analytical results in this method can act as the uncertainty of the results of the similar matrix unknown sample in one concentration section. This evaluation model is a basic statistical method owning the practical application value, which can provide a strong base for the building of model of the following uncertainty evaluation function. However, this model used a lot of samples which cannot simply be applied to other types of samples with different matrix samples. The number of samples is too large to adapt to other type's samples. We will strive for using this study as a basis to establish a reasonable basis of mathematical statistics function mode to be applied to different types of samples.

  18. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jenkins, T.F.; Thorne, P.G.; Myers, K.F.

    Salting-out solvent extraction (SOE) was compared with cartridge and membrane solid-phase extraction (SPE) for preconcentration of nitroaromatics, nitramines, and aminonitroaromatics prior to determination by reversed-phase high-performance liquid chromatography. The solid phases used were manufacturer-cleaned materials, Porapak RDX for the cartridge method and Empore SDB-RPS for the membrane method. Thirty-three groundwater samples from the Naval Surface Warfare Center, Crane, Indiana, were analyzed using the direct analysis protocol specified in SW846 Method 8330, and the results were compared with analyses conducted after preconcentration using SOE with acetonitrile, cartridge-based SPE, and membrane-based SPE. For high-concentration samples, analytical results from the three preconcentration techniquesmore » were compared with results from the direct analysis protocol; good recovery of all target analytes was achieved by all three pre-concentration methods. For low-concentration samples, results from the two SPE methods were correlated with results from the SOE method; very similar data was obtained by the SOE and SPE methods, even at concentrations well below 1 microgram/L.« less

  19. Analytical model of chemical phase and formation of DSB in chromosomes by ionizing radiation.

    PubMed

    Barilla, Jiří; Lokajíček, Miloš; Pisaková, Hana; Simr, Pavel

    2013-03-01

    Mathematical analytical model of the processes running in individual radical clusters during the chemical phase (under the presence of radiomodifiers) proposed by us earlier has been further developed and improved. It has been applied to the data presented by Blok and Loman characterizing the oxygen effect in SSB and DSB formation (in water solution and at low-LET radiation) also in the region of very small oxygen concentrations, which cannot be studied with the help of experiments done with living cells. In this new analysis the values of all reaction rates and diffusion parameters known from literature have been made use of. The great increase of SSB and DSB at zero oxygen concentration may follow from the fact that at small oxygen concentrations the oxygen absorbs other radicals while at higher concentrations the formation of oxygen radicals prevails. It explains the double oxygen effect found already earlier by Ewing. The model may be easily extended to include also the effects of other radiomodifiers present in medium during irradiation.

  20. Concentrations of tritium and strontium-90 in water from selected wells at the Idaho National Engineering Laboratory after purging one, two, and three borehole volumes

    USGS Publications Warehouse

    Bartholomay, R.C.

    1993-01-01

    Water from 11 wells completed in the Snake River Plain aquifer at the Idaho National Engineering Laboratory was sampled as part of the U.S. Geological Survey's quality assurance program to determine the effect of purging different borehole volumes on tritium and strontium-90 concentrations. Wells were selected for sampling on the basis of the length of time it took to purge a borehole volume of water. Samples were collected after purging one, two, and three borehole volumes. The U.S. Department of Energy's Radiological and Environmental Sciences Laboratory provided analytical services. Statistics were used to determine the reproducibility of analytical results. The comparison between tritium and strontium-90 concentrations after purging one and three borehole volumes and two and three borehole volumes showed that all but two sample pairs with defined numbers were in statistical agreement. Results indicate that concentrations of tritium and strontium-90 are not affected measurably by the number of borehole volumes purged.

  1. Thermoelectrically cooled water trap

    DOEpatents

    Micheels, Ronald H [Concord, MA

    2006-02-21

    A water trap system based on a thermoelectric cooling device is employed to remove a major fraction of the water from air samples, prior to analysis of these samples for chemical composition, by a variety of analytical techniques where water vapor interferes with the measurement process. These analytical techniques include infrared spectroscopy, mass spectrometry, ion mobility spectrometry and gas chromatography. The thermoelectric system for trapping water present in air samples can substantially improve detection sensitivity in these analytical techniques when it is necessary to measure trace analytes with concentrations in the ppm (parts per million) or ppb (parts per billion) partial pressure range. The thermoelectric trap design is compact and amenable to use in a portable gas monitoring instrumentation.

  2. Semipermeable membrane devices used to estimate bioconcentration of polychlorinated biphenyls

    USGS Publications Warehouse

    Chambers, D.B.

    1999-01-01

    Aquatic organisms passively accumulate hydrophobic organic compounds, such as polychlorinated biphenyls, even when ambient water concentrations of the contaminant are below analytical detection limits. However, contaminant concentrations in tissue samples are subject to an inherently high level of variability due to differences in species, life stage, and gender bioconcentration potentials. Semipermeable membrane devices (SPMDs) were used to sample Aroclor 1254, a mixture of readily bioconcentrated polychlorinated biphenyls (PCBs), in a contaminated wetland near Flat Top, WV. The devices consisted of triolein, a lipid found in fish, enclosed in a polyethylene membrane. SPMDs were deployed in the water column and in direct contact with wetland sediments along a previously identified concentration gradient of PCBs. The devices were retrieved after a 25-day exposure period. Analytes were recovered by dialyzing the devices in nanograde hexane. Hexane dialysates were condensed and analyzed by gas chromatography. All deployed devices sequestered quantifiable amounts of Aroclor 1254. Water-column SPMDs accumulated PCBs far in excess of ambient water concentrations. The devices contacting sediments accumulated PCBs at all sites, though accumulated concentrations did not exceed concentrations in sediment. Patterns of PCB concentration in the devices corresponded to the identified gradient at the site. Results from the water-column SPMDs were used to estimate the concentration of the dissolved, bioavailable fraction of PCBs present in the water column. These concentrations ranged from 0.01 to 0.09 ??g/L of bioavailable Aroclor 1254.

  3. Quantification and Statistical Modeling—Part I: Breathing-Zone Concentrations of Monomeric and Polymeric 1,6-Hexamethylene Diisocyanate

    PubMed Central

    Fent, Kenneth W.; Gaines, Linda G. Trelles; Thomasen, Jennifer M.; Flack, Sheila L.; Ding, Kai; Herring, Amy H.; Whittaker, Stephen G.; Nylander-French, Leena A.

    2009-01-01

    We conducted a repeated exposure-assessment survey for task-based breathing-zone concentrations (BZCs) of monomeric and polymeric 1,6-hexamethylene diisocyanate (HDI) during spray painting on 47 automotive spray painters from North Carolina and Washington State. We report here the use of linear mixed modeling to identify the primary determinants of the measured BZCs. Both one-stage (N = 98 paint tasks) and two-stage (N = 198 paint tasks) filter sampling was used to measure concentrations of HDI, uretidone, biuret, and isocyanurate. The geometric mean (GM) level of isocyanurate (1410 μg m−3) was higher than all other analytes (i.e. GM < 7.85 μg m−3). The mixed models were unique to each analyte and included factors such as analyte-specific paint concentration, airflow in the paint booth, and sampler type. The effect of sampler type was corroborated by side-by-side one- and two-stage personal air sampling (N = 16 paint tasks). According to paired t-tests, significantly higher concentrations of HDI (P = 0.0363) and isocyanurate (P = 0.0035) were measured using one-stage samplers. Marginal R2 statistics were calculated for each model; significant fixed effects were able to describe 25, 52, 54, and 20% of the variability in BZCs of HDI, uretidone, biuret, and isocyanurate, respectively. Mixed models developed in this study characterize the processes governing individual polyisocyanate BZCs. In addition, the mixed models identify ways to reduce polyisocyanate BZCs and, hence, protect painters from potential adverse health effects. PMID:19622637

  4. CO-occurring exposure to perchlorate, nitrate and thiocyanate alters thyroid function in healthy pregnant women.

    PubMed

    Horton, Megan K; Blount, Benjamin C; Valentin-Blasini, Liza; Wapner, Ronald; Whyatt, Robin; Gennings, Chris; Factor-Litvak, Pam

    2015-11-01

    Adequate maternal thyroid function during pregnancy is necessary for normal fetal brain development, making pregnancy a critical window of vulnerability to thyroid disrupting insults. Sodium/iodide symporter (NIS) inhibitors, namely perchlorate, nitrate, and thiocyanate, have been shown individually to competitively inhibit uptake of iodine by the thyroid. Several epidemiologic studies examined the association between these individual exposures and thyroid function. Few studies have examined the effect of this chemical mixture on thyroid function during pregnancy We examined the cross sectional association between urinary perchlorate, thiocyanate and nitrate concentrations and thyroid function among healthy pregnant women living in New York City using weighted quantile sum (WQS) regression. We measured thyroid stimulating hormone (TSH) and free thyroxine (FreeT4) in blood samples; perchlorate, thiocyanate, nitrate and iodide in urine samples collected from 284 pregnant women at 12 (±2.8) weeks gestation. We examined associations between urinary analyte concentrations and TSH or FreeT4 using linear regression or WQS adjusting for gestational age, urinary iodide and creatinine. Individual analyte concentrations in urine were significantly correlated (Spearman's r 0.4-0.5, p<0.001). Linear regression analyses did not suggest associations between individual concentrations and thyroid function. The WQS revealed a significant positive association between the weighted sum of urinary concentrations of the three analytes and increased TSH. Perchlorate had the largest weight in the index, indicating the largest contribution to the WQS. Co-exposure to perchlorate, nitrate and thiocyanate may alter maternal thyroid function, specifically TSH, during pregnancy. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

  5. Co-occurring exposure to perchlorate, nitrate and thiocyanate alters thyroid function in healthy pregnant women

    PubMed Central

    Horton, Megan K.; Blount, Benjamin C.; Valentin-Blasini, Liza; Wapner, Ronald; Whyatt, Robin; Gennings, Chris; Factor-Litvak, Pam

    2015-01-01

    Background Adequate maternal thyroid function during pregnancy is necessary for normal fetal brain development, making pregnancy a critical window of vulnerability to thyroid disrupting insults. Sodium/iodide symporter (NIS) inhibitors, namely perchlorate, nitrate, and thiocyanate, have been shown individually to competitively inhibit uptake of iodine by the thyroid. Several epidemiologic studies examined the association between these individual exposures and thyroid function. Few studies have examined the effect of this chemical mixture on thyroid function during pregnancy. Objectives We examined the cross sectional association between urinary perchlorate, thiocyanate and nitrate concentrations and thyroid function among healthy pregnant women living in New York City using weighted quantile sum (WQS) regression. Methods We measured thyroid stimulating hormone (TSH) and free thyroxine (FreeT4) in blood samples; perchlorate, thiocyanate, nitrate and iodide in urine samples collected from 284 pregnant women at 12 (± 2.8) weeks gestation. We examined associations between urinary analyte concentrations and TSH or FreeT4 using linear regression or WQS adjusting for gestational age, urinary iodide and creatinine. Results Individual analyte concentrations in urine were significantly correlated (Spearman’s r 0.4–0.5, p < 0.001). Linear regression analyses did not suggest associations between individual concentrations and thyroid function. The WQS revealed a significant positive association between the weighted sum of urinary concentrations of the three analytes and increased TSH. Perchlorate had the largest weight in the index, indicating the largest contribution to the WQS. Conclusions Co-exposure to perchlorate, nitrate and thiocyanate may alter maternal thyroid function, specifically TSH, during pregnancy. PMID:26408806

  6. Runoff of pharmaceuticals and personal care products following application of dewatered municipal biosolids to an agricultural field.

    PubMed

    Sabourin, Lyne; Beck, Andrew; Duenk, Peter W; Kleywegt, Sonya; Lapen, David R; Li, Hongxia; Metcalfe, Chris D; Payne, Michael; Topp, Edward

    2009-08-01

    Municipal biosolids are a useful source of nutrients for crop production, and commonly used in agriculture. In this field study, we applied dewatered municipal biosolids at a commercial rate using broadcast application followed by incorporation. Precipitation was simulated at 1, 3, 7, 21 and 34 days following the application on 2 m(2) microplots to evaluate surface runoff of various pharmaceuticals and personal care products (PPCPs), namely atenolol, carbamazepine, cotinine, caffeine, gemfibrozil, naproxen, ibuprofen, acetaminophen, sulfamethoxazole, triclosan and triclocarban. There was little temporal coherence in the detection of PPCPs in runoff, various compounds being detected maximally on days 1, 3, 7 or 36. Maximum concentrations in runoff ranged from below detection limit (gemfibrozil) to 109.7 ng L(-1) (triclosan). Expressing the total mass exported as a percentage of that applied, some analytes revealed little transport potential (<1% exported; triclocarban, triclosan, sulfamethoxazole, ibuprofen, naproxen and gemfibrozil) whereas others were readily exported (>1% exported; acetaminophen, carbamazepine, caffeine, cotinine, atenolol). Those compounds with little transport potential had log K(ow) values of 3.18 or greater, whereas those that were readily mobilized had K(ow) values of 2.45 or less. Maximal concentrations of all analytes were below toxic concentrations using a variety of endpoints available in the literature. In summary, this study has quantified the transport potential in surface runoff of PPCPs from land receiving biosolids, identified that log K(ow) may be a determinant of runoff transport potential of these analytes, and found maximal concentrations of all chemicals tested to be below toxic concentrations using a variety of endpoints.

  7. Improved partition equilibrium model for predicting analyte response in electrospray ionization mass spectrometry.

    PubMed

    Du, Lihong; White, Robert L

    2009-02-01

    A previously proposed partition equilibrium model for quantitative prediction of analyte response in electrospray ionization mass spectrometry is modified to yield an improved linear relationship. Analyte mass spectrometer response is modeled by a competition mechanism between analyte and background electrolytes that is based on partition equilibrium considerations. The correlation between analyte response and solution composition is described by the linear model over a wide concentration range and the improved model is shown to be valid for a wide range of experimental conditions. The behavior of an analyte in a salt solution, which could not be explained by the original model, is correctly predicted. The ion suppression effects of 16:0 lysophosphatidylcholine (LPC) on analyte signals are attributed to a combination of competition for excess charge and reduction of total charge due to surface tension effects. In contrast to the complicated mathematical forms that comprise the original model, the simplified model described here can more easily be employed to predict analyte mass spectrometer responses for solutions containing multiple components. Copyright (c) 2008 John Wiley & Sons, Ltd.

  8. Regional geochemical maps of the Tonopah 1 degree by 2 degrees Quadrangle, Nevada, based on samples of stream sediment and nonmagnetic heavy-mineral concentrate

    USGS Publications Warehouse

    Nash, J.T.; Siems, D.F.

    1988-01-01

    The geochemical maps in this report are based on analytical results reported by Fairfield and others (1985), Hill and others (1986), and Siems and others (1986). These reports also describe the sample preparation and analytical methods and provide information on the location of the sample sites.

  9. The relationship between purely stochastic sampling error and the number of technical replicates used to estimate concentration at an extreme dilution

    USDA-ARS?s Scientific Manuscript database

    For any analytical system the population mean (mu) number of entities (e.g., cells or molecules) per tested volume, surface area, or mass also defines the population standard deviation (sigma = square root of mu ). For a preponderance of analytical methods, sigma is very small relative to mu due to...

  10. Use of airborne hyperspectral imagery to map soil parameters in tilled agricultural fields

    USGS Publications Warehouse

    Hively, W. Dean; McCarty, Gregory W.; Reeves, James B.; Lang, Megan W.; Oesterling, Robert A.; Delwiche, Stephen R.

    2011-01-01

    Soil hyperspectral reflectance imagery was obtained for six tilled (soil) agricultural fields using an airborne imaging spectrometer (400–2450 nm, ~10 nm resolution, 2.5 m spatial resolution). Surface soil samples (n = 315) were analyzed for carbon content, particle size distribution, and 15 agronomically important elements (Mehlich-III extraction). When partial least squares (PLS) regression of imagery-derived reflectance spectra was used to predict analyte concentrations, 13 of the 19 analytes were predicted with R2 > 0.50, including carbon (0.65), aluminum (0.76), iron (0.75), and silt content (0.79). Comparison of 15 spectral math preprocessing treatments showed that a simple first derivative worked well for nearly all analytes. The resulting PLS factors were exported as a vector of coefficients and used to calculate predicted maps of soil properties for each field. Image smoothing with a 3 × 3 low-pass filter prior to spectral data extraction improved prediction accuracy. The resulting raster maps showed variation associated with topographic factors, indicating the effect of soil redistribution and moisture regime on in-field spatial variability. High-resolution maps of soil analyte concentrations can be used to improve precision environmental management of farmlands.

  11. Selectivity in analytical chemistry: two interpretations for univariate methods.

    PubMed

    Dorkó, Zsanett; Verbić, Tatjana; Horvai, George

    2015-01-01

    Selectivity is extremely important in analytical chemistry but its definition is elusive despite continued efforts by professional organizations and individual scientists. This paper shows that the existing selectivity concepts for univariate analytical methods broadly fall in two classes: selectivity concepts based on measurement error and concepts based on response surfaces (the response surface being the 3D plot of the univariate signal as a function of analyte and interferent concentration, respectively). The strengths and weaknesses of the different definitions are analyzed and contradictions between them unveiled. The error based selectivity is very general and very safe but its application to a range of samples (as opposed to a single sample) requires the knowledge of some constraint about the possible sample compositions. The selectivity concepts based on the response surface are easily applied to linear response surfaces but may lead to difficulties and counterintuitive results when applied to nonlinear response surfaces. A particular advantage of this class of selectivity is that with linear response surfaces it can provide a concentration independent measure of selectivity. In contrast, the error based selectivity concept allows only yes/no type decision about selectivity. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. The use of selective adsorbents in capillary electrophoresis-mass spectrometry for analyte preconcentration and microreactions: a powerful three-dimensional tool for multiple chemical and biological applications.

    PubMed

    Guzman, N A; Stubbs, R J

    2001-10-01

    Much attention has recently been directed to the development and application of online sample preconcentration and microreactions in capillary electrophoresis using selective adsorbents based on chemical or biological specificity. The basic principle involves two interacting chemical or biological systems with high selectivity and affinity for each other. These molecular interactions in nature usually involve noncovalent and reversible chemical processes. Properly bound to a solid support, an "affinity ligand" can selectively adsorb a "target analyte" found in a simple or complex mixture at a wide range of concentrations. As a result, the isolated analyte is enriched and highly purified. When this affinity technique, allowing noncovalent chemical interactions and biochemical reactions to occur, is coupled on-line to high-resolution capillary electrophoresis and mass spectrometry, a powerful tool of chemical and biological information is created. This paper describes the concept of biological recognition and affinity interaction on-line with high-resolution separation, the fabrication of an "analyte concentrator-microreactor", optimization conditions of adsorption and desorption, the coupling to mass spectrometry, and various applications of clinical and pharmaceutical interest.

  13. Methods for determination of inorganic substances in water and fluvial sediments

    USGS Publications Warehouse

    Fishman, Marvin J.; Friedman, Linda C.

    1989-01-01

    Chapter Al of the laboratory manual contains methods used by the U.S. Geological Survey to analyze samples of water, suspended sediments, and bottom material for their content of inorganic constituents. Included are methods for determining the concentration of dissolved constituents in water, the total recoverable and total of constituents in water-suspended sediment samples, and the recoverable and total concentrations of constituents in samples of bottom material. The introduction to the manual includes essential definitions and a brief discussion of the use of significant figures in calculating and reporting analytical results. Quality control in the water-analysis laboratory is discussed, including the accuracy and precision of analyses, the use of standard-reference water samples, and the operation of an effective quality-assurance program. Methods for sample preparation and pretreatment are given also. A brief discussion of the principles of the analytical techniques involved and their particular application to water and sediment analysis is presented. The analytical methods of these techniques are arranged alphabetically by constituent. For each method, the general topics covered are the application, the principle of the method, the interferences, the apparatus and reagents required, a detailed description of the analytical procedure, reporting results, units and significant figures, and analytical precision data, when available. More than 126 methods are given for the determination of 70 inorganic constituents and physical properties of water, suspended sediment, and bottom material.

  14. Methods for determination of inorganic substances in water and fluvial sediments

    USGS Publications Warehouse

    Fishman, Marvin J.; Friedman, Linda C.

    1985-01-01

    Chapter Al of the laboratory manual contains methods used by the Geological Survey to analyze samples of water, suspended sediments, and bottom material for their content of inorganic constituents. Included are methods for determining the concentration of dissolved constituents in water, total recoverable and total of constituents in water-suspended sediment samples, and recoverable and total concentrations of constituents in samples of bottom material. Essential definitions are included in the introduction to the manual, along with a brief discussion of the use of significant figures in calculating and reporting analytical results. Quality control in the water-analysis laboratory is discussed, including accuracy and precision of analyses, the use of standard reference water samples, and the operation of an effective quality assurance program. Methods for sample preparation and pretreatment are given also.A brief discussion of the principles of the analytical techniques involved and their particular application to water and sediment analysis is presented. The analytical methods involving these techniques are arranged alphabetically according to constituent. For each method given, the general topics covered are application, principle of the method, interferences, apparatus and reagents required, a detailed description of the analytical procedure, reporting results, units and significant figures, and analytical precision data, when available. More than 125 methods are given for the determination of 70 different inorganic constituents and physical properties of water, suspended sediment, and bottom material.

  15. Stochastic modeling of macrodispersion in unsaturated heterogeneous porous media. Final report

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yeh, T.C.J.

    1995-02-01

    Spatial heterogeneity of geologic media leads to uncertainty in predicting both flow and transport in the vadose zone. In this work an efficient and flexible, combined analytical-numerical Monte Carlo approach is developed for the analysis of steady-state flow and transient transport processes in highly heterogeneous, variably saturated porous media. The approach is also used for the investigation of the validity of linear, first order analytical stochastic models. With the Monte Carlo analysis accurate estimates of the ensemble conductivity, head, velocity, and concentration mean and covariance are obtained; the statistical moments describing displacement of solute plumes, solute breakthrough at a compliancemore » surface, and time of first exceedance of a given solute flux level are analyzed; and the cumulative probability density functions for solute flux across a compliance surface are investigated. The results of the Monte Carlo analysis show that for very heterogeneous flow fields, and particularly in anisotropic soils, the linearized, analytical predictions of soil water tension and soil moisture flux become erroneous. Analytical, linearized Lagrangian transport models also overestimate both the longitudinal and the transverse spreading of the mean solute plume in very heterogeneous soils and in dry soils. A combined analytical-numerical conditional simulation algorithm is also developed to estimate the impact of in-situ soil hydraulic measurements on reducing the uncertainty of concentration and solute flux predictions.« less

  16. Suspended sediment concentration and optical property observations of mixed-turbidity, coastal waters through multispectral ocean color inversion

    EPA Science Inventory

    Multispectral satellite ocean color data from high-turbidity areas of the coastal ocean contain information about the surface concentrations and optical properties of suspended sediments and colored dissolved organic matter (CDOM). Empirical and semi-analytical inversion algorit...

  17. Stability studies of amphetamine and ephedrine derivatives in urine.

    PubMed

    Jiménez, C; de la Torre, R; Ventura, M; Segura, J; Ventura, R

    2006-10-20

    Knowledge of the stability of drugs in biological specimens is a critical consideration for the interpretation of analytical results. Identification of proper storage conditions has been a matter of concern for most toxicology laboratories (both clinical and forensic), and the stability of drugs of abuse has been extensively studied. This concern should be extended to other areas of analytical chemistry like antidoping control. In this work, the stability of ephedrine derivatives (ephedrine, norephedrine, methylephedrine, pseudoephedrine, and norpseudoephedrine), and amphetamine derivatives (amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), and 3,4-methylenedioxymethamphetamine (MDMA)) in urine has been studied. Spiked urine samples were prepared for stability testing. Urine samples were quantified by GC/NPD or GC/MS. The homogeneity of each batch of sample was verified before starting the stability study. The stability of analytes was evaluated in sterilized and non-sterilized urine samples at different storage conditions. For long-term stability testing, analyte concentration in urine stored at 4 degrees C and -20 degrees C was determined at different time intervals for 24 months for sterile urine samples, and for 6 months for non-sterile samples. For short-term stability testing, analyte concentration was evaluated in liquid urine stored at 37 degrees C for 7 days. The effect of repeated freezing (at -20 degrees C) and thawing (at room temperature) was also studied in sterile urine for up to three cycles. No significant loss of the analytes under study was observed at any of the investigated conditions. These results show the feasibility of preparing reference materials containing ephedrine and amphetamine derivatives to be used for quality control purposes.

  18. Impact of phase ratio, polydimethylsiloxane volume and size, and sampling temperature and time on headspace sorptive extraction recovery of some volatile compounds in the essential oil field.

    PubMed

    Bicchi, Carlo; Cordero, Chiara; Liberto, Erica; Rubiolo, Patrizia; Sgorbini, Barbara; Sandra, Pat

    2005-04-15

    This study evaluates concentration capability of headspace sorptive extraction (HSSE) and the influence of sampling conditions on HSSE recovery of an analyte. A standard mixture in water of six high-to-medium volatility analytes (isobutyl methyl ketone, 3-hexanol, isoamyl acetate, 1,8-cineole, linalool and carvone) was used to sample the headspace by HSSE with stir bars coated with different polydimethylsiloxane (PDMS) volumes (20, 40, 55 and 110 microL, respectively), headspace vial volumes (8, 21.2, 40, 250 and 1000 mL), sampling temperatures (25, 50 and 75 degrees C) and sampling times (30, 60 and 120 min, and 4, 8 and 16 h). The concentration factors (CFs) of HSSE versus static headspace (S-HS) were also determined. Analytes sampled by the PDMS stir bars were recovered by thermal desorption (TDS) and analysed by capillary GC-MS. This study demonstrates how analyte recovery depends on its physico-chemical characteristics and affinity for PDMS (octanol-water partition coefficients), sampling temperatures (50 degrees C) and times (60 min), the volumes of headspace (40 mL) and of PDMS (in particular, for high volatility analytes). HSSE is also shown to be very effective for trace analysis. The HSSE CFs calculated versus S-HS with a 1000 mL headspace volumes at 25 degrees C during 4 h sampling ranged between 10(3) and 10(4) times for all analytes investigated while the limits of quantitation determined under the same conditions were in the nmol/L range.

  19. Comprehensive two-dimensional gas chromatography and food sensory properties: potential and challenges.

    PubMed

    Cordero, Chiara; Kiefl, Johannes; Schieberle, Peter; Reichenbach, Stephen E; Bicchi, Carlo

    2015-01-01

    Modern omics disciplines dealing with food flavor focus the analytical efforts on the elucidation of sensory-active compounds, including all possible stimuli of multimodal perception (aroma, taste, texture, etc.) by means of a comprehensive, integrated treatment of sample constituents, such as physicochemical properties, concentration in the matrix, and sensory properties (odor/taste quality, perception threshold). Such analyses require detailed profiling of known bioactive components as well as advanced fingerprinting techniques to catalog sample constituents comprehensively, quantitatively, and comparably across samples. Multidimensional analytical platforms support comprehensive investigations required for flavor analysis by combining information on analytes' identities, physicochemical behaviors (volatility, polarity, partition coefficient, and solubility), concentration, and odor quality. Unlike other omics, flavor metabolomics and sensomics include the final output of the biological phenomenon (i.e., sensory perceptions) as an additional analytical dimension, which is specifically and exclusively triggered by the chemicals analyzed. However, advanced omics platforms, which are multidimensional by definition, pose challenging issues not only in terms of coupling with detection systems and sample preparation, but also in terms of data elaboration and processing. The large number of variables collected during each analytical run provides a high level of information, but requires appropriate strategies to exploit fully this potential. This review focuses on advances in comprehensive two-dimensional gas chromatography and analytical platforms combining two-dimensional gas chromatography with olfactometry, chemometrics, and quantitative assays for food sensory analysis to assess the quality of a given product. We review instrumental advances and couplings, automation in sample preparation, data elaboration, and a selection of applications.

  20. Liquid Metering Centrifuge Sticks (LMCS): A Centrifugal Approach to Metering Known Sample Volumes for Colorimetric Solid Phase Extraction (C-SPE)

    NASA Technical Reports Server (NTRS)

    Gazda, Daniel B.; Schultz, John R.; Clarke, Mark S.

    2007-01-01

    Phase separation is one of the most significant obstacles encountered during the development of analytical methods for water quality monitoring in spacecraft environments. Removing air bubbles from water samples prior to analysis is a routine task on earth; however, in the absence of gravity, this routine task becomes extremely difficult. This paper details the development and initial ground testing of liquid metering centrifuge sticks (LMCS), devices designed to collect and meter a known volume of bubble-free water in microgravity. The LMCS uses centrifugal force to eliminate entrapped air and reproducibly meter liquid sample volumes for analysis with Colorimetric Solid Phase Extraction (C-SPE). C-SPE is a sorption-spectrophotometric platform that is being developed as a potential spacecraft water quality monitoring system. C-SPE utilizes solid phase extraction membranes impregnated with analyte-specific colorimetric reagents to concentrate and complex target analytes in spacecraft water samples. The mass of analyte extracted from the water sample is determined using diffuse reflectance (DR) data collected from the membrane surface and an analyte-specific calibration curve. The analyte concentration can then be calculated from the mass of extracted analyte and the volume of the sample analyzed. Previous flight experiments conducted in microgravity conditions aboard the NASA KC-135 aircraft demonstrated that the inability to collect and meter a known volume of water using a syringe was a limiting factor in the accuracy of C-SPE measurements. Herein, results obtained from ground based C-SPE experiments using ionic silver as a test analyte and either the LMCS or syringes for sample metering are compared to evaluate the performance of the LMCS. These results indicate very good agreement between the two sample metering methods and clearly illustrate the potential of utilizing centrifugal forces to achieve phase separation and metering of water samples in microgravity.

  1. Portable sample preparation and analysis system for micron and sub-micron particle characterization using light scattering and absorption spectroscopy

    DOEpatents

    Stark, Peter C [Los Alamos, NM; Zurek, Eduardo [Barranquilla, CO; Wheat, Jeffrey V [Fort Walton Beach, FL; Dunbar, John M [Santa Fe, NM; Olivares, Jose A [Los Alamos, NM; Garcia-Rubio, Luis H [Temple Terrace, FL; Ward, Michael D [Los Alamos, NM

    2011-07-26

    There is provided a method and device for remote sampling, preparation and optical interrogation of a sample using light scattering and light absorption methods. The portable device is a filtration-based device that removes interfering background particle material from the sample matrix by segregating or filtering the chosen analyte from the sample solution or matrix while allowing the interfering background particles to be pumped out of the device. The segregated analyte is then suspended in a diluent for analysis. The device is capable of calculating an initial concentration of the analyte, as well as diluting the analyte such that reliable optical measurements can be made. Suitable analytes include cells, microorganisms, bioparticles, pathogens and diseases. Sample matrixes include biological fluids such as blood and urine, as well as environmental samples including waste water.

  2. Effects of pore-scale dispersion, degree of heterogeneity, sampling size, and source volume on the concentration moments of conservative solutes in heterogeneous formations

    Treesearch

    Daniele Tonina; Alberto Bellin

    2008-01-01

    Pore-scale dispersion (PSD), aquifer heterogeneity, sampling volume, and source size influence solute concentrations of conservative tracers transported in heterogeneous porous formations. In this work, we developed a new set of analytical solutions for the concentration ensemble mean, variance, and coefficient of variation (CV), which consider the effects of all these...

  3. Dielectrophoresis-Enhanced Plasmonic Sensing with Gold Nanohole Arrays

    PubMed Central

    2015-01-01

    We experimentally demonstrate dielectrophoretic concentration of biological analytes on the surface of a gold nanohole array, which concurrently acts as a nanoplasmonic sensor and gradient force generator. The combination of nanohole-enhanced dielectrophoresis, electroosmosis, and extraordinary optical transmission through the periodic gold nanohole array enables real-time label-free detection of analyte molecules in a 5 μL droplet using concentrations as low as 1 pM within a few minutes, which is more than 1000 times faster than purely diffusion-based binding. The nanohole-based optofluidic platform demonstrated here is straightforward to construct, applicable to both charged and neutral molecules, and performs a novel function that cannot be accomplished using conventional surface plasmon resonance sensors. PMID:24646075

  4. Development of a Novel Method for in vivo Determination of Activation Energy of Glucose Transport Across S. cerevisiae Cellular Membranes. A Biosensor-like Approach.

    PubMed

    Kormes, Diego J; Cortón, Eduardo

    2009-01-01

    Whereas biosensors have been usually proposed as analytical tools, used to investigate the surrounding media pursuing an analytical answer, we have used a biosensor-like device to characterize the microbial cells immobilized on it. We have studied the kinetics of transport and degradation of glucose at different concentrations and temperatures. When glucose concentrations of 15 and 1.5 mM were assayed, calculated activation energies were 25.2 and 18.4 kcal mol(-1), respectively, in good agreement with previously published data. The opportunity and convenience of using Arrhenius plots to estimate the activation energy in metabolic-related processes is also discussed.

  5. Noncircular orifice holes and advanced fabrication techniques for liquid rocket injectors. Phase 3: Analytical and cold-flow experimental evaluation of rectangular concentric tube injector elements for gas/liquid application. Phase 4: Analytical and experimental evaluation of noncircular injector elements for gas/liquid and liquid/liquid application

    NASA Technical Reports Server (NTRS)

    Mchale, R. M.

    1974-01-01

    Results are presented of a cold-flow and hot-fire experimental study of the mixing and atomization characteristics of injector elements incorporating noncircular orifices. Both liquid/liquid and gas/liquid element types are discussed. Unlike doublet and triplet elements (circular orifices only) were investigated for the liquid/liquid case while concentric tube elements were investigated for the gas/liquid case. It is concluded that noncircular shape can be employed to significant advantage in injector design for liquid rocket engines.

  6. Standard reference materials (SRMs) for determination of organic contaminants in environmental samples.

    PubMed

    Wise, Stephen A; Poster, Dianne L; Kucklick, John R; Keller, Jennifer M; Vanderpol, Stacy S; Sander, Lane C; Schantz, Michele M

    2006-10-01

    For the past 25 years the National Institute of Standards and Technology (NIST) has developed certified reference materials (CRMs), known as standard reference materials (SRMs), for determination of organic contaminants in environmental matrices. Assignment of certified concentrations has usually been based on combining results from two or more independent analytical methods. The first-generation environmental-matrix SRMs were issued with certified concentrations for a limited number (5 to 10) of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Improvements in the analytical certification approach significantly expanded the number and classes of contaminants determined. Environmental-matrix SRMs currently available include air and diesel particulate matter, coal tar, marine and river sediment, mussel tissue, fish oil and tissue, and human serum, with concentrations typically assigned for 50 to 90 organic contaminants, for example PAHs, nitro-substituted PAHs, PCBs, chlorinated pesticides, and polybrominated diphenyl ethers (PBDEs).

  7. Stabilization of glucose-oxidase in the graphene paste for screen-printed glucose biosensor

    NASA Astrophysics Data System (ADS)

    Pepłowski, Andrzej; Janczak, Daniel; Jakubowska, Małgorzata

    2015-09-01

    Various methods and materials for enzyme stabilization within screen-printed graphene sensor were analyzed. Main goal was to develop technology allowing immediate printing of the biosensors in single printing process. Factors being considered were: toxicity of the materials used, ability of the material to be screen-printed (squeezed through the printing mesh) and temperatures required in the fabrication process. Performance of the examined sensors was measured using chemical amperometry method, then appropriate analysis of the measurements was conducted. The analysis results were then compared with the medical requirements. Parameters calculated were: correlation coefficient between concentration of the analyte and the measured electrical current (0.986) and variation coefficient for the particular concentrations of the analyte used as the calibration points. Variation of the measured values was significant only in ranges close to 0, decreasing for the concentrations of clinical importance. These outcomes justify further development of the graphene-based biosensors fabricated through printing techniques.

  8. A review of the occurrence, analyses, toxicity, and biodegradation of naphthenic acids.

    PubMed

    Clemente, Joyce S; Fedorak, Phillip M

    2005-07-01

    Naphthenic acids occur naturally in crude oils and in oil sands bitumens. They are toxic components in refinery wastewaters and in oil sands extraction waters. In addition, there are many industrial uses for naphthenic acids, so there is a potential for their release to the environment from a variety of activities. Studies have shown that naphthenic acids are susceptible to biodegradation, which decreases their concentration and reduces toxicity. This is a complex group of carboxylic acids with the general formula CnH(2n+Z)O2, where n indicates the carbon number and Z specifies the hydrogen deficiency resulting from ring formation. Measuring the concentrations of naphthenic acids in environmental samples and determining the chemical composition of a naphthenic acids mixture are huge analytical challenges. However, new analytical methods are being applied to these problems and progress is being made to better understand this mixture of chemically similar compounds. This paper reviews a variety of analytical methods and their application to assessing biodegradation of naphthenic acids.

  9. Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of chromium in water by graphite furnace atomic absorption spectrophotometry

    USGS Publications Warehouse

    McLain, B.J.

    1993-01-01

    Graphite furnace atomic absorption spectrophotometry is a sensitive, precise, and accurate method for the determination of chromium in natural water samples. The detection limit for this analytical method is 0.4 microg/L with a working linear limit of 25.0 microg/L. The precision at the detection limit ranges from 20 to 57 percent relative standard deviation (RSD) with an improvement to 4.6 percent RSD for concentrations more than 3 microg/L. Accuracy of this method was determined for a variety of reference standards that was representative of the analytical range. The results were within the established standard deviations. Samples were spiked with known concentrations of chromium with recoveries ranging from 84 to 122 percent. In addition, a comparison of data between graphite furnace atomic absorption spectrophotometry and direct-current plasma atomic emission spectrometry resulted in suitable agreement between the two methods, with an average deviation of +/- 2.0 microg/L throughout the analytical range.

  10. Reverse phase protein microarrays: fluorometric and colorimetric detection.

    PubMed

    Gallagher, Rosa I; Silvestri, Alessandra; Petricoin, Emanuel F; Liotta, Lance A; Espina, Virginia

    2011-01-01

    The Reverse Phase Protein Microarray (RPMA) is an array platform used to quantitate proteins and their posttranslationally modified forms. RPMAs are applicable for profiling key cellular signaling pathways and protein networks, allowing direct comparison of the activation state of proteins from multiple samples within the same array. The RPMA format consists of proteins immobilized directly on a nitrocellulose substratum. The analyte is subsequently probed with a primary antibody and a series of reagents for signal amplification and detection. Due to the diversity, low concentration, and large dynamic range of protein analytes, RPMAs require stringent signal amplification methods, high quality image acquisition, and software capable of precisely analyzing spot intensities on an array. Microarray detection strategies can be either fluorescent or colorimetric. The choice of a detection system depends on (a) the expected analyte concentration, (b) type of microarray imaging system, and (c) type of sample. The focus of this chapter is to describe RPMA detection and imaging using fluorescent and colorimetric (diaminobenzidine (DAB)) methods.

  11. Application of elevated temperature-dispersive liquid-liquid microextraction for determination of organophosphorus pesticides residues in aqueous samples followed by gas chromatography-flame ionization detection.

    PubMed

    Farajzadeh, Mir Ali; Afshar Mogaddam, Mohammad Reza; Rezaee Aghdam, Samaneh; Nouri, Nina; Bamorrowat, Mahdi

    2016-12-01

    In the present study, an elevated temperature, dispersive, liquid-liquid microextraction/gas chromatography-flame ionization detection was investigated for the determination, pre-concentration, and extraction of six organophosphorus pesticides (malathion, phosalone, dichlorvos, diazinon, profenofos, and chlorpyrifos) residues in fruit juice and aqueous samples. A mixture of 1,2-dibromoethane (extraction solvent) and dimethyl sulfoxide (disperser solvent) was injected rapidly into the sample solution heated at an elevated temperature. Analytical parameters, including enrichment factors (1600-2075), linearity (r>0.994), limits of detection (0.82-2.72ngmL(-1)) and quantification (2.60-7.36ngmL(-1)), relative standard deviations (<7%) and extraction recoveries (64-83%), showed the high efficiency of the method developed for analysis of the target analytes. The proposed procedure was used effectively to analyse selected analytes in river water and fruit juice, and diazinon was found at ngmL(-1) concentrations in apple juice. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Turbidimetric Estimation of Alcohol Concentration in Aqueous-Alcohol Mixtures

    ERIC Educational Resources Information Center

    Swinehart, William E.; Zimmerman, Bonnie L.; Powell, Kinsey; Moore, Stephen D.; Iordanov, Tzvetelin D.

    2014-01-01

    A concept of the turbidimetric method for determining the concentration of ethanol in water-ethanol mixtures is described. A closed sample cell containing the analyte was heated to achieve vapor saturation and subsequent condensation. As the condensation occurred, the decrease in percentage transmittance with time due to light scattering was…

  13. Results of quality-control sampling of water, bed sediment, and tissue in the Western Lake Michigan Drainages study unit of the National Water-Quality Assessment Program

    USGS Publications Warehouse

    Fitzgerald, S.A.

    1997-01-01

    This report contains the quality control results of the Western Lake Michigan Drainages study unit of the National Water Quality Assessment Program. Quality control samples were collected in the same manner and contemporaneously with environmental samples during the first highintensity study phase in the unit (1992 through 1995) and amounted to approximately 15 percent of all samples collected. The accuracy and precision of hundreds of chemical analyses of surface and ground-water, bed sediment, and tissue was determined through the collection and analysis of field blanks, field replicates and splits, matrix spikes, and surrogates. Despite the several detections of analytes in the field blanks, the concentrations of most constituents in the environmental samples will likely be an order of magnitude or higher than those in the blanks. However, frequent detections, and high concentrations, of dissolved organic carbon (DOC) in several surface and ground-water blanks are probably significant with respect to commonly measured environmental concentrations, and the environmental data will have to be qualified accordingly. The precision of sampling of water on a percent basis, as determined from replicates and splits, was generally proportional to the concentration of the constituents, with constituents present in relatively high concentrations generally having less sampling variability than those with relatively low concentrations. In general, analytes with relatively high variability between replicates were present at concentrations near the reporting limit or were associated with relatively small absolute concentration differences, or both. Precision of replicates compared to that for splits in bed sediment samples was similar, thus eliminating sampling as a major source of variability in analyte concentrations. In the case the phthalates in bed sediment, contamination in either the field or laboratory could have caused the relatively large variability between replicate samples and between split samples.Variability of analyte concentrations in tissue samples was relatively low, being 29 percent or less for all constituents. Recoveries of most laboratory schedule 2001/2010 pesticide spike compounds in surfacewater samples were reasonably good. Low intrinsic method recovery resulted in relatively low recovery forp,p'-DDE, metribuzin, and propargite. In the case of propargite, decomposition with the environmental sample matrices was also indicated. Recoveries of two compounds, cyanazine and thiobencarb, might have been biased high due to interferences. The one laboratory schedule 2050/2051 field matrix pesticide spike indicated numerous operational problems with this method that biased recoveries either low or high. Recoveries of pesticides from both pesticide schedules in field spikes of ground-water samples generally were similar to those of field matrix spikes of surface- water samples. High maximum recoveries were noted for tebuthiuron, disulfoton, DCPA, and permethrin, which indicates the possible presence of interferents in the matrices for these compounds. Problems in the recoveries of pesticides on schedule 2050/2051 from ground-water samples generally were the same as those for surfacewater samples. Recoveries of VOCs in field matrix spikes were reasonable when consideration was given for the use of the micropipettor that delivered only about 80 percent on average of the nominal mass of spiked analytes. Finally, the recoveries of most surrogate compounds in surface and ground-water samples were reasonable. Problems in sample handling (for example, spillage) were likely not the cause of any of the low recoveries of spiked compounds.

  14. Dynamically analyte-responsive macrocyclic host-fluorophore systems.

    PubMed

    Ghale, Garima; Nau, Werner M

    2014-07-15

    CONSPECTUS: Host-guest chemistry commenced to a large degree with the work of Pedersen, who in 1967 first reported the synthesis of crown ethers. The past 45 years have witnessed a substantial progress in the field, from the design of highly selective host molecules as receptors to their application in drug delivery and, particularly, analyte sensing. Much effort has been expended on designing receptors and signaling mechanism for detecting compounds of biological and environmental relevance. Traditionally, the design of a chemosensor comprises one component for molecular recognition, frequently macrocycles of the cyclodextrin, cucurbituril, cyclophane, or calixarene type. The second component, used for signaling, is typically an indicator dye which changes its photophysical properties, preferably its fluorescence, upon analyte binding. A variety of signal transduction mechanisms are available, of which displacement of the dye from the macrocyclic binding site is one of the simplest and most popular ones. This constitutes the working principle of indicator displacement assays. However, indicator displacement assays have been predominantly exploited in a static fashion, namely, to determine absolute analyte concentrations, or, by using combinations of several reporter pairs, to achieve a differential sensing and, thus, identification of specific food products or brands. In contrast, their use in biological systems, for example, with membranes, cells, or with enzymes has been comparably less explored, which led us to the design of the so-called tandem assays, that is, dynamically analyte-responsive host-dye systems, in which the change in analyte concentrations is induced by a biological reaction or process. This methodological variation has practical application potential, because the ability to monitor these biochemical pathways or to follow specific molecules in real time is of paramount interest for both biochemical laboratories and the pharmaceutical industry. We will begin by describing the underlying principles that govern the use of macrocycle-fluorescent dye complexes to monitor time-dependent changes in analyte concentrations. Suitable chemosensing ensembles are introduced, along with their fluorescence responses (switch-on or switch-off). This includes supramolecular tandem assays in their product- and substrate-selective variants, and in their domino and enzyme-coupled modifications, with assays for amino acid decarboxylases, diamine, and choline oxidase, proteases, methyl transferases, acetylcholineesterase (including an unpublished direct tandem assay), choline oxidase, and potato apyrase as examples. It also includes the very recently introduced tandem membrane assays in their published influx and unpublished efflux variants, with the outer membrane protein F as channel protein and protamine as bidirectionally translocated analyte. As proof-of-principle for environmental monitoring applications, we describe sensing ensembles for volatile hydrocarbons.

  15. Polymeric assemblies for sensitive colorimetric assays

    DOEpatents

    Charych, Deborah

    2000-01-01

    The presently claimed invention relates to polymeric assemblies which visibly change color in the presence of analyte. In particular, the presently claimed invention relates to liposomes comprising a plurality of lipid monomers, which comprises a polymerizable group, a hydrophilic head group and a hydrophobic tail group, and one or more ligands. Overall carbon chain length, and polymerizable group positioning on the monomer influence color change sensitivity to analyte concentrations.

  16. Multi-residue pesticide analysis (gas chromatography-tandem mass spectrometry detection)-Improvement of the quick, easy, cheap, effective, rugged, and safe method for dried fruits and fat-rich cereals-Benefit and limit of a standardized apple purée calibration (screening).

    PubMed

    Rasche, Claudia; Fournes, Britta; Dirks, Uwe; Speer, Karl

    2015-07-17

    Some steps of the QuEChERS method for the analysis of pesticides with GC-MS/MS in cereals and dried fruits were improved or simplified. For the latter, a mixing vessel with stator-rotor-system proved to be advantageous. The extraction procedure of dried fruits is much easier and safer than the Ultra Turrax and results in excellent validation data at a concentration level of 0.01mg/kg (116 of 118 analytes with recoveries in the range of 70-120%, 117 of 118 analytes with RSD <20%). After qualifying problematic lipophilic pesticides in fat-rich cereals (fat content >7%), predominantly organochlorines showed recoveries of <70% in quantification when the standard QuEChERS method with water was used. A second extraction was carried out analogous to the QuEChERS method, however, without the addition of water. With this simple modification, the problematic lipophilic pesticides, which had been strongly affected by the fat content of the commodities, could be determined with recoveries above 70% even at a concentration level of 0.01mg/kg. Moreover, a GC-MS/MS screening method for 120 pesticides at a concentration level of 0.01mg/kg was established by employing analyte protectants (ethylglycerol, gulonolactone, and sorbitol). The use of only one standardized calibration, made of an apple purée extract in combination with analyte protectants, allowed for a qualitative and quantitative analysis of 120 pesticides in different matrix extracts (tomato, red pepper, sour cherries, dried apples, black currant powder, raisins, wheat flour, rolled oats, wheat germ). The analyte protectants leveled the differences in the matrix-induced protection effect of the analyzed extracts over a wide range. The majority of the pesticides were analyzed with good analytical results (recoveries in the range of 70-120% and RSD <20%). Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Novel and versatile solid-state chemiluminescence sensor based on TiO2-Ru(bpy)32+ nanoparticles for pharmaceutical drugs detection

    NASA Astrophysics Data System (ADS)

    Al-Hetlani, Entesar; Amin, Mohamed O.; Madkour, Metwally

    2018-02-01

    This work describes a novel and versatile solid-state chemiluminescence sensor for analyte detection using TiO2-Ru(bpy)32+-Ce(IV). Herein, we report the synthesis, characterization, optimization and application of a new type of hybrid nanoparticles (NPs). Mesoporous TiO2-Ru(bpy)32+ NPs were prepared using a modified sol-gel method by incorporating Ru(bpy)32+ into the initial reaction mixture at various concentrations. The resultant bright orange precipitate was characterized via transmission electron microscopy, N2 sorpometry, inductively coupled plasma-optical emission spectrometer (ICP-OES), Raman and UV-Vis spectroscopy techniques. The concentration of Ru(bpy)32+ complex in the NPs was quantified using ICP-OES, and its chemiluminescence (CL) response was measured and compared with the same concentration in the liquid phase using oxalate as model analyte. The results showed that this type of hybrid material exhibited a higher CL signal compared with the liquid phase due to the enlarged surface area of the hybrid NPs ( 149.6 m2/g). The amount of TiO2-Ru(bpy)32+ NPs and the effect of the analyte flow rate were also investigated to optimize the CL signal. The optimized system was further used to detect oxalate and two pharmaceutical drugs, namely, imipramine and promazine. The linear range for both drugs was 1-100 pm with limits of detection (LOD) of 0.1 and 0.5 pm, respectively. This approach is considered to be simple, low cost and facile and can be applied to a wide range of analytes.

  18. Modeling convection-diffusion-reaction systems for microfluidic molecular communications with surface-based receivers in Internet of Bio-Nano Things

    PubMed Central

    Akan, Ozgur B.

    2018-01-01

    We consider a microfluidic molecular communication (MC) system, where the concentration-encoded molecular messages are transported via fluid flow-induced convection and diffusion, and detected by a surface-based MC receiver with ligand receptors placed at the bottom of the microfluidic channel. The overall system is a convection-diffusion-reaction system that can only be solved by numerical methods, e.g., finite element analysis (FEA). However, analytical models are key for the information and communication technology (ICT), as they enable an optimisation framework to develop advanced communication techniques, such as optimum detection methods and reliable transmission schemes. In this direction, we develop an analytical model to approximate the expected time course of bound receptor concentration, i.e., the received signal used to decode the transmitted messages. The model obviates the need for computationally expensive numerical methods by capturing the nonlinearities caused by laminar flow resulting in parabolic velocity profile, and finite number of ligand receptors leading to receiver saturation. The model also captures the effects of reactive surface depletion layer resulting from the mass transport limitations and moving reaction boundary originated from the passage of finite-duration molecular concentration pulse over the receiver surface. Based on the proposed model, we derive closed form analytical expressions that approximate the received pulse width, pulse delay and pulse amplitude, which can be used to optimize the system from an ICT perspective. We evaluate the accuracy of the proposed model by comparing model-based analytical results to the numerical results obtained by solving the exact system model with COMSOL Multiphysics. PMID:29415019

  19. Comparison of procedures for correction of matrix interferences in the analysis of soils by ICP-OES with CCD detection

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sadler, D.A.; Sun, F.; Littlejohn, D.

    1995-12-31

    ICP-OES is a useful technique for multi-element analysis of soils. However, as a number of elements are present in relatively high concentrations, matrix interferences can occur and examples have been widely reported. The availability of CCD detectors has increased the opportunities for rapid multi-element, multi-wave-length determination of elemental concentrations in soils and other environmental samples. As the composition of soils from industrial sites can vary considerably, especially when taken from different pit horizons, procedures are required to assess the extent of interferences and correct the effects, on a simultaneous multi-element basis. In single element analysis, plasma operating conditions can sometimesmore » be varied to minimize or even remove multiplicative interferences. In simultaneous multi-element analysis, the scope for this approach may be limited, depending on the spectrochemical characteristics of the emitting analyte species. Matrix matching, by addition of major sample components to the analyte calibrant solutions, can be used to minimize inaccuracies. However, there are also limitations to this procedure, when the sample composition varies significantly. Multiplicative interference effects can also be assessed by a {open_quotes}single standard addition{close_quotes} of each analyte to the sample solution and the information obtained may be used to correct the analyte concentrations determined directly. Each of these approaches has been evaluated to ascertain the best procedure for multi-element analysis of industrial soils by ICP-OES with CCD detection at multiple wavelengths. Standard reference materials and field samples have been analyzed to illustrate the efficacy of each procedure.« less

  20. Looking for new biomarkers of skin wound vitality with a cytokine-based multiplex assay: preliminary study.

    PubMed

    Peyron, Pierre-Antoine; Baccino, Éric; Nagot, Nicolas; Lehmann, Sylvain; Delaby, Constance

    2017-02-01

    Determination of skin wound vitality is an important issue in forensic practice. No reliable biomarker currently exists. Quantification of inflammatory cytokines in injured skin with MSD ® technology is an innovative and promising approach. This preliminary study aims to develop a protocol for the preparation and the analysis of skin samples. Samples from ante mortem wounds, post mortem wounds, and intact skin ("control samples") were taken from corpses at the autopsy. After an optimization of the pre-analytical protocol had been performed in terms of skin homogeneisation and proteic extraction, the concentration of TNF-α was measured in each sample with the MSD ® approach. Then five other cytokines of interest (IL-1β, IL-6, IL-10, IL-12p70 and IFN-γ) were simultaneously quantified with a MSD ® multiplex assay. The optimal pre-analytical conditions consist in a proteic extraction from a 6 mm diameter skin sample, in a PBS buffer with triton 0,05%. Our results show the linearity and the reproductibility of the TNF-α quantification with MSD ® , and an inter- and intra-individual variability of the concentrations of proteins. The MSD ® multiplex assay is likely to detect differential skin concentrations for each cytokine of interest. This preliminary study was used to develop and optimize the pre-analytical and analytical conditions of the MSD ® method using injured and healthy skin samples, for the purpose of looking for and identifying the cytokine, or the set of cytokines, that may be biomarkers of skin wound vitality.

  1. Modeling convection-diffusion-reaction systems for microfluidic molecular communications with surface-based receivers in Internet of Bio-Nano Things.

    PubMed

    Kuscu, Murat; Akan, Ozgur B

    2018-01-01

    We consider a microfluidic molecular communication (MC) system, where the concentration-encoded molecular messages are transported via fluid flow-induced convection and diffusion, and detected by a surface-based MC receiver with ligand receptors placed at the bottom of the microfluidic channel. The overall system is a convection-diffusion-reaction system that can only be solved by numerical methods, e.g., finite element analysis (FEA). However, analytical models are key for the information and communication technology (ICT), as they enable an optimisation framework to develop advanced communication techniques, such as optimum detection methods and reliable transmission schemes. In this direction, we develop an analytical model to approximate the expected time course of bound receptor concentration, i.e., the received signal used to decode the transmitted messages. The model obviates the need for computationally expensive numerical methods by capturing the nonlinearities caused by laminar flow resulting in parabolic velocity profile, and finite number of ligand receptors leading to receiver saturation. The model also captures the effects of reactive surface depletion layer resulting from the mass transport limitations and moving reaction boundary originated from the passage of finite-duration molecular concentration pulse over the receiver surface. Based on the proposed model, we derive closed form analytical expressions that approximate the received pulse width, pulse delay and pulse amplitude, which can be used to optimize the system from an ICT perspective. We evaluate the accuracy of the proposed model by comparing model-based analytical results to the numerical results obtained by solving the exact system model with COMSOL Multiphysics.

  2. Alzheimer's disease cerebrospinal fluid biomarkers are not influenced by gravity drip or aspiration extraction methodology.

    PubMed

    Rembach, Alan; Evered, Lisbeth A; Li, Qiao-Xin; Nash, Tabitha; Vidaurre, Lesley; Fowler, Christopher J; Pertile, Kelly K; Rumble, Rebecca L; Trounson, Brett O; Maher, Sarah; Mooney, Francis; Farrow, Maree; Taddei, Kevin; Rainey-Smith, Stephanie; Laws, Simon M; Macaulay, S Lance; Wilson, William; Darby, David G; Martins, Ralph N; Ames, David; Collins, Steven; Silbert, Brendan; Masters, Colin L; Doecke, James D

    2015-11-19

    Cerebrospinal fluid (CSF) biomarkers, although of established utility in the diagnostic evaluation of Alzheimer's disease (AD), are known to be sensitive to variation based on pre-analytical sample processing. We assessed whether gravity droplet collection versus syringe aspiration was another factor influencing CSF biomarker analyte concentrations and reproducibility. Standardized lumbar puncture using small calibre atraumatic spinal needles and CSF collection using gravity fed collection followed by syringe aspirated extraction was performed in a sample of elderly individuals participating in a large long-term observational research trial. Analyte assay concentrations were compared. For the 44 total paired samples of gravity collection and aspiration, reproducibility was high for biomarker CSF analyte assay concentrations (concordance correlation [95%CI]: beta-amyloid1-42 (Aβ42) 0.83 [0.71 - 0.90]), t-tau 0.99 [0.98 - 0.99], and phosphorylated tau (p-tau) 0.82 [95 % CI 0.71 - 0.89]) and Bonferroni corrected paired sample t-tests showed no significant differences (group means (SD): Aβ42 366.5 (86.8) vs 354.3 (82.6), p = 0.10; t-tau 83.9 (46.6) vs 84.7 (47.4) p = 0.49; p-tau 43.5 (22.8) vs 40.0 (17.7), p = 0.05). The mean duration of collection was 10.9 minutes for gravity collection and <1 minute for aspiration. Our results demonstrate that aspiration of CSF is comparable to gravity droplet collection for AD biomarker analyses but could considerably accelerate throughput and improve the procedural tolerability for assessment of CSF biomarkers.

  3. Electrodialytic in-line preconcentration for ionic solute analysis.

    PubMed

    Ohira, Shin-Ichi; Yamasaki, Takayuki; Koda, Takumi; Kodama, Yuko; Toda, Kei

    2018-04-01

    Preconcentration is an effective way to improve analytical sensitivity. Many types of methods are used for enrichment of ionic solute analytes. However, current methods are batchwise and include procedures such as trapping and elution. In this manuscript, we propose in-line electrodialytic enrichment of ionic solutes. The method can enrich ionic solutes within seconds by quantitative transfer of analytes from the sample solution to the acceptor solution under an electric field. Because of quantitative ion transfer, the enrichment factor (the ratio of the concentration in the sample and to that in the obtained acceptor solution) only depends on the flow rate ratio of the sample solution to the acceptor solution. The ratios of the concentrations and flow rates are equal for ratios up to 70, 20, and 70 for the tested ionic solutes of inorganic cations, inorganic anions, and heavy metal ions, respectively. The sensitivity of ionic solute determinations is also improved based on the enrichment factor. The method can also simultaneously achieve matrix isolation and enrichment. The method was successively applied to determine the concentrations of trace amounts of chloroacetic acids in tap water. The regulated concentration levels cannot be determined by conventional high-performance liquid chromatography with ultraviolet detection (HPLC-UV) without enrichment. However, enrichment with the present method is effective for determination of tap water quality by improving the limits of detection of HPLC-UV. The standard addition test with real tap water samples shows good recoveries (94.9-109.6%). Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Design and Analysis of a Preconcentrator for the ChemLab

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    WONG,CHUNGNIN C.; FLEMMING,JEB H.; MANGINELL,RONALD P.

    2000-07-17

    Preconcentration is a critical analytical procedure when designing a microsystem for trace chemical detection, because it can purify a sample mixture and boost the small analyte concentration to a much higher level allowing a better analysis. This paper describes the development of a micro-fabricated planar preconcentrator for the {mu}ChemLab{trademark} at Sandia. To guide the design, an analytical model to predict the analyte transport, adsorption and resorption process in the preconcentrator has been developed. Experiments have also been conducted to analyze the adsorption and resorption process and to validate the model. This combined effort of modeling, simulation, and testing has ledmore » us to build a reliable, efficient preconcentrator with good performance.« less

  5. Implantable medical sensor system

    DOEpatents

    Darrow, Christopher B.; Satcher, Jr., Joe H.; Lane, Stephen M.; Lee, Abraham P.; Wang, Amy W.

    2001-01-01

    An implantable chemical sensor system for medical applications is described which permits selective recognition of an analyte using an expandable biocompatible sensor, such as a polymer, that undergoes a dimensional change in the presence of the analyte. The expandable polymer is incorporated into an electronic circuit component that changes its properties (e.g., frequency) when the polymer changes dimension. As the circuit changes its characteristics, an external interrogator transmits a signal transdermally to the transducer, and the concentration of the analyte is determined from the measured changes in the circuit. This invention may be used for minimally invasive monitoring of blood glucose levels in diabetic patients.

  6. Chemical sensor system

    DOEpatents

    Darrow, Christopher B.; Satcher, Jr., Joe H.; Lane, Stephen M.; Lee, Abraham P.; Wang, Amy W.

    2002-01-01

    An implantable chemical sensor system for medical applications is described which permits selective recognition of an analyte using an expandable biocompatible sensor, such as a polymer, that undergoes a dimensional change in the presence of the analyte. The expandable polymer is incorporated into an electronic circuit component that changes its properties (e.g., frequency) when the polymer changes dimension. As the circuit changes its characteristics, an external interrogator transmits a signal transdermally to the transducer, and the concentration of the analyte is determined from the measured changes in the circuit. This invention may be used for minimally invasive monitoring of blood glucose levels in diabetic patients.

  7. Analysis of dissolved organic carbon concentration and 13C isotopic signature by TOC-IRMS - assessment of analytical performance

    NASA Astrophysics Data System (ADS)

    Kirkels, Frédérique; Cerli, Chiara; Federherr, Eugen; Kalbitz, Karsten

    2013-04-01

    Stable carbon isotopes provide a powerful tool to assess carbon pools and their dynamics. Dissolved organic carbon (DOC) has been recognized to play an important role in ecosystem functioning and carbon cycling and has therefore gained increased research interest. However, direct measurement of 13C isotopic signature of carbon in the dissolved phase is technically challenging particularly using high temperature combustion. Until recently, mainly custom-made systems existed which were modified for coupling of TOC instruments with IRMS for simultaneous assessment of C content and isotopic signature. The variety of coupled systems showed differences in their analytical performances. For analysis of DOC high temperature combustion is recognized as best performing method, owing to its high efficiency of conversion to CO2 also for highly refractory components (e.g. humic, fulvic acids) present in DOC and soil extracts. Therefore, we tested high temperature combustion TOC coupled to IRMS (developed by Elementar Group) for bulk measurements of DOC concentration and 13C signature. The instruments are coupled via an Interface to exchange the carrier gas from O2 to He and to concentrate the derived CO2 for the isotope measurement. Analytical performance of the system was assessed for a variety of organic compounds characterized by different stability and complexity, including humic acid and DOM. We tested injection volumes between 0.2-3 ml, thereby enabling measurement of broad concentration ranges. With an injection volume of 0.5 ml (n=3, preceded by 1 discarded injection), DOC and 13C signatures for concentrations between 5-150 mg C/L were analyzed with high precision (standard deviation (SD) predominantly <0.1‰), good accuracy and linearity (overall SD <0.9‰). For the same settings, slightly higher variation in precision was observed among the lower concentration range and depending upon specific system conditions. Differences in 13C signatures of about 50‰ among samples did not affect the precision of the analysis of natural abundance and labeled samples. Natural DOM, derived from different soils and assessed at various concentrations, was measured with similar good analytical performance, and also tested for the effect of freezing and re-dissolving. We found good performance of TOC-IRMS in comparison with other systems capable of determining C concentration and isotopic signatures. We recognize the advantages of this system providing: - High sample throughput, short measurement time (15 minutes), flexible sample volume - Easy maintenance, handling, rapid sample preparation (no pretreatment) This preliminary assessment highlights wide-ranging opportunities for further research on concentrations and isotopic signatures by TOC-IRMS to elucidate the role of dissolved carbon in terrestrial and aquatic systems.

  8. Comparison of methods for determination of total oil sands-derived naphthenic acids in water samples.

    PubMed

    Hughes, Sarah A; Huang, Rongfu; Mahaffey, Ashley; Chelme-Ayala, Pamela; Klamerth, Nikolaus; Meshref, Mohamed N A; Ibrahim, Mohamed D; Brown, Christine; Peru, Kerry M; Headley, John V; Gamal El-Din, Mohamed

    2017-11-01

    There are several established methods for the determination of naphthenic acids (NAs) in waters associated with oil sands mining operations. Due to their highly complex nature, measured concentration and composition of NAs vary depending on the method used. This study compared different common sample preparation techniques, analytical instrument methods, and analytical standards to measure NAs in groundwater and process water samples collected from an active oil sands operation. In general, the high- and ultrahigh-resolution methods, namely high performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOF-MS) and Orbitrap mass spectrometry (Orbitrap-MS), were within an order of magnitude of the Fourier transform infrared spectroscopy (FTIR) methods. The gas chromatography mass spectrometry (GC-MS) methods consistently had the highest NA concentrations and greatest standard error. Total NAs concentration was not statistically different between sample preparation of solid phase extraction and liquid-liquid extraction. Calibration standards influenced quantitation results. This work provided a comprehensive understanding of the inherent differences in the various techniques available to measure NAs and hence the potential differences in measured amounts of NAs in samples. Results from this study will contribute to the analytical method standardization for NA analysis in oil sands related water samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Determination of fluorine concentrations using wavelength dispersive X-ray fluorescence (WDXRF) spectrometry to analyze fluoride precipitates.

    NASA Astrophysics Data System (ADS)

    Lee, H. A.; Lee, J.; Kwon, E.; Kim, D.; Yoon, H. O.

    2015-12-01

    In recent times, fluorine has been receiving increasing attention due to the possibility for chemical (HF) leakage accidents and its high toxicity to human and environment. In this respect, a novel approach for the determination of fluorine concentrations in water samples using wavelength dispersive X-ray fluorescence (WDXRF) spectrometry was investigated in this study. The main disadvantage of WDXRF technique for fluorine analysis is low analytical sensitivity for light elements with atomic number (Z) less than 15. To overcome this problem, we employed the precipitation reaction which fluoride is reacted with cation such as Al3+ and/or Ca2+ prior to WDXRF analysis because of their high analytical sensitivity. The cation was added in fluoride solutions to form precipitate (AlF3 and/or CaF2) and then the solution was filtered through Whatman filter. After drying at 60 °C for 5 min, the filter was coated with X-ray film and directly analyzed using WDXRF spectrometry. Consequently, we analyzed the cation on filter and subsequently fluorine concentration was calculated inversely based on chemical form of precipitate. This method can improve the analytical sensitivity of WDXRF technique for fluorine analysis and be applicable to various elements that can make precipitate.

  10. A comparison of serum and plasma cytokine values using a multiplexed assay in cats.

    PubMed

    Gruen, Margaret E; Messenger, Kristen M; Thomson, Andrea E; Griffith, Emily H; Paradise, Hayley; Vaden, Shelly; Lascelles, B D X

    2016-12-01

    Degenerative joint disease (DJD) is highly prevalent in cats, and pain contributes to morbidity. In humans, alterations of cytokine concentrations have been associated with joint deterioration and pain. Similar changes have not been investigated in cats. Cytokine concentrations can be measured using multiplex technology with small samples of serum or plasma, however, serum and plasma are not interchangeable for most bioassays. Correlations for cytokine concentrations between serum and plasma have not been evaluated in cats. To evaluate the levels of detection and agreement between serum and plasma samples in cats. Paired serum and plasma samples obtained from 38 cats. Blood was collected into anti-coagulant free and EDTA Vacutainer ® tubes, serum or plasma extracted, and samples frozen at -80°C until testing. Duplicate samples were tested using a 19-plex feline cytokine/chemokine magnetic bead panel. Agreement between serum and plasma for many analytes was high, however correlation coefficients ranged from -0.01 to 0.97. Results from >50% of samples were below the lower limit of quantification for both serum and plasma for nine analytes, and for an additional three analytes for plasma only. While serum and plasma agreement was generally good, detection was improved using serum samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Evaluation of Biomonitoring Data from the CDC National ...

    EPA Pesticide Factsheets

    BACKGROUND: Biomonitoring data reported in the National Report on Human Exposure to Environmental Chemicals (NER) provide information on the presence and concentrations of more than 400 chemicals in human blood and urine. Biomonitoring Equivalents (BEs) and other risk assessment-based values now allow interpretation of these biomonitoring data in a public health risk context. OBJECTIVES: Compare the measured biomarker concentrations in the NER with BEs and similar risk assessment values to provide an across-chemical risk assessment perspective on the measured levels for approximately 130 analytes in the NER. METHODS: Available risk assessment-based biomarker screening values, including BEs and Human Biomonitoring-I (HBM-I) values from the German Human Biomonitoring Commission, were identified. Geometric mean and 95th percentile population biomarker concentrations from the NER were compared to the available screening values to generate chemical-specific hazard quotients (HQ) or cancer risk estimates. CONCLUSIONS: Several analytes in the NER approach or exceed HQ values of 1 or cancer risks greater than 1x 10-4 at the geometric mean or 95th percentile, suggesting exposure levels exceed what is considered safe in a large fraction of the population. Analytes of concern include acrylamide, dioxin-like chemicals, benzene, xylene, several metals, di-2(ethylhexyl)phthalate, and some legacy organochlorine pesticides. This analysis provides for the first time a mean

  12. An active learning representative subset selection method using net analyte signal.

    PubMed

    He, Zhonghai; Ma, Zhenhe; Luan, Jingmin; Cai, Xi

    2018-05-05

    To guarantee accurate predictions, representative samples are needed when building a calibration model for spectroscopic measurements. However, in general, it is not known whether a sample is representative prior to measuring its concentration, which is both time-consuming and expensive. In this paper, a method to determine whether a sample should be selected into a calibration set is presented. The selection is based on the difference of Euclidean norm of net analyte signal (NAS) vector between the candidate and existing samples. First, the concentrations and spectra of a group of samples are used to compute the projection matrix, NAS vector, and scalar values. Next, the NAS vectors of candidate samples are computed by multiplying projection matrix with spectra of samples. Scalar value of NAS is obtained by norm computation. The distance between the candidate set and the selected set is computed, and samples with the largest distance are added to selected set sequentially. Last, the concentration of the analyte is measured such that the sample can be used as a calibration sample. Using a validation test, it is shown that the presented method is more efficient than random selection. As a result, the amount of time and money spent on reference measurements is greatly reduced. Copyright © 2018 Elsevier B.V. All rights reserved.

  13. An active learning representative subset selection method using net analyte signal

    NASA Astrophysics Data System (ADS)

    He, Zhonghai; Ma, Zhenhe; Luan, Jingmin; Cai, Xi

    2018-05-01

    To guarantee accurate predictions, representative samples are needed when building a calibration model for spectroscopic measurements. However, in general, it is not known whether a sample is representative prior to measuring its concentration, which is both time-consuming and expensive. In this paper, a method to determine whether a sample should be selected into a calibration set is presented. The selection is based on the difference of Euclidean norm of net analyte signal (NAS) vector between the candidate and existing samples. First, the concentrations and spectra of a group of samples are used to compute the projection matrix, NAS vector, and scalar values. Next, the NAS vectors of candidate samples are computed by multiplying projection matrix with spectra of samples. Scalar value of NAS is obtained by norm computation. The distance between the candidate set and the selected set is computed, and samples with the largest distance are added to selected set sequentially. Last, the concentration of the analyte is measured such that the sample can be used as a calibration sample. Using a validation test, it is shown that the presented method is more efficient than random selection. As a result, the amount of time and money spent on reference measurements is greatly reduced.

  14. Liquid-absorption preconcentrator sampling instrument

    DOEpatents

    Zaromb, Solomon

    1990-01-01

    A system for detecting trace concentrations of an analyte in air and includes a preconcentrator for the analyte and an analyte detector. The preconcentrator includes an elongated tubular container in which is disposed a wettable material extending substantially the entire length of the container. One end of the wettable material is continuously wetted with an analyte-sorbing liquid, which flows to the other end of the container. Sample air is flowed through the container in contact with the wetted material for trapping and preconcentrating the traces of analyte in the sorbing liquid, which is then collected at the other end of the container and discharged to the detector. The wetted material may be a wick comprising a bundle of fibers, one end of which is immersed in a reservoir of the analyte-sorbing liquid, or may be a liner disposed on the inner surface of the container, with the sorbing liquid being centrifugally dispersed onto the liner at one end thereof. The container is preferably vertically oriented so that gravity effects the liquid flow.

  15. Liquid-absorption preconcentrator sampling instrument

    DOEpatents

    Zaromb, S.

    1990-12-11

    A system is described for detecting trace concentrations of an analyte in air and includes a preconcentrator for the analyte and an analyte detector. The preconcentrator includes an elongated tubular container in which is disposed a wettable material extending substantially the entire length of the container. One end of the wettable material is continuously wetted with an analyte-sorbing liquid, which flows to the other end of the container. Sample air is flowed through the container in contact with the wetted material for trapping and preconcentrating the traces of analyte in the sorbing liquid, which is then collected at the other end of the container and discharged to the detector. The wetted material may be a wick comprising a bundle of fibers, one end of which is immersed in a reservoir of the analyte-sorbing liquid, or may be a liner disposed on the inner surface of the container, with the sorbing liquid being centrifugally dispersed onto the liner at one end thereof. The container is preferably vertically oriented so that gravity effects the liquid flow. 4 figs.

  16. Analytical fingerprint for tantalum ores from African deposits

    NASA Astrophysics Data System (ADS)

    Melcher, F.; Graupner, T.; Sitnikova, M.; Oberthür, T.; Henjes-Kunst, F.; Gäbler, E.; Rantitsch, G.

    2009-04-01

    Illegal mining of gold, diamonds, copper, cobalt and, in the last decade, "coltan" has fuelled ongoing armed conflicts and civil war in a number of African countries. Following the United Nations initiative to fingerprint the origin of conflict materials and to develop a traceability system, our working group is investigating "coltan" (i.e. columbite-tantalite) mineralization especially in Africa, also within the wider framework of establishing certified trading chains (CTC). Special attention is directed towards samples from the main Ta-Nb-Sn provinces in Africa: DR Congo, Rwanda, Mozambique, Ethiopia, Egypt and Namibia. The following factors are taken into consideration in a methodological approach capable of distinguishing the origin of tantalum ores and concentrates with the utmost probability: (1) Quality and composition of coltan concentrates vary considerably. (2) Mineralogical and chemical compositions of Ta-Nb ores are extremely complex due to the wide range of the columbite-tantalite solid solution series and its ability to incorporate many additional elements. (3) Coltan concentrates may contain a number of other tantalum-bearing minerals besides columbite-tantalite. In our approach, coltan concentrates are analyzed in a step-by-step mode. State-of-the-art analytical tools employed are automated scanning electron microscopy (Mineral Liberation Analysis; MLA), electron microprobe analysis (major and trace elements), laser ablation-ICP-MS (trace elements, isotopes), and TIMS (U-Pb dating). Mineral assemblages in the ore concentrates, major and trace element concentration patterns, and zoning characteristics in the different pegmatites from Africa distinctly differ from each other. Chondrite-normalized REE distribution patterns vary significantly between columbite, tantalite, and microlite, and also relative to major element compositions of columbites. Some locations are characterized by low REE concentrations, others are highly enriched. Samples with Kibaran age either show flat patterns for most tantalites, rising values from the LREE to the HREE, or trough-like patterns. Eu anomalies are strongly negative in columbite-tantalite from the Alto Ligonha Province in Mozambique, from the Namaqualand Province (Namibia, South Africa), and from Zimbabwe. Four main age populations of coltan deposits in Africa were revealed: (1) Archean (>2.5 Ga), (2) Paleoproterozoic (2.1-1.9 Ga), (3) early Neoproterozoic ("Kibaran", 1.0-0.9 Ga), and (4) late Neoproterozoic to early Paleozoic (Pan-African; ca. 0.6-0.4 Ga). Currently, we focus on the resolution of the fingerprinting system from region via ore province down to deposit scale, establishing a large and high-quality analytical data base, and developing fast-screening and low-cost methods. Analytical flow-charts and identification schemes for coltan ores will be presented at the Conference. The analytical results obtained so far indicate that a certification scheme including fingerprinting of sources of coltan ores is feasible. The methodology developed is capable to assist in the establishment of a control instrument in an envisaged certification of the production and trade chain of coltan.

  17. U.S. Geological Survey external quality-assurance project report to the National Atmospheric Deposition Program / National Trends Network and Mercury Deposition Network, 2007-08

    USGS Publications Warehouse

    Wetherbee, Gregory A.; Latysh, Natalie E.; Chesney, Tanya A.

    2010-01-01

    The U.S. Geological Survey (USGS) used six distinct programs to provide external quality-assurance monitoring for the National Atmospheric Deposition Program / National Trends Network (NTN) and Mercury Deposition Network (MDN) during 2007-08. The field-audit program assessed the effects of onsite exposure, sample handling, and shipping on the chemistry of NTN samples, and a system-blank program assessed the same effects for MDN. Two interlaboratory-comparison programs assessed the bias and variability of the chemical analysis data from the Central Analytical Laboratory (CAL), Mercury (Hg) Analytical Laboratory (HAL), and 12 other participating laboratories. A blind-audit program was also implemented for the MDN to evaluate analytical bias in HAL total Hg concentration data. A co-located-sampler program was used to identify and quantify potential shifts in NADP data resulting from replacement of original network instrumentation with new electronic recording rain gages (E-gages) and prototype precipitation collectors. The results indicate that NADP data continue to be of sufficient quality for the analysis of spatial distributions and time trends of chemical constituents in wet deposition across the U.S. NADP data-quality objectives continued to be achieved during 2007-08. Results also indicate that retrofit of the NADP networks with the new E-gages is not likely to create step-function type shifts in NADP precipitation-depth records, except for sites where annual precipitation depth is dominated by snow because the E-gages tend to catch more snow than the original NADP rain gages. Evaluation of prototype precipitation collectors revealed no difference in sample volumes and analyte concentrations between the original NADP collectors and modified, deep-bucket collectors, but the Yankee Environmental Systems, Inc. (YES) collector obtained samples of significantly higher volumes and analyte concentrations than the standard NADP collector.

  18. Analytical results for minicipal biosolids samples from a monitoring program near Deer Trail, Colorado (U.S.A.) 2010

    USGS Publications Warehouse

    Crock, J.G.; Smith, D.B.; Yager, T.J.B.; Berry, C.J.; Adams, M.G.

    2011-01-01

    Since late 1993, Metro Wastewater Reclamation District of Denver (Metro District), a large wastewater treatment plant in Denver, Colo., has applied Grade I, Class B biosolids to about 52,000 acres of nonirrigated farmland and rangeland near Deer Trail, Colo., U.S.A. In cooperation with the Metro District in 1993, the U.S. Geological Survey (USGS) began monitoring groundwater at part of this site. In 1999, the USGS began a more comprehensive monitoring study of the entire site to address stakeholder concerns about the potential chemical effects of biosolids applications to water, soil, and vegetation. This more comprehensive monitoring program was recently extended through the end of 2010 and is now completed. Monitoring components of the more comprehensive study include biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock groundwater, and stream-bed sediment. Streams at the site are dry most of the year, so samples of stream-bed sediment deposited after rain were used to indicate surface-water runoff effects. This report summarizes analytical results for the biosolids samples collected at the Metro District wastewater treatment plant in Denver and analyzed for 2010. In general, the objective of each component of the study was to determine whether concentrations of nine trace elements ("priority analytes") (1) were higher than regulatory limits, (2) were increasing with time, or (3) were significantly higher in biosolids-applied areas than in a similar farmed area where biosolids were not applied (background). Previous analytical results indicate that the elemental composition of biosolids from the Denver plant was consistent during 1999-2009, and this consistency continues with the samples for 2010. Total concentrations of regulated trace elements remain consistently lower than the regulatory limits for the entire monitoring period. Concentrations of none of the priority analytes appear to have increased during the 12 years of this study.

  19. Analytical results for municipal biosolids samples from a monitoring program near Deer Trail, Colorado (U.S.A.), 2009

    USGS Publications Warehouse

    Crock, J.G.; Smith, D.B.; Yager, T.J.B.; Berry, C.J.; Adams, M.G.

    2010-01-01

    Since late 1993, Metro Wastewater Reclamation District of Denver, a large wastewater treatment plant in Denver, Colo., has applied Grade I, Class B biosolids to about 52,000 acres of nonirrigated farmland and rangeland near Deer Trail, Colo., U.S.A. In cooperation with the Metro District in 1993, the U.S. Geological Survey began monitoring groundwater at part of this site. In 1999, the Survey began a more comprehensive monitoring study of the entire site to address stakeholder concerns about the potential chemical effects of biosolids applications to water, soil, and vegetation. This more comprehensive monitoring program has recently been extended through the end of 2010. Monitoring components of the more comprehensive study include biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock groundwater, and stream-bed sediment. Streams at the site are dry most of the year, so samples of stream-bed sediment deposited after rain were used to indicate surface-water effects. This report presents analytical results for the biosolids samples collected at the Metro District wastewater treatment plant in Denver and analyzed for 2009. In general, the objective of each component of the study was to determine whether concentrations of nine trace elements ('priority analytes') (1) were higher than regulatory limits, (2) were increasing with time, or (3) were significantly higher in biosolids-applied areas than in a similar farmed area where biosolids were not applied. Previous analytical results indicate that the elemental composition of biosolids from the Denver plant was consistent during 1999-2008, and this consistency continues with the samples for 2009. Total concentrations of regulated trace elements remain consistently lower than the regulatory limits for the entire monitoring period. Concentrations of none of the priority analytes appear to have increased during the 11 years of this study.

  20. Development of a dynamic headspace gas chromatography-mass spectrometry method for on-site analysis of sulfur mustard degradation products in sediments.

    PubMed

    Magnusson, R; Nordlander, T; Östin, A

    2016-01-15

    Sampling teams performing work at sea in areas where chemical munitions may have been dumped require rapid and reliable analytical methods for verifying sulfur mustard leakage from suspected objects. Here we present such an on-site analysis method based on dynamic headspace GC-MS for analysis of five cyclic sulfur mustard degradation products that have previously been detected in sediments from chemical weapon dumping sites: 1,4-oxathiane, 1,3-dithiolane, 1,4-dithiane, 1,4,5-oxadithiephane, and 1,2,5-trithiephane. An experimental design involving authentic Baltic Sea sediments spiked with the target analytes was used to develop an optimized protocol for sample preparation, headspace extraction and analysis that afforded recoveries of up to 60-90%. The optimized method needs no organic solvents, uses only two grams of sediment on a dry weight basis and involves a unique sample presentation whereby sediment is spread uniformly as a thin layer inside the walls of a glass headspace vial. The method showed good linearity for analyte concentrations of 5-200 ng/g dw, good repeatability, and acceptable carry-over. The method's limits of detection for spiked sediment samples ranged from 2.5 to 11 μg/kg dw, with matrix interference being the main limiting factor. The instrumental detection limits were one to two orders of magnitude lower. Full-scan GC-MS analysis enabled the use of automated mass spectral deconvolution for rapid identification of target analytes. Using this approach, analytes could be identified in spiked sediment samples at concentrations down to 13-65 μg/kg dw. On-site validation experiments conducted aboard the research vessel R/V Oceania demonstrated the method's practical applicability, enabling the successful identification of four cyclic sulfur mustard degradation products at concentrations of 15-308μg/kg in sediments immediately after being collected near a wreck at the Bornholm Deep dumpsite in the Baltic Sea. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Validation of a two-dimensional gas chromatography mass spectrometry method for the simultaneous quantification of cannabidiol, Delta(9)-tetrahydrocannabinol (THC), 11-hydroxy-THC, and 11-nor-9-carboxy-THC in plasma.

    PubMed

    Karschner, Erin L; Barnes, Allan J; Lowe, Ross H; Scheidweiler, Karl B; Huestis, Marilyn A

    2010-05-01

    A sensitive analytical method for simultaneous quantification of sub-nanogram concentrations of cannabidiol (CBD), Delta(9)-tetrahydrocannabinol (THC), 11-hydroxy-THC (11-OH-THC), and 11-nor-9-carboxy-THC (THCCOOH) in plasma is presented for monitoring cannabinoid pharmacotherapy and illicit cannabis use. Analytes were extracted from 1 mL plasma by solid-phase extraction, derivatized with N,O-bis(trimethylsilyl) trifluoroacetamide with 1% trimethylchlorosilane, and analyzed by two-dimensional gas chromatography mass spectrometry (2D-GCMS) with cryofocusing. The lower calibration curve was linear from 0.25-25 ng/mL for CBD and THC, 0.125-25 ng/mL for 11-OH-THC and 0.25-50 ng/mL for THCCOOH. A second higher linear range from 5-100 ng/mL, achieved through modification of injection parameters, was validated for THC, 11-OH-THC, and THCCOOH and was only implemented if concentrations exceeded the lower curve upper limit of linearity. This procedure prevented laborious re-extraction by allowing the same specimen to be re-injected for quantification on the high calibration curve. Intra- and inter-assay imprecision, determined at four quality control concentrations, were or=72.9% for all analytes. Analytes were stable when stored at 22 degrees C for 16 h, 4 degrees C for 48 h, after three freeze-thaw cycles at -20 degrees C and when stored on the autosampler for 48 h. This sensitive and specific 2D-GCMS assay provides a new means of simultaneously quantifying CBD, THC and metabolite biomarkers in clinical medicine, forensic toxicology, workplace drug testing, and driving under the influence of drugs programs.

  2. Detection, characterization and quantification of inorganic engineered nanomaterials: A review of techniques and methodological approaches for the analysis of complex samples.

    PubMed

    Laborda, Francisco; Bolea, Eduardo; Cepriá, Gemma; Gómez, María T; Jiménez, María S; Pérez-Arantegui, Josefina; Castillo, Juan R

    2016-01-21

    The increasing demand of analytical information related to inorganic engineered nanomaterials requires the adaptation of existing techniques and methods, or the development of new ones. The challenge for the analytical sciences has been to consider the nanoparticles as a new sort of analytes, involving both chemical (composition, mass and number concentration) and physical information (e.g. size, shape, aggregation). Moreover, information about the species derived from the nanoparticles themselves and their transformations must also be supplied. Whereas techniques commonly used for nanoparticle characterization, such as light scattering techniques, show serious limitations when applied to complex samples, other well-established techniques, like electron microscopy and atomic spectrometry, can provide useful information in most cases. Furthermore, separation techniques, including flow field flow fractionation, capillary electrophoresis and hydrodynamic chromatography, are moving to the nano domain, mostly hyphenated to inductively coupled plasma mass spectrometry as element specific detector. Emerging techniques based on the detection of single nanoparticles by using ICP-MS, but also coulometry, are in their way to gain a position. Chemical sensors selective to nanoparticles are in their early stages, but they are very promising considering their portability and simplicity. Although the field is in continuous evolution, at this moment it is moving from proofs-of-concept in simple matrices to methods dealing with matrices of higher complexity and relevant analyte concentrations. To achieve this goal, sample preparation methods are essential to manage such complex situations. Apart from size fractionation methods, matrix digestion, extraction and concentration methods capable of preserving the nature of the nanoparticles are being developed. This review presents and discusses the state-of-the-art analytical techniques and sample preparation methods suitable for dealing with complex samples. Single- and multi-method approaches applied to solve the nanometrological challenges posed by a variety of stakeholders are also presented. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Characterization of renal biomarkers for use in clinical trials: biomarker evaluation in healthy volunteers

    PubMed Central

    Brott, David A; Adler, Scott H; Arani, Ramin; Lovick, Susan C; Pinches, Mark; Furlong, Stephen T

    2014-01-01

    Background Several preclinical urinary biomarkers have been qualified and accepted by the health authorities (US Food and Drug Administration, European Medicines Agency, and Pharmaceuticals and Medical Devices Agency) for detecting drug-induced kidney injury during preclinical toxicologic testing. Validated human assays for many of these biomarkers have become commercially available, and this study was designed to characterize some of the novel clinical renal biomarkers. The objective of this study was to evaluate clinical renal biomarkers in a typical Phase I healthy volunteer population to determine confidence intervals (pilot reference intervals), intersubject and intrasubject variability, effects of food intake, effect of sex, and vendor assay comparisons. Methods Spot urine samples from 20 male and 19 female healthy volunteers collected on multiple days were analyzed using single analyte and multiplex assays. The following analytes were measured: α-1-microglobulin, β-2-microglobulin, calbindin, clusterin, connective tissue growth factor, creatinine, cystatin C, glutathione S-transferase-α, kidney injury marker-1, microalbumin, N-acetyl-β-(D) glucosaminidase, neutrophil gelatinase-associated lipocalin, osteopontin, Tamm-Horsfall urinary glycoprotein, tissue inhibitor of metalloproteinase 1, trefoil factor 3, and vascular endothelial growth factor. Results Confidence intervals were determined from the single analyte and multiplex assays. Intersubject and intrasubject variability ranged from 38% to 299% and from 29% to 82% for biomarker concentration, and from 24% to 331% and from 10% to 67% for biomarker concentration normalized to creatinine, respectively. There was no major effect of food intake or sex. Single analyte and multiplex assays correlated with r2≥0.700 for five of six biomarkers when evaluating biomarker concentration, but for only two biomarkers when evaluating concentration normalized to creatinine. Conclusion Confidence intervals as well as intersubject and intrasubject variability were determined for novel clinical renal biomarkers/assays, which should be considered for evaluation in the next steps of the qualification process. PMID:24611000

  4. Characterization of renal biomarkers for use in clinical trials: biomarker evaluation in healthy volunteers.

    PubMed

    Brott, David A; Adler, Scott H; Arani, Ramin; Lovick, Susan C; Pinches, Mark; Furlong, Stephen T

    2014-01-01

    Several preclinical urinary biomarkers have been qualified and accepted by the health authorities (US Food and Drug Administration, European Medicines Agency, and Pharmaceuticals and Medical Devices Agency) for detecting drug-induced kidney injury during preclinical toxicologic testing. Validated human assays for many of these biomarkers have become commercially available, and this study was designed to characterize some of the novel clinical renal biomarkers. The objective of this study was to evaluate clinical renal biomarkers in a typical Phase I healthy volunteer population to determine confidence intervals (pilot reference intervals), intersubject and intrasubject variability, effects of food intake, effect of sex, and vendor assay comparisons. Spot urine samples from 20 male and 19 female healthy volunteers collected on multiple days were analyzed using single analyte and multiplex assays. The following analytes were measured: α-1-microglobulin, β-2-microglobulin, calbindin, clusterin, connective tissue growth factor, creatinine, cystatin C, glutathione S-transferase-α, kidney injury marker-1, microalbumin, N-acetyl-β-(D) glucosaminidase, neutrophil gelatinase-associated lipocalin, osteopontin, Tamm-Horsfall urinary glycoprotein, tissue inhibitor of metalloproteinase 1, trefoil factor 3, and vascular endothelial growth factor. Confidence intervals were determined from the single analyte and multiplex assays. Intersubject and intrasubject variability ranged from 38% to 299% and from 29% to 82% for biomarker concentration, and from 24% to 331% and from 10% to 67% for biomarker concentration normalized to creatinine, respectively. There was no major effect of food intake or sex. Single analyte and multiplex assays correlated with r (2)≥0.700 for five of six biomarkers when evaluating biomarker concentration, but for only two biomarkers when evaluating concentration normalized to creatinine. Confidence intervals as well as intersubject and intrasubject variability were determined for novel clinical renal biomarkers/assays, which should be considered for evaluation in the next steps of the qualification process.

  5. Development of a System Model for Non-Invasive Quantification of Bilirubin in Jaundice Patients

    NASA Astrophysics Data System (ADS)

    Alla, Suresh K.

    Neonatal jaundice is a medical condition which occurs in newborns as a result of an imbalance between the production and elimination of bilirubin. Excess bilirubin in the blood stream diffuses into the surrounding tissue leading to a yellowing of the skin. An optical system integrated with a signal processing system is used as a platform to noninvasively quantify bilirubin concentration through the measurement of diffuse skin reflectance. Initial studies have lead to the generation of a clinical analytical model for neonatal jaundice which generates spectral reflectance data for jaundiced skin with varying levels of bilirubin concentration in the tissue. The spectral database built using the clinical analytical model is then used as a test database to validate the signal processing system in real time. This evaluation forms the basis for understanding the translation of this research to human trials. The clinical analytical model and signal processing system have been successful validated on three spectral databases. First spectral database is constructed using a porcine model as a surrogate for neonatal skin tissue. Samples of pig skin were soaked in bilirubin solutions of varying concentrations to simulate jaundice skin conditions. The resulting skins samples were analyzed with our skin reflectance systems producing bilirubin concentration values that show a high correlation (R2 = 0.94) to concentration of the bilirubin solution that each porcine tissue sample is soaked in. The second spectral database is the spectral measurements collected on human volunteers to quantify the different chromophores and other physical properties of the tissue such a Hematocrit, Hemoglobin etc. The third spectral database is the spectral data collected at different time periods from the moment a bruise is induced.

  6. Second-order data obtained by beta-cyclodextrin complexes: a novel approach for multicomponent analysis with three-way multivariate calibration methods.

    PubMed

    Khani, Rouhollah; Ghasemi, Jahan B; Shemirani, Farzaneh

    2014-10-01

    This research reports the first application of β-cyclodextrin (β-CD) complexes as a new method for generation of three way data, combined with second-order calibration methods for quantification of a binary mixture of caffeic (CA) and vanillic (VA) acids, as model compounds in fruit juices samples. At first, the basic experimental parameters affecting the formation of inclusion complexes between target analytes and β-CD were investigated and optimized. Then under the optimum conditions, parallel factor analysis (PARAFAC) and bilinear least squares/residual bilinearization (BLLS/RBL) were applied for deconvolution of trilinear data to get spectral and concentration profiles of CA and VA as a function of β-CD concentrations. Due to severe concentration profile overlapping between CA and VA in β-CD concentration dimension, PARAFAC could not be successfully applied to the studied samples. So, BLLS/RBL performed better than PARAFAC. The resolution of the model compounds was possible due to differences in the spectral absorbance changes of the β-CD complexes signals of the investigated analytes, opening a new approach for second-order data generation. The proposed method was validated by comparison with a reference method based on high-performance liquid chromatography photodiode array detection (HPLC-PDA), and no significant differences were found between the reference values and the ones obtained with the proposed method. Such a chemometrics-based protocol may be a very promising tool for more analytical applications in real samples monitoring, due to its advantages of simplicity, rapidity, accuracy, sufficient spectral resolution and concentration prediction even in the presence of unknown interferents. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Modeling ventilation time in forage tower silos.

    PubMed

    Bahloul, A; Chavez, M; Reggio, M; Roberge, B; Goyer, N

    2012-10-01

    The fermentation process in forage tower silos produces a significant amount of gases, which can easily reach dangerous concentrations and constitute a hazard for silo operators. To maintain a non-toxic environment, silo ventilation is applied. Literature reviews show that the fermentation gases reach high concentrations in the headspace of a silo and flow down the silo from the chute door to the feed room. In this article, a detailed parametric analysis of forced ventilation scenarios built via numerical simulation was performed. The methodology is based on the solution of the Navier-Stokes equations, coupled with transport equations for the gas concentrations. Validation was achieved by comparing the numerical results with experimental data obtained from a scale model silo using the tracer gas testing method for O2 and CO2 concentrations. Good agreement was found between the experimental and numerical results. The set of numerical simulations made it possible to establish a simple analytical model to predict the minimum time required to ventilate a silo to make it safe to enter. This ventilation time takes into account the headspace above the forage, the airflow rate, and the initial concentrations of O2 and CO2. The final analytical model was validated with available results from the literature.

  8. Specific interaction between negative atmospheric ions and organic compounds in atmospheric pressure corona discharge ionization mass spectrometry.

    PubMed

    Sekimoto, Kanako; Sakai, Mami; Takayama, Mitsuo

    2012-06-01

    The interaction between negative atmospheric ions and various types of organic compounds were investigated using atmospheric pressure corona discharge ionization (APCDI) mass spectrometry. Atmospheric negative ions such as O(2)(-), HCO(3)(-), COO(-)(COOH), NO(2)(-), NO(3)(-), and NO(3)(-)(HNO(3)) having different proton affinities served as the reactant ions for analyte ionization in APCDI in negative-ion mode. The individual atmospheric ions specifically ionized aliphatic and aromatic compounds with various functional groups as atmospheric ion adducts and deprotonated analytes. The formation of the atmospheric ion adducts under certain discharge conditions is most likely attributable to the affinity between the analyte and atmospheric ion and the concentration of the atmospheric ion produced under these conditions. The deprotonated analytes, in contrast, were generated from the adducts of the atmospheric ions with higher proton affinity attributable to efficient proton abstraction from the analyte by the atmospheric ion.

  9. Technical Report on the Behavior of Trace Elements, Stable Isotopes, and Radiogenic Isotopes During the Processing of Uranium Ore to Uranium Ore Concentrate

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Marks, N. E.; Borg, L. E.; Eppich, G. R.

    2015-07-09

    The goals of this SP-1 effort were to understand how isotopic and elemental signatures behave during mining, milling, and concentration and to identify analytes that might preserve geologic signatures of the protolith ores. The impurities that are preserved through the concentration process could provide useful forensic signatures and perhaps prove diagnostic of sample origin.

  10. High Throughput Determination of Critical Human Dosing ...

    EPA Pesticide Factsheets

    High throughput toxicokinetics (HTTK) is a rapid approach that uses in vitro data to estimate TK for hundreds of environmental chemicals. Reverse dosimetry (i.e., reverse toxicokinetics or RTK) based on HTTK data converts high throughput in vitro toxicity screening (HTS) data into predicted human equivalent doses that can be linked with biologically relevant exposure scenarios. Thus, HTTK provides essential data for risk prioritization for thousands of chemicals that lack TK data. One critical HTTK parameter that can be measured in vitro is the unbound fraction of a chemical in plasma (Fub). However, for chemicals that bind strongly to plasma, Fub is below the limits of detection (LOD) for high throughput analytical chemistry, and therefore cannot be quantified. A novel method for quantifying Fub was implemented for 85 strategically selected chemicals: measurement of Fub was attempted at 10%, 30%, and 100% of physiological plasma concentrations using rapid equilibrium dialysis assays. Varying plasma concentrations instead of chemical concentrations makes high throughput analytical methodology more likely to be successful. Assays at 100% plasma concentration were unsuccessful for 34 chemicals. For 12 of these 34 chemicals, Fub could be quantified at 10% and/or 30% plasma concentrations; these results imply that the assay failure at 100% plasma concentration was caused by plasma protein binding for these chemicals. Assay failure for the remaining 22 chemicals may

  11. Gas-Permeable Membrane-Based Conductivity Probe Capable of In Situ Real-Time Monitoring of Ammonia in Aquatic Environments.

    PubMed

    Li, Tianling; Panther, Jared; Qiu, Yuan; Liu, Chang; Huang, Jianyin; Wu, Yonghong; Wong, Po Keung; An, Taicheng; Zhang, Shanqing; Zhao, Huijun

    2017-11-21

    Aquatic ammonia has toxic effects on aquatic life. This work reports a gas-permeable membrane-based conductivity probe (GPMCP) developed for real-time monitoring of ammonia in aquatic environments. The GPMCP innovatively combines a gas-permeable membrane with a boric acid receiving phase to selectively extract ammonia from samples and form ammonium at the inner membrane interface. The rate of the receiving phase conductivity increase is directly proportional to the instantaneous ammonia concentration in the sample, which can be rapidly and sensitively determined by the embedded conductivity detector. A precalibration strategy was developed to eliminate the need for an ongoing calibration. The analytical principle and GPMCP performance were systematically validated. The laboratory results showed that ammonia concentrations ranging from 2 to 50 000 μg L -1 can be detected. The field deployment results demonstrated the GPMCP's ability to obtain high-resolution continuous ammonia concentration profiles and the absolute average ammonia concentration over a prolonged deployment period. By inputting the temperature and pH data, the ammonium concentration can be simultaneously derived from the corresponding ammonia concentration. The GPMCP embeds a sophisticated analytical principle with the inherent advantages of high selectivity, sensitivity, and accuracy, and it can be used as an effective tool for long-term, large-scale, aquatic-environment assessments.

  12. Dynamic OCT monitoring and quantification of light penetration enhancement for normal, benign and cancerous human lung tissues at different concentrations of glycerol

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shu-wen Tan; Ying Jin; Hui Yu

    2013-10-31

    We have evaluated the dynamic effects of the analyte diffusion on the 1/e light penetration depths of normal, benign and cancerous human lung tissue in vitro, as well as have monitored and quantified the dynamic change in the light penetration depths of the mentioned human lung tissue after application of 25 % and 50 % glycerol solution, respectively. The light penetration depths of the analyte diffusion in the lung tissue are measured using the Fourierdomain optical coherence tomography (FD-OCT). Experimental results show that the application of glycerol as a chemical agent can significantly enhance light penetration depths into the humanmore » normal lung (NL), lung benign granulomatosis (LBG) and lung squamous cell carcinoma (LSCC) tissue. In-depth transport of the glycerol molecules in the NL, LBG and LSCC tissue at a lower glycerol concentration (25 %) are faster than those at a higher glycerol concentration (50 %), and the 1/e light penetration depths at a lower glycerol concentration (25 %) are smaller than those at a higher glycerol concentration (50 %), respectively. Their differences in the maximal 1/e light penetration depths of the NL, LBG and LSCC tissue at a higher and a lower glycerol concentrations were only 8.8 %, 6.8 % and 4.7 %, respectively. (biophotonics)« less

  13. Multiplexed Paper Analytical Device for Quantification of Metals using Distance-Based Detection

    PubMed Central

    Cate, David M.; Noblitt, Scott D.; Volckens, John; Henry, Charles S.

    2015-01-01

    Exposure to metal-containing aerosols has been linked with adverse health outcomes for almost every organ in the human body. Commercially available techniques for quantifying particulate metals are time-intensive, laborious, and expensive; often sample analysis exceeds $100. We report a simple technique, based upon a distance-based detection motif, for quantifying metal concentrations of Ni, Cu, and Fe in airborne particulate matter using microfluidic paper-based analytical devices. Paper substrates are used to create sensors that are self-contained, self-timing, and require only a drop of sample for operation. Unlike other colorimetric approaches in paper microfluidics that rely on optical instrumentation for analysis, with distance-based detection, analyte is quantified visually based on the distance of a colorimetric reaction, similar to reading temperature on a thermometer. To demonstrate the effectiveness of this approach, Ni, Cu, and Fe were measured individually in single-channel devices; detection limits as low as 0.1, 0.1, and 0.05 µg were reported for Ni, Cu, and Fe. Multiplexed analysis of all three metals was achieved with detection limits of 1, 5, and 1 µg for Ni, Cu, and Fe. We also extended the dynamic range for multi-analyte detection by printing concentration gradients of colorimetric reagents using an off the shelf inkjet printer. Analyte selectivity was demonstrated for common interferences. To demonstrate utility of the method, Ni, Cu, and Fe were measured from samples of certified welding fume; levels measured with paper sensors matched known values determined gravimetrically. PMID:26009988

  14. Determination of atrazine and its major degradation products in soil pore water by solid-phase extraction, chemical derivatization, and gas chromatography/mass spectrometry

    USGS Publications Warehouse

    Carter, D.S.

    1996-01-01

    This report describes a method for the determination of atrazine, desethylatrazine, deisopropylatrazine, didealkylatrazine, and hydroxyatrazine from soil pore waters by use of solid-phase extractionfollowed by chemical derivatization and gas chromatography/mass spectrometry. The analytes are isolated from the pore-water matrix byextraction onto a graphitized carbon-black cartridge. The cartridge is dried under vacuum, and adsorbed analytes are removed by elution with ethyl acetate followed by dichloromethane/methanol (7:3, volume/volume). Water is removed from the ethyl acetate fraction on an anhydrous sodium sulfate column. The combined fractions are solvent exchanged into acetonitrile, evaporated by use of a nitrogen stream, and derivatized by use of N- methyl-N-(tert-butyldimethylsilyl)- trifluoroacetamide. The derivatized extracts are analyzed by capillary-column gaschromatography/electron-impact mass spectrometry in the scan mode. Estimated method detection limits range from 0.03 to 0.07 micrograms per liter. The mean recoveries of all analytes and surrogates determined at 0.74 to 0.82 micrograms per liter in reagent water in soil pore water were 94 percent and 98 percent, respectively. The mean recoveries of all analytes and surrogates determined at 7.4 to 8.2 micrograms per liter in reagent water and in soil pore water were 96 percent and 97 percent,respectively. Recoveries were 90 percent or higher, regardless of analyte concentration or matrix composition, for all compounds excepthydroxyatrazine, whose recoveries were slightly lower (77 percent) at the low concentration.

  15. An approximate analytical methodology for the concentration CDF and corresponding adverse health effects in 3D heterogeneous aquifers

    NASA Astrophysics Data System (ADS)

    Zarlenga, Antonio; de Barros, Felipe; Fiori, Aldo

    2017-04-01

    Predicting solutes displacement in ecosystems is a complex task because of heterogeneity of hydrogeological properties and limited financial resources for characterization. As a consequence, solute transport model predictions are subject to uncertainty and probabilistic methods are invoked. Despite the significant theoretical advances in subsurface hydrology, there is a compelling need to transfer those specialized know-hows into an easy-to-use practical tool. The deterministic approach is able to capture some features of the transport behavior but its adoption in practical applications (e.g. remediation strategies or health risk assessment) is often inadequate because of its inability to accurately model the phenomena triggered by the spatial heterogeneity. The rigorous evaluation of the local contaminant concentration in natural aquifers requires an accurate estimate of the domain properties and huge computational times; those aspects limit the adoption of fully 3D numerical models. In this presentation, we illustrate a physically-based methodology to analytically estimate of the statistics of the solute concentration in natural aquifers and the related health risk. Our methodology aims to provide a simple tool for a quick assessment of the contamination level in aquifers, as function of a few relevant, physically based parameters such as the log conductivity variance, the mean flow velocity, the Péclet number. Solutions of the 3D analytical model adopt the results of previous works: transport model is based on the solutions proposed by Zarlenga and Fiori (2013, 2014) where semi-analytical relations for the statics of local contaminant concentration are carry out through a Lagrangian first-order model. As suggested in de Barros and Fiori (2014), the Beta distribution is assumed for the concentration cumulative density function (CDF). We illustrate the use of the closed-form equations for the probability of local contaminant concentration and health risk in a series of problems of practical relevance. The basic scenario is constituted by a steady state plume in a 3D heterogeneous formation. In this case the non-reactive transport is ruled by interplay of the spreading (lateral and vertical) and dilution. The second scenario considers two different dynamics of degradation in aerobic and anaerobic conditions which allows the contaminant abatement. The final example links the environmental concentration with adverse health effects. For this case, additional information on toxicological and behavioral parameters are required. Despite the simplifying assumptions adopted, the proposed solutions are appealing in applications due to their simplicity and the fact that they allow to easily propagate the uncertainty from different sources in the final risk endpoint. de Barros, F.P., Fiori, A., 2014. First-order based cumulative distribution function for solute concentration in heterogeneous aquifers: theoretical analysis and implications for human health risk assessment. Water Resour. Res. 50, 4018-4037. Zarlenga, A., Fiori, A., 2013. Steady plumes in heterogeneous porous formations: a stochastic lagrangian approach. Water Resour. Res. 49, 864-873. Zarlenga, A., Fiori, A., 2014. Stochastic analytical modeling of the biodegradation of steady plumes. J. Contam. Hydrol. 157, 106-116.

  16. Quality of nutrient data from streams and ground water sampled during water years 1992-2001

    USGS Publications Warehouse

    Mueller, David K.; Titus, Cindy J.

    2005-01-01

    Proper interpretation of water-quality data requires consideration of the effects that bias and variability might have on measured constituent concentrations. In this report, methods are described to estimate the bias due to contamination of samples in the field or laboratory and the variability due to sample collection, processing, shipment, and analysis. Contamination can adversely affect interpretation of measured concentrations in comparison to standards or criteria. Variability can affect interpretation of small differences between individual measurements or mean concentrations. Contamination and variability are determined for nutrient data from quality-control samples (field blanks and replicates) collected as part of the National Water-Quality Assessment (NAWQA) Program during water years 1992-2001. Statistical methods are used to estimate the likelihood of contamination and variability in all samples. Results are presented for five nutrient analytes from stream samples and four nutrient analytes from ground-water samples. Ammonia contamination can add at least 0.04 milligram per liter in up to 5 percent of all samples. This could account for more than 22 percent of measured concentrations at the low range of aquatic-life criteria (0.18 milligram per liter). Orthophosphate contamination, at least 0.019 milligram per liter in up to 5 percent of all samples, could account for more than 38 percent of measured concentrations at the limit to avoid eutrophication (0.05 milligram per liter). Nitrite-plus-nitrate and Kjeldahl nitrogen contamination is less than 0.4 milligram per liter in 99 percent of all samples; thus there is no significant effect on measured concentrations of environmental significance. Sampling variability has little or no effect on reported concentrations of ammonia, nitrite-plus-nitrate, orthophosphate, or total phosphorus sampled after 1998. The potential errors due to sampling variability are greater for the Kjeldahl nitrogen analytes and for total phosphorus sampled before 1999. The uncertainty in a mean of 10 concentrations caused by sampling variability is within a small range (1 to 7 percent) for all nutrients. These results can be applied to interpretation of environmental data collected during water years 1992-2001 in 52 NAWQA study units.

  17. An investigation of the stability of free and glucuronidated 11-nor-delta9-tetrahydrocannabinol-9-carboxylic acid in authentic urine samples.

    PubMed

    Skopp, Gisela; Pötsch, Lucia

    2004-01-01

    Preanalytical stability of a drug and its major metabolites is an important consideration in pharmacokinetic studies or whenever the analyte pattern is used to estimate drug habits. Firstly, the stability of free and glucuronidated 11-nor-delta9-tetrahydrocannabinol-9-carboxylic acid (THCCOOH, THCCOOglu) in authentic urine samples was investigated. Random urine samples of cannabis users (n = 38) were stored at -20, 4, and 20 degrees C up to 15 days and up to 5 days at 40 degrees C, and alterations of the analyte pattern during storage were followed by liquid chromatography-tandem mass spectrometry. Secondly, the influence of pH (range 5.0-8.0) on the stability of the analytes was studied using spiked urine to elucidate the results obtained from authentic samples. In authentic urine samples, the initial pH ranged from 5.1 to 8.8. The glucuronide was found to be highly labile at a storage temperature of 4 degrees C and above. Initially, 18 urine samples tested positive for THCCOOH. After 2 days storage at 20 degrees C, THCCOOH was detectable in a further 4 samples, and 7 more samples tested positive for THCCOOH (5-81 ng/mL) after 15 days. Depending on time and temperature, the glucuronide concentration decreased, resulting in an increase of THCCOOH concentration. However, a loss in mean total THCCOOH concentration was found, which was significantly higher in deteriorated samples than in samples without signs of deterioration after 15 days of storage at 20 degrees C. In the drug-free urine sample separately spiked with THCCOOglu or THCCOOH, the investigations on the stability of the target analytes at various pH values revealed that THCCOOH was stable at pH 5.0. At higher pH values, its concentration slightly decreased with time, and about 69% of the initial THCCOOH concentration was still present at pH 8.0 on day 5. THCCOOglu concentrations rapidly decreased with increasing pH value. For example, only 72% of the initial THCCOOglu concentration could be detected at pH 5.0 on day 1. Degradation of the glucuronide resulted in formation of THCCOOH, which was observed even at pH 5.0. In light of the present findings, advanced forensic interpretations based on the presence of THCCOOH or the pattern of THCCOOH and THCCOOglu in stored urine samples seems questionable.

  18. Mission-Adaptable Chemical Sensor (MACS)

    DTIC Science & Technology

    2009-03-27

    with very high PDF and very low PFA (0.9999 and 0.0001, respectively). These objectives and more were met by the Phase 1 system, which is covered...area/volume ratio as possible (to reduce possible secondary sorption of analyte). In the current embodiment of the 2D concentrator, the sorbent is...and two porous layer open tubular (PLOT) columns have been assessed using approximately 60 sorbent/analyte combinations. The sorption /desorption

  19. Amplitudes of doping striations: comparison of numerical calculations and analytical approaches

    NASA Astrophysics Data System (ADS)

    Jung, T.; Müller, G.

    1997-02-01

    Transient, axisymmetric numerical calculations of the heat and species transport including convection were performed for a simplified vertical gradient freeze (Bridgman) process with bottom seeding for GaAs. Periodical oscillations were superimposed onto the transient heater temperature profile. The amplitudes of the resulting oscillations of the growth rate and the dopant concentration (striations) in the growing crystals are compared with the predictions of analytical models.

  20. Sub-micron surface plasmon resonance sensor systems

    NASA Technical Reports Server (NTRS)

    Glazier, James A. (Inventor); Amarie, Dragos (Inventor)

    2013-01-01

    Wearable or implantable devices combining microfluidic control of sample and reagent flow and micro-cavity surface plasmon resonance sensors functionalized with surface treatments or coatings capable of specifically binding to target analytes, ligands, or molecules in a bodily fluid are provided. The devices can be used to determine the presence and concentration of target analytes in the bodily fluids and thereby help diagnose, monitor or detect changes in disease conditions.

  1. National Water Quality Laboratory, 1995 services catalog

    USGS Publications Warehouse

    Timme, P.J.

    1995-01-01

    This Services Catalog contains information about field supplies and analytical services available from the National Water Quality Laboratory in Denver, Colo., and field supplies available from the Quality Water Service Unit in Ocala, Fla., to members of the U.S. Geological Survey. To assist personnel in the selection of analytical services, this catalog lists sample volume, required containers, applicable concentration range, detection level, precision of analysis, and preservation requirements for samples.

  2. Investigation of the matrix effect in determining microimpurities in boron and its compounds by atomic-emission spectrometry

    NASA Astrophysics Data System (ADS)

    Lebedeva, R. V.; Tumanova, A. N.; Mashin, N. I.

    2007-07-01

    We carried out a systematic study of the influence of the main component on the change of analytical signal during atomic-emission analysis of boron compounds. Changes in the intensity of spectral lines of microimpurities as functions of their concentrations in the analytical system based on graphite powder with a variable content of boric acid and boron oxide are presented.

  3. Fabricating Simple Wax Screen-Printing Paper-Based Analytical Devices to Demonstrate the Concept of Limiting Reagent in Acid- Base Reactions

    ERIC Educational Resources Information Center

    Namwong, Pithakpong; Jarujamrus, Purim; Amatatongchai, Maliwan; Chairam, Sanoe

    2018-01-01

    In this article, a low-cost, simple, and rapid fabrication of paper-based analytical devices (PADs) using a wax screen-printing method is reported here. The acid-base reaction is implemented in the simple PADs to demonstrate to students the chemistry concept of a limiting reagent. When a fixed concentration of base reacts with a gradually…

  4. New trends in the analytical determination of emerging contaminants and their transformation products in environmental waters.

    PubMed

    Agüera, Ana; Martínez Bueno, María Jesús; Fernández-Alba, Amadeo R

    2013-06-01

    Since the so-called emerging contaminants were established as a new group of pollutants of environmental concern, a great effort has been devoted to the knowledge of their distribution, fate and effects in the environment. After more than 20 years of work, a significant improvement in knowledge about these contaminants has been achieved, but there is still a large gap of information on the growing number of new potential contaminants that are appearing and especially of their unpredictable transformation products. Although the environmental problem arising from emerging contaminants must be addressed from an interdisciplinary point of view, it is obvious that analytical chemistry plays an important role as the first step of the study, as it allows establishing the presence of chemicals in the environment, estimate their concentration levels, identify sources and determine their degradation pathways. These tasks involve serious difficulties requiring different analytical solutions adjusted to purpose. Thus, the complexity of the matrices requires highly selective analytical methods; the large number and variety of compounds potentially present in the samples demands the application of wide scope methods; the low concentrations at which these contaminants are present in the samples require a high detection sensitivity, and high demands on the confirmation and high structural information are needed for the characterisation of unknowns. New developments on analytical instrumentation have been applied to solve these difficulties. Furthermore and not less important has been the development of new specific software packages intended for data acquisition and, in particular, for post-run analysis. Thus, the use of sophisticated software tools has allowed successful screening analysis, determining several hundreds of analytes, and assisted in the structural elucidation of unknown compounds in a timely manner.

  5. Ultrasensitive SERS Flow Detector Using Hydrodynamic Focusing

    PubMed Central

    Negri, Pierre; Jacobs, Kevin T.; Dada, Oluwatosin O.; Schultz, Zachary D.

    2013-01-01

    Label-free, chemical specific detection in flow is important for high throughput characterization of analytes in applications such as flow injection analysis, electrophoresis, and chromatography. We have developed a surface-enhanced Raman scattering (SERS) flow detector capable of ultrasensitive optical detection on the millisecond time scale. The device employs hydrodynamic focusing to improve SERS detection in a flow channel where a sheath flow confines analyte molecules eluted from a fused silica capillary over a planar SERS-active substrate. Increased analyte interactions with the SERS substrate significantly improve detection sensitivity. The performance of this flow detector was investigated using a combination of finite element simulations, fluorescence imaging, and Raman experiments. Computational fluid dynamics based on finite element analysis was used to optimize the flow conditions. The modeling indicates that a number of factors, such as the capillary dimensions and the ratio of the sheath flow to analyte flow rates, are critical for obtaining optimal results. Sample confinement resulting from the flow dynamics was confirmed using wide-field fluorescence imaging of rhodamine 6G (R6G). Raman experiments at different sheath flow rates showed increased sensitivity compared with the modeling predictions, suggesting increased adsorption. Using a 50-millisecond acquisitions, a sheath flow rate of 180 μL/min, and a sample flow rate of 5 μL/min, a linear dynamic range from nanomolar to micromolar concentrations of R6G with a LOD of 1 nM is observed. At low analyte concentrations, rapid analyte desorption is observed, enabling repeated and high-throughput SERS detection. The flow detector offers substantial advantages over conventional SERS-based assays such as minimal sample volumes and high detection efficiency. PMID:24074461

  6. Fingerprint Analysis: Moving Toward Multiattribute Determination via Individual Markers.

    PubMed

    Brunelle, Erica; Huynh, Crystal; Alin, Eden; Eldridge, Morgan; Le, Anh Minh; Halámková, Lenka; Halámek, Jan

    2018-01-02

    Forensic science will be forever revolutionized if law enforcement can identify personal attributes of a person of interest solely from a fingerprint. For the past 2 years, the goal of our group has been to establish a way to identify originator attributes, specifically biological sex, from a single analyte. To date, an enzymatic assay and two chemical assays have been developed for the analysis of multiple analytes. In this manuscript, two additional assays have been developed. This time, however, the assays utilize only one amino acid each. The enzymatic assay targets alanine and employs alanine transaminase (ALT), pyruvate oxidase (POx), and horseradish peroxidase (HRP). The other, a chemical assay, is known as the Sakaguchi test and targets arginine. It is important to note that alanine has a significantly higher concentration than arginine in the fingerprint content of both males and females. Both assays proved to be capable of accurately differentiating between male and female fingerprints, regardless of their respective average concentration. The ability to target a single analyte will transform forensic science as each originator attribute can be correlated to a different analyte. This would then lead to the possibility of identifying multiple attributes from a single fingerprint sample. Ultimately, this would allow for a profile of a person of interest to be established without the need for time-consuming lab processes.

  7. Development of a method for the determination of 9 currently used cotton pesticides by gas chromatography with electron capture detection.

    PubMed

    Zhang, Baohong; Pan, Xiaoping; Venne, Louise; Dunnum, Suzy; McMurry, Scott T; Cobb, George P; Anderson, Todd A

    2008-05-30

    A reliable, sensitive, and reproducible method was developed for quantitative determination of nine new generation pesticides currently used in cotton agriculture. Injector temperature significantly affected analyte response as indicated by electron capture detector (ECD) chromatograms. A majority of the analytes had an enhanced response at injector temperatures between 240 and 260 degrees C, especially analytes such as acephate that overall had a poor response on the ECD. The method detection limits (MDLs) were 0.13, 0.05, 0.29, 0.35, 0.08, 0.10, 0.32, 0.05, and 0.59 ng/mL for acephate, trifuralin, malathion, thiamethozam, pendimethalin, DEF6, acetamiprid, brifenthrin, and lambda-cyhalothrin. This study provides a precision (0.17-13.1%), accuracy (recoveries=88-107%) and good reproducible method for the analytes of interest. At relatively high concentrations, only lambda-cyhalothrin was unstable at room temperature (20-25 degrees C) and 4 degrees C over 10 days. At relatively low concentrations, acephate and acetamiprid were also unstable regardless of temperature. After 10 days storage at room temperature, 30-40% degradation of lambda-cyhalothrin was observed. It is recommended that acephate, acetamiprid, and lambda-cyhalothrin be stored at -20 degrees C or analyzed immediately after extraction.

  8. Pharmacokinetics of reduced iso-α-acids in volunteers following clear bottled beer consumption.

    PubMed

    Rodda, Luke N; Gerostamoulos, Dimitri; Drummer, Olaf H

    2015-05-01

    Reduced iso-α-acids (reduced IAA) consisting of the rho-, tetrahydro- and hexahydro-IAA groups (RIAA, TIAA and HIAA, respectively) are ingredient congeners specific to beer and generally found in clear and also occasionally green bottled beer. Concentrations of reduced IAA were determined in the blood and urine of five volunteers over 6h following the consumption of small volumes of beer containing each of the reduced IAA. The reduced IAA were absorbed and bioavailable with peak concentrations at 0.5h followed by a drop of generally fivefold by 2h. Preliminary pharmacokinetics of these compounds in humans shows relatively small inter-individual differences and an estimated short half-life varying between ∼38 and 46min for the three groups. Comparison of RIAA analyte ratios within the group indicate that some analytes eliminate relatively faster than others and the formation of metabolite products was observed. Preliminary urine analysis showed only unmodified RIAA analytes were detectable throughout 6h and suggests extensive phase I metabolism of TIAA and HIAA analytes. In authentic forensic casework where clear or green bottled beers are consumed, the identification of reduced IAA groups may provide a novel method to target ingredient congeners consistent with beer ingestion and suggest the type of beer consumed. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  9. Monitoring the Presence of 13 Active Compounds in Surface Water Collected from Rural Areas in Northwestern Spain

    PubMed Central

    Iglesias, Alejandra; Nebot, Carolina; Vázquez, Beatriz I.; Coronel-Olivares, Claudia; Franco Abuín, Carlos M.; Cepeda, Alberto

    2014-01-01

    Drug residues are considered environmental contaminants, and their occurrence has recently become a matter of concern. Analytical methods and monitoring systems are therefore required to control the continuous input of these drug residues into the environment. This article presents a suitable HPLC-ESI-MS/MS method for the simultaneous extraction, detection and quantification of residues of 13 drugs (antimicrobials, glucocorticosteroids, anti-inflammatories, anti-hypertensives, anti-cancer drugs and triphenylmethane dyes) in surface water. A monitoring study with 549 water samples was carried out in northwestern Spain to detect the presence of drug residues over two sampling periods during 2010, 2011 and 2012. Samples were collected from rural areas with and without farming activity and from urban areas. The 13 analytes were detected, and 18% of the samples collected showed positive results for the presence of at least one analyte. More collection sites were located in rural areas than in urban areas. However, more positive samples with higher concentrations and a larger number of analytes were detected in samples collected from sites located after the discharge of a WWTP. Results indicated that the WWTPs seems to act as a concentration point. Positive samples were also detected at a site located near a drinking water treatment plant. PMID:24837665

  10. Monitoring the presence of 13 active compounds in surface water collected from rural areas in northwestern Spain.

    PubMed

    Iglesias, Alejandra; Nebot, Carolina; Vázquez, Beatriz I; Coronel-Olivares, Claudia; Abuín, Carlos M Franco; Cepeda, Alberto

    2014-05-15

    Drug residues are considered environmental contaminants, and their occurrence has recently become a matter of concern. Analytical methods and monitoring systems are therefore required to control the continuous input of these drug residues into the environment. This article presents a suitable HPLC-ESI-MS/MS method for the simultaneous extraction, detection and quantification of residues of 13 drugs (antimicrobials, glucocorticosteroids, anti-inflammatories, anti-hypertensives, anti-cancer drugs and triphenylmethane dyes) in surface water. A monitoring study with 549 water samples was carried out in northwestern Spain to detect the presence of drug residues over two sampling periods during 2010, 2011 and 2012. Samples were collected from rural areas with and without farming activity and from urban areas. The 13 analytes were detected, and 18% of the samples collected showed positive results for the presence of at least one analyte. More collection sites were located in rural areas than in urban areas. However, more positive samples with higher concentrations and a larger number of analytes were detected in samples collected from sites located after the discharge of a WWTP. Results indicated that the WWTPs seems to act as a concentration point. Positive samples were also detected at a site located near a drinking water treatment plant.

  11. Integrated assessment of runoff from concentrated animal feeding operations: Analytical approaches, in vitro bioassays, and in vivo fish exposures

    EPA Science Inventory

    While the trend toward using concentrated animal feeding operations (CAFOs) has resulted in increased efficiency in food production, this has prompted concern regarding the impact these operations have on the environment. For example, animal waste from CAFOs can contain natural a...

  12. Microtrap assembly for greenhouse gas and air pollution monitoring

    DOEpatents

    Mitra, Somenath; Saridara, Chutarat

    2015-08-25

    A microtrap assembly includes a carbon nanotube sorbent. The microtrap assembly may be employed as a preconcentrator operable to deliver a sample to an analytical device to measure the concentrations of greenhouse gases. A system includes a microtrap having a carbon nanotube sorbent for measuring the concentrations of greenhouse gases in a sample.

  13. SEASONAL AND REGIONAL VARIATIONS OF PRIMARY AND SECONDARY ORGANIC AEROSOLS OVER THE CONTINENTAL UNITED STATES: OBSERVATION-BASED ESTIMATES AND MODEL EVALUATION

    EPA Science Inventory

    Due to the lack of an analytical technique for directly quantifying the atmospheric concentrations of primary (OCpri) and secondary (OCsec) organic carbon aerosols, different indirect methods have been developed to estimate their concentrations. In this stu...

  14. USE OF HOPANE AS A CONSERVATIVE BIOMARKER FOR MONITORING THE BIOREMEDIATION EFFECTIVENESS OF CRUDE OIL CONTAMINATING A SANDY BEACH

    EPA Science Inventory

    Much of the variability inherent in crude oil bioremediation field studies can be eliminated by normalizing analyte concentrations to the concentration of a nonbiodegradable biomarker such as hopane. This was demonstrated with data from a field study in which crude oil was intent...

  15. Presence, concentrations and risk assessment of selected antibiotic residues in sediments and near-bottom waters collected from the Polish coastal zone in the southern Baltic Sea - Summary of 3years of studies.

    PubMed

    Siedlewicz, Grzegorz; Białk-Bielińska, Anna; Borecka, Marta; Winogradow, Aleksandra; Stepnowski, Piotr; Pazdro, Ksenia

    2018-04-01

    Concentrations of selected antibiotic compounds from different groups were measured in sediment samples (14 analytes) and in near-bottom water samples (12 analytes) collected in 2011-2013 from the southern Baltic Sea (Polish coastal zone). Antibiotics were determined at concentration levels of a few to hundreds of ng g -1 d.w. in sediments and ng L -1 in near-bottom waters. The most frequently detected compounds were sulfamethoxazole, trimethoprim, oxytetracycline in sediments and sulfamethoxazole and trimethoprim in near-bottom waters. The occurrence of the identified antibiotics was characterized by spatial and temporal variability. A statistically important correlation was observed between sediment organic matter content and the concentrations of sulfachloropyridazine and oxytetracycline. Risk assessment analyses revealed a potential high risk of sulfamethoxazole contamination in near-bottom waters and of contamination by sulfamethoxazole, trimethoprim and tetracyclines in sediments. Both chemical and risk assessment analyses show that the coastal area of the southern Baltic Sea is highly exposed to antibiotic residues. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Study of radon dispersion in typical dwelling using CFD modeling combined with passive-active measurements

    NASA Astrophysics Data System (ADS)

    Rabi, R.; Oufni, L.

    2017-10-01

    Inhalation of radon (222Rn) and its decay products are a major source of natural radiation exposure. It is known from recent surveys in many countries that radon and its progeny contribute significantly to total inhalation dose and it is fairly established that radon when inhaled in large quantity causes lung disorder. Indoor air conditions and ventilation systems strongly influence the indoor radon concentration. This study focuses on investigating both numerically and experimentally the influence of environmental conditions on the indoor radon concentration and spatial distribution. The numerical results showed that ventilation rate, temperature and humidity have significant impacts on both radon content and distribution. The variations of radon concentration with the ventilation, temperature and relative humidity are discussed. The measurement results show the diurnal variations of the indoor radon concentration are found to exhibit a positive correlation with relative humidity and negatively correlate with the air temperature. The analytic solution is used to validate the numeric results. The comparison amongst analytical, numerical and measurement results shows close agreement.

  17. Melamine sensing based on evanescent field enhanced optical fiber sensor

    NASA Astrophysics Data System (ADS)

    Luo, Ji; Yao, Jun; Wang, Wei-min; Zhuang, Xu-ye; Ma, Wen-ying; Lin, Qiao

    2013-08-01

    Melamine is an insalubrious chemical, and has been frequently added into milk products illegally, to make the products more protein-rich. However, it can cause some various diseases, such as kidney stones and bladder cancer. In this paper, a novel optical fiber sensor with high sensitivity based on absorption of the evanescent field for melamine detection is successfully proposed and developed. Different concentrations of melamine changing from 0 to 10mg/mL have been detected using the micro/nano-sensing fiber decorated with silver nanoparticles cluster layer. As the concentration increases, the sensing fiber's output intensity gradually deceases and the absorption of the analyte becomes large. The concentration changing of 1mg/ml can cause the absorbance varying 0.664 and the limit of the melamine detectable concentration is 1ug/mL. Besides, the coupling properties between silver nanoparticles have also been analyzed by the FDTD method. Overall, this evanescent field enhanced optical fiber sensor has potential to be used in oligo-analyte detection and will promote the development of biomolecular and chemical sensing applications.

  18. Anodic stripping voltammetry enhancement by redox magnetohydrodynamics.

    PubMed

    Clark, Emily A; Fritsch, Ingrid

    2004-04-15

    The effect of an external magnetic field on linear scan anodic stripping voltammetry (ASV) in solutions of 10(-6)-10(-7) M concentrations of lead, cadmium, and copper at mercury films on glassy carbon electrodes has been investigated. A high concentration of Hg(2+) was added to the analyte solution to induce a large cathodic current during the deposition step. Therefore, a large Lorentz force from the net flux of charge through the magnetic field resulted in convection due to magnetohydrodynamics. The faster delivery of analytes to the mercury film electrode during deposition caused an increase in the anodic stripping peaks. The effect of varying Hg(2+) concentrations (0-60 mM) and magnetic field strengths (0-1.77 T) on the enhancement of the stripping peaks was investigated. Enhancements as large as 129% for peak currents and 167% for peak areas were observed. An enhancement of approximately 100% was observed when 60 mM Fe(3+) replaced high concentrations of Hg(2+). This method of convection exhibits promise for small-volume ASV analysis with possible improved limits of detection and decreased preconcentration times.

  19. Concentrations of tritium and strontium-90 in water from selected wells at the Idaho National Engineering Laboratory after purging one, two, and three borehole volumes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bartholomay, R.C.

    1993-12-31

    Water from 11 wells completed in the Snake River Plain aquifer at the Idaho National Engineering Laboratory was sampled as Part of the US. Geological Survey`s quality assurance program to determine the effect of Purging different borehole volumes on tritium and strontium-90 concentrations. Wells were selected for sampling on the basis of the length of time it took to purge a borehole volume of water. Samples were collected after purging one, two, and three borehole volumes. The US Department of Energy`s Radiological and Environmental Sciences Laboratory provided analytical services. Statistics were used to determine the reproducibility of analytical results. Themore » comparison between tritium and strontium-90 concentrations after purging one and three borehole volumes and two and three borehole volumes showed that all but two sample pairs with defined numbers were in statistical agreement. Results indicate that concentrations of tritium and strontium-90 are not affected measurably by the number of borehole volumes purged.« less

  20. Method and apparatus for concentrating vapors for analysis

    DOEpatents

    Grate, Jay W [West Richland, WA; Baldwin, David L [Kennewick, WA; Anheier, Jr., Norman C.

    2012-06-05

    A pre-concentration device and a method are disclosed for concentrating gaseous vapors for analysis. Vapors sorbed and concentrated within the bed of the pre-concentration device are thermally desorbed, achieving at least partial separation of the vapor mixtures. The pre-concentration device is suitable, e.g., for pre-concentration and sample injection, and provides greater resolution of peaks for vapors within vapor mixtures, yielding detection levels that are 10-10,000 times better than direct sampling and analysis systems. Features are particularly useful for continuous unattended monitoring applications. The invention finds application in conjunction with, e.g., analytical instruments where low detection limits for gaseous vapors are desirable.

  1. Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of inorganic and organic constituents in water and fluvial sediments

    USGS Publications Warehouse

    Fishman, M. J.

    1993-01-01

    Methods to be used to analyze samples of water, suspended sediment and bottom material for their content of inorganic and organic constituents are presented. Technology continually changes, and so this laboratory manual includes new and revised methods for determining the concentration of dissolved constituents in water, whole water recoverable constituents in water-suspended sediment samples, and recoverable concentration of constit- uents in bottom material. For each method, the general topics covered are the application, the principle of the method, interferences, the apparatus and reagents required, a detailed description of the analytical procedure, reporting results, units and significant figures, and analytical precision data. Included in this manual are 30 methods.

  2. Reversible thrombin detection by aptamer functionalized STING sensors

    PubMed Central

    Actis, Paolo; Rogers, Adam; Nivala, Jeff; Vilozny, Boaz; Seger, R. Adam; Jejelowo, Olufisayo; Pourmand, Nader

    2011-01-01

    Signal Transduction by Ion NanoGating (STING) is a label-free technology based on functionalized quartz nanopipettes. The nanopipette pore can be decorated with a variety of recognition elements and the molecular interaction is transduced via a simple electrochemical system. A STING sensor can be easily and reproducibly fabricated and tailored at the bench starting from inexpensive quartz capillaries. The analytical application of this new biosensing platform, however, was limited due to the difficult correlation between the measured ionic current and the analyte concentration in solution. Here we show that STING sensors functionalized with aptamers allow the quantitative detection of thrombin. The binding of thrombin generates a signal that can be directly correlated to its concentration in the bulk solution. PMID:21636261

  3. Development of a Novel Method for in vivo Determination of Activation Energy of Glucose Transport Across S. cerevisiae Cellular Membranes. A Biosensor-like Approach

    PubMed Central

    Kormes, Diego J.; Cortón, Eduardo

    2009-01-01

    Whereas biosensors have been usually proposed as analytical tools, used to investigate the surrounding media pursuing an analytical answer, we have used a biosensor-like device to characterize the microbial cells immobilized on it. We have studied the kinetics of transport and degradation of glucose at different concentrations and temperatures. When glucose concentrations of 15 and 1.5 mM were assayed, calculated activation energies were 25.2 and 18.4 kcal mol−1, respectively, in good agreement with previously published data. The opportunity and convenience of using Arrhenius plots to estimate the activation energy in metabolic-related processes is also discussed. PMID:22573975

  4. Cartilage analysis by reflection spectroscopy

    NASA Astrophysics Data System (ADS)

    Laun, T.; Muenzer, M.; Wenzel, U.; Princz, S.; Hessling, M.

    2015-07-01

    A cartilage bioreactor with analytical functions for cartilage quality monitoring is being developed. For determining cartilage composition, reflection spectroscopy in the visible (VIS) and near infrared (NIR) spectral region is evaluated. Main goal is the determination of the most abundant cartilage compounds water, collagen I and collagen II. Therefore VIS and NIR reflection spectra of different cartilage samples of cow, pig and lamb are recorded. Due to missing analytical instrumentation for identifying the cartilage composition of these samples, typical literature concentration values are used for the development of chemometric models. In spite of these limitations the chemometric models provide good cross correlation results for the prediction of collagen I and II and water concentration based on the visible and the NIR reflection spectra.

  5. Assessment of the analytical capabilities of inductively coupled plasma-mass spectrometry

    USGS Publications Warehouse

    Taylor, Howard E.; Garbarino, John R.

    1988-01-01

    A thorough assessment of the analytical capabilities of inductively coupled plasma-mass spectrometry was conducted for selected analytes of importance in water quality applications and hydrologic research. A multielement calibration curve technique was designed to produce accurate and precise results in analysis times of approximately one minute. The suite of elements included Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, Pb, Se, Sr, V, and Zn. The effects of sample matrix composition on the accuracy of the determinations showed that matrix elements (such as Na, Ca, Mg, and K) that may be present in natural water samples at concentration levels greater than 50 mg/L resulted in as much as a 10% suppression in ion current for analyte elements. Operational detection limits are presented.

  6. Penning Ionization Electron Spectroscopy in Glow Discharge: A New Dimension for Gas Chromatography Detectors

    NASA Technical Reports Server (NTRS)

    Sheverev, V. A.; Khromov, N. A.; Kojiro, D. R.; Fonda, Mark (Technical Monitor)

    2002-01-01

    Admixtures to helium of 100 ppm and 5 ppm of nitrogen, and 100 ppm and 10 ppm of carbon monoxide were identified and measured in the helium discharge afterglow using an electrical probe placed into the plasma. For nitrogen and carbon monoxide gases, the measured electron energy spectra display distinct characteristic peaks (fingerprints). Location of the peaks on the energy scale is determined by the ionization energies of the analyte molecules. Nitrogen and carbon monoxide fingerprints were also observed in a binary mixture of these gases in helium, and the relative concentration analytes has been predicted. The technically simple and durable method is considered a good candidate for a number of analytical applications, and in particular, in GC and for analytical flight instrumentation.

  7. Ion concentration in micro and nanoscale electrospray emitters.

    PubMed

    Yuill, Elizabeth M; Baker, Lane A

    2018-06-01

    Solution-phase ion transport during electrospray has been characterized for nanopipettes, or glass capillaries pulled to nanoscale tip dimensions, and micron-sized electrospray ionization emitters. Direct visualization of charged fluorophores during the electrospray process is used to evaluate impacts of emitter size, ionic strength, analyte size, and pressure-driven flow on heterogeneous ion transport during electrospray. Mass spectrometric measurements of positively- and negatively-charged proteins were taken for micron-sized and nanopipette emitters under low ionic strength conditions to further illustrate a discrepancy in solution-driven transport of charged analytes. A fundamental understanding of analyte electromigration during electrospray, which is not always considered, is expected to provide control over selective analyte depletion and enrichment, and can be harnessed for sample cleanup. Graphical abstract Fluorescence micrographs of ion migration in nanoscale pipettes while solution is electrosprayed.

  8. Use of dried blood spots for the determination of serum concentrations of tamoxifen and endoxifen.

    PubMed

    Jager, N G L; Rosing, H; Schellens, J H M; Beijnen, J H; Linn, S C

    2014-07-01

    The anti-estrogenic effect of tamoxifen is suggested to be mainly attributable to its metabolite (Z)-endoxifen, and a minimum therapeutic threshold for (Z)-endoxifen in serum has been proposed. The objective of this research was to establish the relationship between dried blood spot (DBS) and serum concentrations of tamoxifen and (Z)-endoxifen to allow the use of DBS sampling, a simple and patient-friendly alternative to venous sampling, in clinical practice. Paired DBS and serum samples were obtained from 50 patients using tamoxifen and analyzed using HPLC-MS/MS. Serum concentrations were calculated from DBS concentrations using the formula calculated serum concentration = DBS concentration/([1-haematocrit (Hct)] + blood cell-to-serum ratio × Hct). The blood cell-to-serum ratio was determined ex vivo by incubating a batch of whole blood spiked with both analytes. The average Hct for female adults was imputed as a fixed value. Calculated and analyzed serum concentrations were compared using weighted Deming regression. Weighted Deming regression analysis comparing 44 matching pairs of DBS and serum samples showed a proportional bias for both analytes. Serum concentrations were calculated using [Tamoxifen] serum, calculated  = [Tamoxifen] DBS /0.779 and [(Z)-Endoxifen] serum, calculated = [(Z)-Endoxifen] DBS /0.663. Calculated serum concentrations were within 20 % of analyzed serum concentrations in 84 and 100 % of patient samples for tamoxifen and (Z)-endoxifen, respectively. In conclusion, DBS concentrations of tamoxifen and (Z)-endoxifen were equal to serum concentrations after correction for Hct and blood cell-to-serum ratio. DBS sampling can be used in clinical practice.

  9. Application of techniques to identify coal-mine and power-generation effects on surface-water quality, San Juan River basin, New Mexico and Colorado

    USGS Publications Warehouse

    Goetz, C.L.; Abeyta, Cynthia G.; Thomas, E.V.

    1987-01-01

    Numerous analytical techniques were applied to determine water quality changes in the San Juan River basin upstream of Shiprock , New Mexico. Eight techniques were used to analyze hydrologic data such as: precipitation, water quality, and streamflow. The eight methods used are: (1) Piper diagram, (2) time-series plot, (3) frequency distribution, (4) box-and-whisker plot, (5) seasonal Kendall test, (6) Wilcoxon rank-sum test, (7) SEASRS procedure, and (8) analysis of flow adjusted, specific conductance data and smoothing. Post-1963 changes in dissolved solids concentration, dissolved potassium concentration, specific conductance, suspended sediment concentration, or suspended sediment load in the San Juan River downstream from the surface coal mines were examined to determine if coal mining was having an effect on the quality of surface water. None of the analytical methods used to analyzed the data showed any increase in dissolved solids concentration, dissolved potassium concentration, or specific conductance in the river downstream from the mines; some of the analytical methods used showed a decrease in dissolved solids concentration and specific conductance. Chaco River, an ephemeral stream tributary to the San Juan River, undergoes changes in water quality due to effluent from a power generation facility. The discharge in the Chaco River contributes about 1.9% of the average annual discharge at the downstream station, San Juan River at Shiprock, NM. The changes in water quality detected at the Chaco River station were not detected at the downstream Shiprock station. It was not possible, with the available data, to identify any effects of the surface coal mines on water quality that were separable from those of urbanization, agriculture, and other cultural and natural changes. In order to determine the specific causes of changes in water quality, it would be necessary to collect additional data at strategically located stations. (Author 's abstract)

  10. Integrated Circuits for Rapid Sample Processing and Electrochemical Detection of Biomarkers

    NASA Astrophysics Data System (ADS)

    Besant, Justin

    The trade-off between speed and sensitivity of detection is a fundamental challenge in the design of point-of-care diagnostics. As the relevant molecules in many diseases exist natively at extremely low levels, many gold-standard diagnostic tests are designed with high sensitivity at the expense of long incubations needed to amplify the target analytes. The central aim of this thesis is to design new strategies to detect biologically relevant analytes with both high speed and sensitivity. The response time of a biosensor is limited by the ability of the target analyte to accumulate to detectable levels at the sensor surface. We overcome this limitation by designing a range of integrated devices to optimize the flux of the analyte to the sensor by increasing the effective analyte concentration, shortening the required diffusion distance, and confining the analyte in close proximity to the sensor. We couple these devices with novel ultrasensitive electrochemical transduction strategies to convert rare analytes into a detectable signal. We showcase the clinical utility of these approaches with several applications including cancer diagnosis, bacterial identification, and antibiotic susceptibility profiling. We design and optimize a device to isolate rare cancer cells from the bloodstream with near 100% efficiency and 10 000-fold specificity. We analyse pathogen specific nucleic acids by lysing bacteria in close proximity to an electrochemical sensor and find that this approach has 10-fold higher sensitivity than standard lysis in bulk solution. We design an electronic chip to readout the antibiotic susceptibility profile with an hour-long incubation by concentrating bacteria into nanoliter chambers with integrated electrodes. Finally, we report a strategy for ultrasensitive visual readout of nucleic acids as low as 100 fM within 10 minutes using an amplification cascade. The strategies presented could guide the development of fast, sensitive and low-cost diagnostics for diseases not previously detectable at the point-of-care.

  11. Surrogate analyte approach for quantitation of endogenous NAD(+) in human acidified blood samples using liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

    PubMed

    Liu, Liling; Cui, Zhiyi; Deng, Yuzhong; Dean, Brian; Hop, Cornelis E C A; Liang, Xiaorong

    2016-02-01

    A high-performance liquid chromatography tandem mass spectrometry (LC-MS/MS) assay for the quantitative determination of NAD(+) in human whole blood using a surrogate analyte approach was developed and validated. Human whole blood was acidified using 0.5N perchloric acid at a ratio of 1:3 (v:v, blood:perchloric acid) during sample collection. 25μL of acidified blood was extracted using a protein precipitation method and the resulting extracts were analyzed using reverse-phase chromatography and positive electrospray ionization mass spectrometry. (13)C5-NAD(+) was used as the surrogate analyte for authentic analyte, NAD(+). The standard curve ranging from 0.250 to 25.0μg/mL in acidified human blood for (13)C5-NAD(+) was fitted to a 1/x(2) weighted linear regression model. The LC-MS/MS response between surrogate analyte and authentic analyte at the same concentration was obtained before and after the batch run. This response factor was not applied when determining the NAD(+) concentration from the (13)C5-NAD(+) standard curve since the percent difference was less than 5%. The precision and accuracy of the LC-MS/MS assay based on the five analytical QC levels were well within the acceptance criteria from both FDA and EMA guidance for bioanalytical method validation. Average extraction recovery of (13)C5-NAD(+) was 94.6% across the curve range. Matrix factor was 0.99 for both high and low QC indicating minimal ion suppression or enhancement. The validated assay was used to measure the baseline level of NAD(+) in 29 male and 21 female human subjects. This assay was also used to study the circadian effect of endogenous level of NAD(+) in 10 human subjects. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Chemical Sensors Based on IR Spectroscopy and Surface-Modified Waveguides

    NASA Technical Reports Server (NTRS)

    Lopez, Gabriel P.; Niemczyk, Thomas

    1999-01-01

    Sol-gel processing techniques have been used to apply thin porous films to the surfaces of planar infrared (IR) waveguides to produce widely useful chemical sensors. The thin- film coating serves to diminish the concentration of water and increase the concentration of the analyte in the region probed by the evanescent IR wave. These porous films are composed of silica, and therefore, conventional silica surface modification techniques can be used to give the surface a specific functional character. The sol-gel film was surface-modified to make the film highly hydrophobic. These sensors were shown to be capable of detecting non-polar organic analytes, such as benzonitrile, in aqueous solution with detection limits in the ppb range. Further, these porous sol-gel structures allow the analytes to diffuse into and out of the films rapidly, thus reaching equilibrium in less than ten seconds. These sensors are unique because of the fact that their operation is based on the measurement of an IR absorption spectrum. Thus, these sensors are able to identify the analytes as well as measure concentration with high sensitivity. These developments have been documented in previous reports and publications. Recently, we have also targeted detection of the polar organic molecules acetone and isopropanol in aqueous solution. Polar organics are widely used in industrial and chemical processes, hence it is of interest to monitor their presence in effluents or decontamination process flows. Although large improvements in detection limits were expected with non-polar organic molecules in aqueous solutions using very hydrophobic porous sol-gel films on silicon attenuated total reflectance (Si ATR) waveguides, it was not as clear what the detection enhancements might be for polar organic molecules. This report describes the use of modified sol-gel-coated Si ATR sensors for trace detection and quantitation of small polar organic molecules in aqueous solutions. The detection of both acetone and isopropanol molecules in aqueous solution has been previously reported for chalcogenide fiber optic sensors. The sol-gel film was produced using a mixture of ethyltriethoxysilane and tetraethoxysilane and the surface modification was carried out using trimethylchlorosilane. We have demonstrated that this film concentrates the target polar analytes from aqueous solution in the region probed by the evanescent wave to improve detection limits by as much as a factor of 450.

  13. Stable oxygen and hydrogen isotopes of brines - comparing isotope ratio mass spectrometry and isotope ratio infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Ahrens, Christian; Koeniger, Paul; van Geldern, Robert; Stadler, Susanne

    2013-04-01

    Today's standard analytical methods for high precision stable isotope analysis of fluids are gas-water equilibration and high temperature pyrolysis coupled to isotope ratio mass spectrometers (IRMS). In recent years, relatively new laser-based analytical instruments entered the market that are said to allow high isotope precision data on nearly every media. This optical technique is referred to as isotope ratio infrared spectroscopy (IRIS). The objective of this study is to evaluate the capability of this new instrument type for highly saline solutions and a comparison of the analytical results with traditional IRMS analysis. It has been shown for the equilibration method that the presence of salts influences the measured isotope values depending on the salt concentration (see Lécuyer et al, 2009; Martineau, 2012). This so-called 'isotope salt effect' depends on the salt type and salt concentration. These factors change the activity in the fluid and therefore shift the isotope ratios measured by the equilibration method. Consequently, correction factors have to be applied to these analytical data. Direct conversion techniques like pyrolysis or the new laser instruments allow the measurement of the water molecule from the sample directly and should therefore not suffer from the salt effect, i.e. no corrections of raw values are necessary. However, due to high salt concentrations this might cause technical problems with the analytical hardware and may require labor-intensive sample preparation (e.g. vacuum distillation). This study evaluates the salt isotope effect for the IRMS equilibration technique (Thermo Gasbench II coupled to Delta Plus XP) and the laser-based IRIS instruments with liquid injection (Picarro L2120-i). Synthetic salt solutions (NaCl, KCl, CaCl2, MgCl2, MgSO4, CaSO4) and natural brines collected from the Stassfurt Salt Anticline (Germany; Stadler et al., 2012) were analysed with both techniques. Salt concentrations ranged from seawater salinity up to full saturation. References Lécuyer, C. et al. (2009). Chem. Geol., 264, 122-126. [doi:10.1016/j.chemgeo.2009.02.017] Martineau, F. et al. (2012). Chem. Geol., 291, 236-240. [doi:10.1016/j.chemgeo.2011.10.017] Stadler, S. et al. (2012). Chem. Geol., 294-295, 226-242. [doi:10.1016/j.chemgeo.2011.12.006

  14. Pseudo-Boltzmann model for modeling the junctionless transistors

    NASA Astrophysics Data System (ADS)

    Avila-Herrera, F.; Cerdeira, A.; Roldan, J. B.; Sánchez-Moreno, P.; Tienda-Luna, I. M.; Iñiguez, B.

    2014-05-01

    Calculation of the carrier concentrations in semiconductors using the Fermi-Dirac integral requires complex numerical calculations; in this context, practically all analytical device models are based on Boltzmann statistics, even though it is known that it leads to an over-estimation of carriers densities for high doping concentrations. In this paper, a new approximation to Fermi-Dirac integral, called Pseudo-Boltzmann model, is presented for modeling junctionless transistors with high doping concentrations.

  15. Pattern Recognition Algorithm for High-Sensitivity Odorant Detection in Unknown Environments

    NASA Technical Reports Server (NTRS)

    Duong, Tuan A.

    2012-01-01

    In a realistic odorant detection application environment, the collected sensory data is a mix of unknown chemicals with unknown concentrations and noise. The identification of the odorants among these mixtures is a challenge in data recognition. In addition, deriving their individual concentrations in the mix is also a challenge. A deterministic analytical model was developed to accurately identify odorants and calculate their concentrations in a mixture with noisy data.

  16. Correlation of Lethal Concentrations of Heavy Metals with Tissue Levels of Earthworms

    DTIC Science & Technology

    1988-08-01

    mentioned in the contract i.e. mercury , arsenic, ’cadmium and copper. We will find out the 50 % lethal concentrations (LC50) and the smallest...concentrations, blanks, and background worm stock has been limited to copper and cadmium. In fact, mercury and arsenic request special analytical device...the other boxes but without toxic components. Contaminants to study are heavy metals : cadmium, copper and mercury , and arsenic. We chose following

  17. Exact analytic flux distributions for two-dimensional solar concentrators.

    PubMed

    Fraidenraich, Naum; Henrique de Oliveira Pedrosa Filho, Manoel; Vilela, Olga C; Gordon, Jeffrey M

    2013-07-01

    A new approach for representing and evaluating the flux density distribution on the absorbers of two-dimensional imaging solar concentrators is presented. The formalism accommodates any realistic solar radiance and concentrator optical error distribution. The solutions obviate the need for raytracing, and are physically transparent. Examples illustrating the method's versatility are presented for parabolic trough mirrors with both planar and tubular absorbers, Fresnel reflectors with tubular absorbers, and V-trough mirrors with planar absorbers.

  18. Determination of perfluorinated carboxylic acids in fish fillet by micro-solid phase extraction, followed by liquid chromatography-triple quadrupole mass spectrometry.

    PubMed

    Lashgari, Maryam; Lee, Hian Kee

    2014-11-21

    In the current study, a simple, fast and efficient combination of protein precipitation and micro-solid phase extraction (μ-SPE) followed by liquid chromatography-triple quadrupole tandem mass spectrometry (LC-MS/MS) was developed for the determination of perfluorinated carboxylic acids (PFCAs) in fish fillet. Ten PFCAs with different hydrocarbon chain lengths (C5-C14) were analysed simultaneously using this method. Protein precipitation by acetonitrile and μ-SPE by surfactant-incorporated ordered mesoporous silica were applied to the extraction and concentration of the PFCAs as well as for removal of interferences. Determination of the PFCAs was carried out by LC-MS/MS in negative electrospray ionization mode. MS/MS parameters were optimized for multiple reaction monitoring of the analytes. (13)C mass labelled PFOA as a stable-isotopic internal standard, was used for calibration. The detection limits of the method ranged from 0.97 ng/g to 2.7 ng/g, with a relative standard deviation of between 5.4 and 13.5. The recoveries were evaluated for each analyte and were ranged from 77% to 120%. The t-test at 95% confidence level showed that for all the analytes, the relative recoveries did not depend on their concentrations in the explored concentration range. The effect of the matrix on MS signals (suppression or enhancement) was also evaluated. Contamination at low levels was detected for some analytes in the fish samples. The protective role of the polypropylene membrane used in μ-SPE in the elimination of matrix effects was evaluated by parallel experiments in classical dispersive solid phase extraction. The results evidently showed that the polypropylene membrane was significantly effective in reducing matrix effects. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Enantioselective determination of representative profens in wastewater by a single-step sample treatment and chiral liquid chromatography-tandem mass spectrometry.

    PubMed

    Caballo, C; Sicilia, M D; Rubio, S

    2015-03-01

    This manuscript describes, for the first time, the simultaneous enantioselective determination of ibuprofen, naproxen and ketoprofen in wastewater based on liquid chromatography tandem mass spectrometry (LC-MS/MS). The method uses a single-step sample treatment based on microextraction with a supramolecular solvent made up of hexagonal inverted aggregates of decanoic acid, formed in situ in the wastewater sample through a spontaneous self-assembly process. Microextraction of profens was optimized and the analytical method validated. Isotopically labeled internal standards were used to compensate for both matrix interferences and recoveries. Apparent recoveries for the six enantiomers in influent and effluent wastewater samples were in the interval 97-103%. Low method detection limits (MDLs) were obtained (0.5-1.2 ng L(-1)) as a result of the high concentration factors achieved in the microextraction process (i.e. actual concentration factors 469-736). No analyte derivatization or evaporation of extracts, as it is required with GC-MS, was necessary. Relative standard deviations for enantiomers in wastewater were always below 8%. The method was applied to the determination of the concentrations and enantiomeric fractions of the targeted analytes in influents and effluents from three wastewater treatment plants. All the values found for profen enantiomers were consistent with those previously reported and confirmed again the suitability of using the enantiomeric fraction of ibuprofen as an indicator of the discharge of untreated or poorly treated wastewaters. Both the analytical and operational features of this method make it applicable to the assessment of the enantiomeric fate of profens in the environment. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Sample distribution in peak mode isotachophoresis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Rubin, Shimon; Schwartz, Ortal; Bercovici, Moran, E-mail: mberco@technion.ac.il

    We present an analytical study of peak mode isotachophoresis (ITP), and provide closed form solutions for sample distribution and electric field, as well as for leading-, trailing-, and counter-ion concentration profiles. Importantly, the solution we present is valid not only for the case of fully ionized species, but also for systems of weak electrolytes which better represent real buffer systems and for multivalent analytes such as proteins and DNA. The model reveals two major scales which govern the electric field and buffer distributions, and an additional length scale governing analyte distribution. Using well-controlled experiments, and numerical simulations, we verify andmore » validate the model and highlight its key merits as well as its limitations. We demonstrate the use of the model for determining the peak concentration of focused sample based on known buffer and analyte properties, and show it differs significantly from commonly used approximations based on the interface width alone. We further apply our model for studying reactions between multiple species having different effective mobilities yet co-focused at a single ITP interface. We find a closed form expression for an effective-on rate which depends on reactants distributions, and derive the conditions for optimizing such reactions. Interestingly, the model reveals that maximum reaction rate is not necessarily obtained when the concentration profiles of the reacting species perfectly overlap. In addition to the exact solutions, we derive throughout several closed form engineering approximations which are based on elementary functions and are simple to implement, yet maintain the interplay between the important scales. Both the exact and approximate solutions provide insight into sample focusing and can be used to design and optimize ITP-based assays.« less

  1. Analyte stability during the total testing process: studies of vitamins A, D and E by LC-MS/MS.

    PubMed

    Albahrani, Ali A; Rotarou, Victor; Roche, Peter J; Greaves, Ronda F

    2016-10-01

    There are limited evidence based studies demonstrating the stability of fat-soluble vitamins (FSV) measured in blood. This study aimed to examine the effects of light, temperature and time on vitamins A, D and E throughout the total testing process. Four experiments were conducted. Three investigated the sample matrix, of whole blood, serum and the extracted sample, against the variables of temperature and light; and the fourth experiment investigated the sample during the extraction process against the variable of light. All samples were analysed via our simultaneous FSV method using liquid chromatography-tandem mass spectrometry technology. The allowable clinical percentage change was calculated based on biological variation and desirable method imprecision for each analyte. The total change limit was ±7.3% for 25-OH-vitamin D3, ±11.8% for retinol and ±10.8% for α-tocopherol. Vitamins D and E were stable in the investigated conditions (concentration changes <4%) in the pre-analytical and analytical stages. Vitamin A showed photosensitivity in times >48 h with concentration changes of -6.8% (blood) and -6.5% (serum), both are within the allowable clinical percentage change. By contrast, the extracted retinol sample demonstrated a concentration change of -18.4% after 48 h of light exposure. However, vitamin A in the serum and extracted solution was stable for one month when stored at -20°C. Blood samples for vitamins D and E analyses can be processed in normal laboratory conditions of lighting and temperature. The required conditions for vitamin A analysis are similar when performed within 48 h. For longer-term storage, serum and vitamin A extracts should be stored at -20°C.

  2. Studies on transport phenomena in electrothermal vaporization sample introduction applied to inductively coupled plasma for optical emission and mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kántor, T.; Maestre, S.; de Loos-Vollebregt, M. T. C.

    2005-10-01

    In the present work electrothermal vaporization (ETV) was used in both inductively coupled plasma mass spectrometry (ICP-MS) and optical emission spectrometry (OES) for sample introduction of solution samples. The effect of (Pd + Mg)-nitrate modifier and CaCl 2 matrix/modifier of variable amounts were studied on ETV-ICP-MS signals of Cr, Cu, Fe, Mn and Pb and on ETV-ICP-OES signals of Ag, Cd, Co, Cu, Fe, Ga, Mn and Zn. With the use of matrix-free standard solutions the analytical curves were bent to the signal axes (as expected from earlier studies), which was observed in the 20-800 pg mass range by ICP-MS and in the 1-50 ng mass range by ICP-OES detection. The degree of curvature was, however, different with the use of single element and multi-element standards. When applying the noted chemical modifiers (aerosol carriers) in microgram amounts, linear analytical curves were found in the nearly two orders of magnitude mass ranges. Changes of the CaCl 2 matrix concentration (loaded amount of 2-10 μg Ca) resulted in less than 5% changes in MS signals of 5 elements (each below 1 ng) and OES signals of 22 analytes (each below 15 ng). Exceptions were Pb (ICP-MS) and Cd (ICP-OES), where the sensitivity increase by Pd + Mg modifier was much larger compared to other elements studied. The general conclusions suggest that quantitative analysis with the use of ETV sample introduction requires matrix matching or matrix replacement by appropriate chemical modifier to the specific concentration ranges of analytes. This is a similar requirement to that claimed also by the most commonly used pneumatic nebulization of solutions, if samples with high matrix concentration are concerned.

  3. Micelle to solvent stacking of organic cations in micellar electrokinetic chromatography with sodium dodecyl sulfate.

    PubMed

    Quirino, Joselito P; Aranas, Agnes T

    2011-10-14

    The on-line sample concentration technique, micelle to solvent stacking (MSS), was studied for small organic cations (quaternary ammonium herbicides, β-blocker drugs, and tricyclic antidepressant drugs) in reversed migration micellar electrokinetic chromatography. Electrokinetic chromatography was carried out in fused silica capillaries with a background solution of sodium dodecyl sulfate (SDS) in a low pH phosphate buffer. MSS was performed using anionic SDS micelles in the sample solution for analyte transport and methanol or acetonitrile as organic solvent in the background solution for analyte effective electrophoretic mobility reversal. The solvent also allowed for the separation of the analyte test mixtures. A model for focusing and separation was developed and the mobility reversal that involved micelle collapse was experimentally verified. The effect of analyte retention factor was observed by changing the % organic solvent in the background solution or the concentration of SDS in the sample matrix. With an injection length of 31.9 cm (77% of effective capillary length) for the 7 test drugs, the LODs (S/N=3) of 5-14 ng/mL were 101-346-fold better when compared to typical injection. The linearity (R(2), range=0.025-0.8 μg/mL), intraday and interday repeatability (%RSD, n=10) were ≥0.988, <6.0% and <8.5%, respectively. In addition, analysis of spiked urine samples after 10-fold dilution with the sample matrix yielded LODs=0.02-0.10 μg/mL. These LODs are comparable to published electrophoretic methods that required off-line sample concentration. However, the practicality of the technique for more complex samples will rely on dedicated sample preparation schemes. Copyright © 2011 Elsevier B.V. All rights reserved.

  4. Removal of uranium from soil samples for ICP-OES analysis of RCRA metals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wero, M.; Lederer-Cano, A.; Billy, C.

    1995-12-01

    Soil samples containing high levels of uranium present unique analytical problems when analyzed for toxic metals (Ag, As, Ba, Cd, Cr, Cu, Ni, Pb, Se and Tl) because of the spectral interference of uranium in the ICP-OES emission spectrometer. Methods to remove uranium from the digestates of soil samples, known to be high in uranium, have been developed that reduce the initial uranium concentration (1-3%) to less than 500 ppm. UTEVA ion exchange columns, used as an ICP-OES analytical pre-treatment, reduces uranium to acceptable levels, permitting good analytical results of the RCRA metals by ICP-OES.

  5. Maps and interpretation of geochemical anomalies, Chuckwalla Mountains Wilderness Study Area, Riverside County, California

    USGS Publications Warehouse

    Watts, K.C.

    1986-01-01

    This report discusses and interprets geochemical results as they are seen at the reconnaissance stage. Analytical results for all samples collected are released in a U.S. Geological Survey Open-File Report (Adrian and others, 1985). A statistical summary of the data from heavy-mineral concentrates and sieved stream sediments is shown in table 1. The analytical results for selected elements in rock samples are shown in table 2.

  6. CADDIS Volume 3. Examples and Applications: Analytical Examples

    EPA Pesticide Factsheets

    Examples illustrating the use of statistical analysis to support different types of evidence, stream temperature, temperature inferred from macroinverterbate, macroinvertebrate responses, zinc concentrations, observed trait characteristics.

  7. Optics of two-stage photovoltaic concentrators with dielectric second stages.

    PubMed

    Ning, X; O'Gallagher, J; Winston, R

    1987-04-01

    Two-stage photovoltaic concentrators with Fresnel lenses as primaries and dielectric totally internally reflecting nonimaging concentrators as secondaries are discussed. The general design principles of such two-stage systems are given. Their optical properties are studied and analyzed in detail using computer ray trace procedures. It is found that the two-stage concentrator offers not only a higher concentration or increased acceptance angle, but also a more uniform flux distribution on the photovoltaic cell than the point focusing Fresnel lens alone. Experimental measurements with a two-stage prototype module are presented and compared to the analytical predictions.

  8. Optics of two-stage photovoltaic concentrators with dielectric second stages

    NASA Astrophysics Data System (ADS)

    Ning, Xiaohui; O'Gallagher, Joseph; Winston, Roland

    1987-04-01

    Two-stage photovoltaic concentrators with Fresnel lenses as primaries and dielectric totally internally reflecting nonimaging concentrators as secondaries are discussed. The general design principles of such two-stage systems are given. Their optical properties are studied and analyzed in detail using computer ray trace procedures. It is found that the two-stage concentrator offers not only a higher concentration or increased acceptance angle, but also a more uniform flux distribution on the photovoltaic cell than the point focusing Fresnel lens alone. Experimental measurements with a two-stage prototype module are presented and compared to the analytical predictions.

  9. Quantifying Gold Nanoparticle Concentration in a Dietary Supplement Using Smartphone Colorimetry and Google Applications

    ERIC Educational Resources Information Center

    Campos, Antonio R.; Knutson, Cassandra M.; Knutson, Theodore R.; Mozzetti, Abbie R.; Haynes, Christy L.; Penn, R. Lee

    2016-01-01

    Spectrophotometry and colorimetry experiments are common in high school and college chemistry courses, and nanotechnology is increasingly common in every day products and new devices. Previous work has demonstrated that handheld camera devices can be used to quantify the concentration of a colored analyte in solution in place of traditional…

  10. Concentrations and co-occurrence correlations of 88 volatile organic compounds (VOCs) in the ambient air of 13 semi-rural to urban locations in the United States

    USGS Publications Warehouse

    Pankow, J.F.; Luo, W.; Bender, D.A.; Isabelle, L.M.; Hollingsworth, J.S.; Chen, C.; Asher, W.E.; Zogorski, J.S.

    2003-01-01

    The ambient air concentrations of 88 volatile organic compounds were determined in samples taken at 13 semi-rural to urban locations in Maine, Massachusetts, New Jersey, Pennsylvania, Ohio, Illinois, Louisiana, and California. The sampling periods ranged from 7 to 29 months, yielding a large data set with a total of 23,191 individual air concentration values, some of which were designated "ND" (not detected). For each compound at each sampling site, the air concentrations (ca, ppbV) are reported in terms of means, medians, and means of the detected values. The analytical method utilized adsorption/thermal desorption with air-sampling cartridges. The analytes included numerous halogenated alkanes, halogenated alkenes, ethers, alcohols, nitriles, esters, ketones, aromatics, a disulfide, and a furan. At some sites, the air concentrations of the gasoline-related aromatic compounds and the gasoline additive methyl tert-butyl ether were seasonally dependent, with concentrations that maximized in the winter. For each site studied here, the concentrations of some compounds were highly correlated one with another (e.g., the BTEX group (benzene, toluene, ethylbenzene, and the xylenes). Other aromatic compounds were also all generally correlated with one another, while the concentrations of other compound pairs were not correlated (e.g., benzene was not correlated with CFC-12). The concentrations found for the BTEX group were generally lower than the values that have been previously reported for urbanized and industrialized areas of other nations. ?? 2003 Elsevier Ltd. All rights reserved.

  11. Part-2: Analytical Expressions of Concentrations of Glucose, Oxygen, and Gluconic Acid in a Composite Membrane for Closed-Loop Insulin Delivery for the Non-steady State Conditions.

    PubMed

    Mehala, N; Rajendran, L; Meena, V

    2017-02-01

    A mathematical model developed by Abdekhodaie and Wu (J Membr Sci 335:21-31, 2009), which describes a dynamic process involving an enzymatic reaction and diffusion of reactants and product inside glucose-sensitive composite membrane has been discussed. This theoretical model depicts a system of non-linear non-steady state reaction diffusion equations. These equations have been solved using new approach of homotopy perturbation method and analytical solutions pertaining to the concentrations of glucose, oxygen, and gluconic acid are derived. These analytical results are compared with the numerical results, and limiting case results for steady state conditions and a good agreement is observed. The influence of various kinetic parameters involved in the model has been presented graphically. Theoretical evaluation of the kinetic parameters like the maximal reaction velocity (V max ) and Michaelis-Menten constants for glucose and oxygen (K g and K ox ) is also reported. This predicted model is very much useful for designing the glucose-responsive composite membranes for closed-loop insulin delivery.

  12. Phosphorescence Kinetics of Singlet Oxygen Produced by Photosensitization in Spherical Nanoparticles. Part I. Theory.

    PubMed

    Hovan, Andrej; Datta, Shubhashis; Kruglik, Sergei G; Jancura, Daniel; Miskovsky, Pavol; Bánó, Gregor

    2018-05-24

    The singlet oxygen produced by energy transfer between an excited photosensitizer (pts) and ground-state oxygen molecules plays a key role in photodynamic therapy. Different nanocarrier systems are extensively studied to promote targeted pts delivery in a host body. The phosphorescence kinetics of the singlet oxygen produced by the short laser pulse photosensitization of pts inside nanoparticles is influenced by singlet oxygen diffusion from the particles to the surrounding medium. Two theoretical models are presented in this work: a more complex numerical one and a simple analytical one. Both the models predict the time course of singlet oxygen concentration inside and outside of the spherical particles following short-pulse excitation of pts. On the basis of the comparison of the numerical and analytical results, a semiempirical analytical formula is derived to calculate the characteristic diffusion time of singlet oxygen from the nanoparticles to the surrounding solvent. The phosphorescence intensity of singlet oxygen produced in pts-loaded nanocarrier systems can be calculated as a linear combination of the two concentrations (inside and outside the particles), taking the different phosphorescence emission rate constants into account.

  13. Principles of Micellar Electrokinetic Capillary Chromatography Applied in Pharmaceutical Analysis

    PubMed Central

    Hancu, Gabriel; Simon, Brigitta; Rusu, Aura; Mircia, Eleonora; Gyéresi, Árpád

    2013-01-01

    Since its introduction capillary electrophoresis has shown great potential in areas where electrophoretic techniques have rarely been used before, including here the analysis of pharmaceutical substances. The large majority of pharmaceutical substances are neutral from electrophoretic point of view, consequently separations by the classic capillary zone electrophoresis; where separation is based on the differences between the own electrophoretic mobilities of the analytes; are hard to achieve. Micellar electrokinetic capillary chromatography, a hybrid method that combines chromatographic and electrophoretic separation principles, extends the applicability of capillary electrophoretic methods to neutral analytes. In micellar electrokinetic capillary chromatography, surfactants are added to the buffer solution in concentration above their critical micellar concentrations, consequently micelles are formed; micelles that undergo electrophoretic migration like any other charged particle. The separation is based on the differential partitioning of an analyte between the two-phase system: the mobile aqueous phase and micellar pseudostationary phase. The present paper aims to summarize the basic aspects regarding separation principles and practical applications of micellar electrokinetic capillary chromatography, with particular attention to those relevant in pharmaceutical analysis. PMID:24312804

  14. Fast and efficient mesoporous adsorbents for the separation of toxic compounds from aqueous media.

    PubMed

    Anbia, Mansoor; Mohammadi, Nourali; Mohammadi, Kaveh

    2010-04-15

    The effect of cationic template on the adsorption of chromium (VI), furfural and copperphthalocyanine-3,4',4'',4'''-tetrasulfonic acid tetrasodium salt (CuPc) in MCM-41 and MCM-48 mesoporous materials was investigated in this work. We used cetyltrimethylammonium bromide (CTAB) as the cationic template and sodiummetasilicate (for MCM-41) and tetraethyl-orthosilicon (for MCM-48) as the silica source for the synthesis of mesoporous materials. The properties of synthesized samples were characterized with XRD-low angle, SEM, N(2) adsorption-desorption and TG-DT analysis. The extent of adsorption was investigated as a function of solution pH, shaking speed, contact time, analyte concentration, reaction temperature and supporting electrolyte (sodium chloride) concentration. Langmuir and Freundlich isotherms were used to model the adsorption equilibrium data. The as-synthesized mesoporous samples showed very high adsorption capacity for the analytes and adsorption uptakes were rapid on the adsorbents reaching equilibrium in less than 2 h. The materials without surfactant did not show significant affinity for the analytes. 2009 Elsevier B.V. All rights reserved.

  15. Computational Methodology for Absolute Calibration Curves for Microfluidic Optical Analyses

    PubMed Central

    Chang, Chia-Pin; Nagel, David J.; Zaghloul, Mona E.

    2010-01-01

    Optical fluorescence and absorption are two of the primary techniques used for analytical microfluidics. We provide a thorough yet tractable method for computing the performance of diverse optical micro-analytical systems. Sample sizes range from nano- to many micro-liters and concentrations from nano- to milli-molar. Equations are provided to trace quantitatively the flow of the fundamental entities, namely photons and electrons, and the conversion of energy from the source, through optical components, samples and spectral-selective components, to the detectors and beyond. The equations permit facile computations of calibration curves that relate the concentrations or numbers of molecules measured to the absolute signals from the system. This methodology provides the basis for both detailed understanding and improved design of microfluidic optical analytical systems. It saves prototype turn-around time, and is much simpler and faster to use than ray tracing programs. Over two thousand spreadsheet computations were performed during this study. We found that some design variations produce higher signal levels and, for constant noise levels, lower minimum detection limits. Improvements of more than a factor of 1,000 were realized. PMID:22163573

  16. Comparison of Analytical Methods for the Determination of Uranium in Seawater Using Inductively Coupled Plasma Mass Spectrometry

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wood, Jordana R.; Gill, Gary A.; Kuo, Li-Jung

    2016-04-20

    Trace element determinations in seawater by inductively coupled plasma mass spectrometry are analytically challenging due to the typically very low concentrations of the trace elements and the potential interference of the salt matrix. In this study, we did a comparison for uranium analysis using inductively coupled plasma mass spectrometry (ICP-MS) of Sequim Bay seawater samples and three seawater certified reference materials (SLEW-3, CASS-5 and NASS-6) using seven different analytical approaches. The methods evaluated include: direct analysis, Fe/Pd reductive precipitation, standard addition calibration, online automated dilution using an external calibration with and without matrix matching, and online automated pre-concentration. The methodmore » which produced the most accurate results was the method of standard addition calibration, recovering uranium from a Sequim Bay seawater sample at 101 ± 1.2%. The on-line preconcentration method and the automated dilution with matrix-matched calibration method also performed well. The two least effective methods were the direct analysis and the Fe/Pd reductive precipitation using sodium borohydride« less

  17. Comparative measurements of mineral elements in milk powders with laser-induced breakdown spectroscopy and inductively coupled plasma atomic emission spectroscopy.

    PubMed

    Lei, W Q; El Haddad, J; Motto-Ros, V; Gilon-Delepine, N; Stankova, A; Ma, Q L; Bai, X S; Zheng, L J; Zeng, H P; Yu, J

    2011-07-01

    Mineral elements contained in commercially available milk powders, including seven infant formulae and one adult milk, were analyzed with inductively coupled plasma atomic emission spectrometry (ICP-AES) and laser-induced breakdown spectroscopy (LIBS). The purpose of this work was, through a direct comparison of the analytical results, to provide an assessment of the performance of LIBS, and especially of the procedure of calibration-free LIBS (CF-LIBS), to deal with organic compounds such as milk powders. In our experiments, the matrix effect was clearly observed affecting the analytical results each time laser ablation was employed for sampling. Such effect was in addition directly observed by determining the physical parameters of the plasmas induced on the different samples. The CF-LIBS procedure was implemented to deduce the concentrations of Mg and K with Ca as the internal reference element. Quantitative analytical results with CF-LIBS were validated with ICP-AES measurements and nominal concentrations specified for commercial milks. The obtained good results with the CF-LIBS procedure demonstrate its capacity to take into account the difference in physical parameters of the plasma in the calculation of the concentrations of mineral elements, which allows a significant reduction of the matrix effect related to laser ablation. We finally discuss the way to optimize the implementation of the CF-LIBS procedure for the analysis of mineral elements in organic materials.

  18. Yearly trend of dicarboxylic acids in organic aerosols from south of Sweden and source attribution

    NASA Astrophysics Data System (ADS)

    Hyder, Murtaza; Genberg, Johan; Sandahl, Margareta; Swietlicki, Erik; Jönsson, Jan Åke

    2012-09-01

    Seven aliphatic dicarboxylic acids (C3-C9) along with phthalic acid, pinic acid and pinonic acid were determined in 35 aerosol (PM10) samples collected over the year at Vavihill sampling station in south of Sweden. Mixture of dichloromethane and methanol (ratio 1:3) was preferred over water for extraction of samples and extraction was assisted by ultrasonic agitation. Analytes were derivatized using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) containing 1% trimethylsilyl chloride and analyzed using gas chromatography/mass spectrometry. Among studied analytes, azelaic acid was found maximum with an average concentration of 6.0 ± 3.6 ng m-3 and minimum concentration was found for pimelic acid (1.06 ± 0.63 ng m-3). A correlation coefficients analysis was used for defining the possible sources of analytes. Higher dicarboxylic acids (C7-C9) showed a strong correlation with each other (correlation coefficients (r) range, 0.96-0.97). Pinic and pinonic acids showed an increase in concentration during summer. Lower carbon number dicarboxylic acids (C3-C6) and phthalic acid were found strongly correlated, but showed a poor correlation with higher carbon number dicarboxylic acids (C7-C9), suggesting a different source for them. Biomass burning, vehicle exhaust, photo-oxidation of volatile organic compounds (natural and anthropogenic emissions) were possible sources for dicarboxylic acids.

  19. Measurements for certification of chlortetracycline reference materials within the European Union Standards, Measurements and Testing programme.

    PubMed

    Juhel-Gaugain, M; McEvoy, J D; VanGinkel, L A

    2000-12-01

    The experimental design of a material certification programme is described. The matrix reference materials (RMs) comprised chlortetracycline (CTC)-containing and CTC-free lyophilised porcine liver, kidney and muscle produced under the European Commission's Standards Measurements and Testing (SMT) programme. The aim of the certification programme was to determine accurately and precisely the concentration of CTC and 4-epi-chlortetracycline (epi-CTC) contained in the RMs. A multi-laboratory approach was used to certify analyte concentrations. Participants (n = 19) were instructed to strictly adhere to previously established guidelines. Following the examination of analytical performance criteria, statistical manipulation of results submitted by 13 laboratories, (6 withdrew) allowed an estimate to be made of the true value of the analyte content. The Nalimov test was used for detection of outlying results. The Cochran and Bartlett tests were employed for testing the homogeneity of variances. The normality of results distribution was tested according to the Kolmogorov-Smirnov-Lilliefors test. One-way analysis of variance (ANOVA) was employed to calculate the within and between-laboratory standard deviations, the overall mean and confidence interval for the CTC and epi-CTC content of each of the RMs. Certified values were within or very close to the target concentration ranges specified in the SMT contract. These studies have demonstrated the successful production and certification of CTC-containing and CTC-free porcine RMs.

  20. An Analytical Framework for the Steady State Impact of Carbonate Compensation on Atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Omta, Anne Willem; Ferrari, Raffaele; McGee, David

    2018-04-01

    The deep-ocean carbonate ion concentration impacts the fraction of the marine calcium carbonate production that is buried in sediments. This gives rise to the carbonate compensation feedback, which is thought to restore the deep-ocean carbonate ion concentration on multimillennial timescales. We formulate an analytical framework to investigate the impact of carbonate compensation under various changes in the carbon cycle relevant for anthropogenic change and glacial cycles. Using this framework, we show that carbonate compensation amplifies by 15-20% changes in atmospheric CO2 resulting from a redistribution of carbon between the atmosphere and ocean (e.g., due to changes in temperature, salinity, or nutrient utilization). A counterintuitive result emerges when the impact of organic matter burial in the ocean is examined. The organic matter burial first leads to a slight decrease in atmospheric CO2 and an increase in the deep-ocean carbonate ion concentration. Subsequently, enhanced calcium carbonate burial leads to outgassing of carbon from the ocean to the atmosphere, which is quantified by our framework. Results from simulations with a multibox model including the minor acids and bases important for the ocean-atmosphere exchange of carbon are consistent with our analytical predictions. We discuss the potential role of carbonate compensation in glacial-interglacial cycles as an example of how our theoretical framework may be applied.

  1. Sodium Chloride Diffusion in Low-Acid Foods during Thermal Processing and Storage.

    PubMed

    Bornhorst, Ellen R; Tang, Juming; Sablani, Shyam S

    2016-05-01

    This study aimed at modeling sodium chloride (NaCl) diffusion in foods during thermal processing using analytical and numerical solutions and at investigating the changes in NaCl concentrations during storage after processing. Potato, radish, and salmon samples in 1% or 3% NaCl solutions were heated at 90, 105, or 121 °C for 5 to 240 min to simulate pasteurization and sterilization. Selected samples were stored at 4 or 22 °C for up to 28 d. Radish had the largest equilibrium NaCl concentrations and equilibrium distribution coefficients, but smallest effective diffusion coefficients, indicating that a greater amount of NaCl diffused into the radish at a slower rate. Effective diffusion coefficients determined using the analytical solution ranged from 0.2 × 10(-8) to 2.6 × 10(-8) m²/s. Numerical and analytical solutions showed good agreement with experimental data, with average coefficients of determination for samples in 1% NaCl at 121 °C of 0.98 and 0.95, respectively. During storage, food samples equilibrated to a similar NaCl concentration regardless of the thermal processing severity. The results suggest that sensory evaluation of multiphase (solid and liquid) products should occur at least 14 d after processing to allow enough time for the salt to equilibrate within the product. © 2016 Institute of Food Technologists®

  2. Correction for isotopic interferences between analyte and internal standard in quantitative mass spectrometry by a nonlinear calibration function.

    PubMed

    Rule, Geoffrey S; Clark, Zlatuse D; Yue, Bingfang; Rockwood, Alan L

    2013-04-16

    Stable isotope-labeled internal standards are of great utility in providing accurate quantitation in mass spectrometry (MS). An implicit assumption has been that there is no "cross talk" between signals of the internal standard and the target analyte. In some cases, however, naturally occurring isotopes of the analyte do contribute to the signal of the internal standard. This phenomenon becomes more pronounced for isotopically rich compounds, such as those containing sulfur, chlorine, or bromine, higher molecular weight compounds, and those at high analyte/internal standard concentration ratio. This can create nonlinear calibration behavior that may bias quantitative results. Here, we propose the use of a nonlinear but more accurate fitting of data for these situations that incorporates one or two constants determined experimentally for each analyte/internal standard combination and an adjustable calibration parameter. This fitting provides more accurate quantitation in MS-based assays where contributions from analyte to stable labeled internal standard signal exist. It can also correct for the reverse situation where an analyte is present in the internal standard as an impurity. The practical utility of this approach is described, and by using experimental data, the approach is compared to alternative fits.

  3. Infiltrated photonic crystal cavity as a highly sensitive platform for glucose concentration detection

    NASA Astrophysics Data System (ADS)

    Arafa, Safia; Bouchemat, Mohamed; Bouchemat, Touraya; Benmerkhi, Ahlem; Hocini, Abdesselam

    2017-02-01

    A Bio-sensing platform based on an infiltrated photonic crystal ring shaped holes cavity-coupled waveguide system is proposed for glucose concentration detection. Considering silicon-on-insulator (SOI) technology, it has been demonstrated that the ring shaped holes configuration provides an excellent optical confinement within the cavity region, which further enhances the light-matter interactions at the precise location of the analyte medium. Thus, the sensitivity and the quality factor (Q) can be significantly improved. The transmission characteristics of light in the biosensor under different refractive indices that correspond to the change in the analyte glucose concentration are analyzed by performing finite-difference time-domain (FDTD) simulations. Accordingly, an improved sensitivity of 462 nm/RIU and a Q factor as high as 1.11х105 have been achieved, resulting in a detection limit of 3.03х10-6 RIU. Such combination of attributes makes the designed structure a promising element for performing label-free biosensing in medical diagnosis and environmental monitoring.

  4. A preliminary investigation on the distribution of cannabinoids in man.

    PubMed

    Gronewold, Antonia; Skopp, Gisela

    2011-07-15

    An LC/MS/MS procedure to determine THC along with its major metabolites 11-OH-THC, THC-COOH and its glucuronide as well as the cannabinoids CBD and CBN was applied to 5 post mortem cases to study their distribution into some less commonly studied matrices. Analytes were determined in fluids and tissue homogenates following protein precipitation and liquid-liquid extraction. Gall bladder fluid exhibited maximum concentrations of all analytes except THC, which was detectable in high concentrations in muscle tissue along with CBD. THC was also present in lung specimens, whereas its concentration in liver samples was low or not detectable at all. Liver und kidney specimens contained appreciable amounts of THC-COOglu. Findings from bile support extensive enterohepatic recirculation of the glucuronide. Muscle tissue seems an interesting specimen to detect multiple cannabis use, and brain may serve as an alternative specimen for blood; nevertheless, the present findings should be substantiated by further investigations. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  5. Determination of Minor and Trace Metals in Aluminum and Aluminum Alloys by ICP-AES; Evaluation of the Uncertainty and Limit of Quantitation from Interlaboratory Testing.

    PubMed

    Uemoto, Michihisa; Makino, Masanori; Ota, Yuji; Sakaguchi, Hiromi; Shimizu, Yukari; Sato, Kazuhiro

    2018-01-01

    Minor and trace metals in aluminum and aluminum alloys have been determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) as an interlaboratory testing toward standardization. The trueness of the measured data was successfully investigated to improve the analytical protocols, using certified reference materials of aluminum. Their precision could also be evaluated, feasible to estimate the uncertainties separately. The accuracy (trueness and precision) of the data were finally in good agreement with the certified values and assigned uncertainties. Repeated measurements of aluminum solutions with different concentrations of the analytes revealed the relative standard deviations of the measurements with concentrations, thus enabling their limits of quantitation. They differed separately and also showed slightly higher values with an aluminum matrix than those without one. In addition, the upper limit of the detectable concentration of silicon with simple acid digestion was estimated to be 0.03 % in the mass fraction.

  6. Odor intensity and characterization of jet exhaust and chemical analytical measurements

    NASA Technical Reports Server (NTRS)

    Kendall, D. A.; Levins, P. L.

    1973-01-01

    Odor and chemical analyses were carried out on the exhaust samples from a J-57 combustor can operated over a range of inlet conditions, and with several fuel types and nozzle modifications. The odor characteristics and total intensity of odor for each exhaust were determined over a range of dilutions to allow for a least squares determination of the intensity at 1,000 to 1 dilutions. Analytical measures included the concentration of total hydrocarbons and the concentrations of aromatic organic species and oxygenated organic species from collected samples which were taken concurrently. A correlation was found between the concentration of the odorous oxygenated fraction and the total intensity of aroma. Inlet operating conditions and nozzle modifications which increase the efficiency of combustion as measured by exhaust gas analyses reduce the odor intensity and the quantity of oxygenates in the exhaust. The type of fuel burned altered the intensity of odor in relation to the quantity of oxygenates produced and, in some instances, changed the odor character.

  7. Micro-solid-phase extraction (µ-SPE) of organophosphorous pesticides from wheat followed by LC-MS/MS determination.

    PubMed

    Della Pelle, Flavio; Di Crescenzo, Maria Chiara; Sergi, Manuel; Montesano, Camilla; Di Ottavio, Francesca; Scarpone, Rossana; Scortichini, Giampiero; Compagnone, Dario

    2016-01-01

    A rapid, selective and effective method of extraction, clean-up and concentration of organophosphorous pesticides from wheat followed by electrospray (ESI) LC-MS/MS analysis was developed. The μ-SPE (micro-solid-phase extraction) procedure resulted in good analytical performance and reduced at the same time matrix effects, analysis time and solvent consumption. Limits of detection (LODs) and quantification (LOQs) were in the range of 0.3-10 and 1-30 μg kg(-1), respectively, with good reproducibility (RSD ≤ 13.8) and recoveries between 75% and 109%. Coefficients of determination (r(2)) were greater than 0.996 for the studied pesticides. Despite the reduced sorbent bed mass of μ-SPE tips (4.2 mg), the analytical data showed that no saturation phenomena occurs in the tested range of concentration both for single compounds and mixtures. Several real samples were analysed and the concentrations of the selected pesticides were found to be below the respective maximum residue limit (MRLs).

  8. Reference intervals for urinary renal injury biomarkers KIM-1 and NGAL in healthy children

    PubMed Central

    McWilliam, Stephen J; Antoine, Daniel J; Sabbisetti, Venkata; Pearce, Robin E; Jorgensen, Andrea L; Lin, Yvonne; Leeder, J Steven; Bonventre, Joseph V; Smyth, Rosalind L; Pirmohamed, Munir

    2014-01-01

    Aim The aim of this study was to establish reference intervals in healthy children for two novel urinary biomarkers of acute kidney injury, kidney injury molecule-1 (KIM-1) and neutrophil gelatinase-associated lipocalin (NGAL). Materials & Methods Urinary biomarkers were determined in samples from children in the UK (n = 120) and the USA (n = 171) using both Meso Scale Discovery (MSD) and Luminex-based analytical approaches. Results 95% reference intervals for each biomarker in each cohort are presented and stratified by sex or ethnicity where necessary, and age-related variability is explored using quantile regression. We identified consistently higher NGAL concentrations in females than males (p < 0.0001), and lower KIM-1 concentrations in African–Americans than Caucasians (p = 0.02). KIM-1 demonstrated diurnal variation, with higher concentrations in the morning (p < 0.001). Conclusion This is the first report of reference intervals for KIM-1 and NGAL using two analytical methods in a healthy pediatric population in both UK and US-based populations. PMID:24661102

  9. Simultaneous monitoring the real and imaginary parts of the analyte refractive index using liquid-core photonic bandgap Bragg fibers.

    PubMed

    Li, Jingwen; Qu, Hang; Skorobogatiy, Maksim

    2015-09-07

    We demonstrate simultaneous monitoring of the real and imaginary parts of the liquid analyte refractive index by using a hollow-core Bragg fiber. We apply this two-channel fiber sensor to monitor concentrations of various commercial cooling oils. The sensor operates using spectral monitoring of the fiber bandgap center wavelength, as well as monitoring of the fiber transmission amplitude at mid-bandgap position. The sensitivity of the fiber sensor to changes in the real part of the core refractive index is found to be 1460nm/Refractive index unit (RIU). By using spectral modality and effective medium theory, we determine the concentrations of the two commercial fluids from the measured refractive indices with an accuracy of ~0.57% for both low- and high-loss oils. Moreover, using an amplitude-based detection modality allows determination of the oil concentration with accuracy of ~1.64% for low-loss oils and ~2.81% for the high-loss oils.

  10. Progress and development of analytical methods for gibberellins.

    PubMed

    Pan, Chaozhi; Tan, Swee Ngin; Yong, Jean Wan Hong; Ge, Liya

    2017-01-01

    Gibberellins, as a group of phytohormones, exhibit a wide variety of bio-functions within plant growth and development, which have been used to increase crop yields. Many analytical procedures, therefore, have been developed for the determination of the types and levels of endogenous and exogenous gibberellins. As plant tissues contain gibberellins in trace amounts (usually at the level of nanogram per gram fresh weight or even lower), the sample pre-treatment steps (extraction, pre-concentration, and purification) for gibberellins are reviewed in details. The primary focus of this comprehensive review is on the various analytical methods designed to meet the requirements for gibberellins analyses in complex matrices with particular emphasis on high-throughput analytical methods, such as gas chromatography, liquid chromatography, and capillary electrophoresis, mostly combined with mass spectrometry. The advantages and drawbacks of the each described analytical method are discussed. The overall aim of this review is to provide a comprehensive and critical view on the different analytical methods nowadays employed to analyze gibberellins in complex sample matrices and their foreseeable trends. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Process Analytical Technology for Advanced Process Control in Biologics Manufacturing with the Aid of Macroscopic Kinetic Modeling.

    PubMed

    Kornecki, Martin; Strube, Jochen

    2018-03-16

    Productivity improvements of mammalian cell culture in the production of recombinant proteins have been made by optimizing cell lines, media, and process operation. This led to enhanced titers and process robustness without increasing the cost of the upstream processing (USP); however, a downstream bottleneck remains. In terms of process control improvement, the process analytical technology (PAT) initiative, initiated by the American Food and Drug Administration (FDA), aims to measure, analyze, monitor, and ultimately control all important attributes of a bioprocess. Especially, spectroscopic methods such as Raman or near-infrared spectroscopy enable one to meet these analytical requirements, preferably in-situ. In combination with chemometric techniques like partial least square (PLS) or principal component analysis (PCA), it is possible to generate soft sensors, which estimate process variables based on process and measurement models for the enhanced control of bioprocesses. Macroscopic kinetic models can be used to simulate cell metabolism. These models are able to enhance the process understanding by predicting the dynamic of cells during cultivation. In this article, in-situ turbidity (transmission, 880 nm) and ex-situ Raman spectroscopy (785 nm) measurements are combined with an offline macroscopic Monod kinetic model in order to predict substrate concentrations. Experimental data of Chinese hamster ovary cultivations in bioreactors show a sufficiently linear correlation (R² ≥ 0.97) between turbidity and total cell concentration. PLS regression of Raman spectra generates a prediction model, which was validated via offline viable cell concentration measurement (RMSE ≤ 13.82, R² ≥ 0.92). Based on these measurements, the macroscopic Monod model can be used to determine different process attributes, e.g., glucose concentration. In consequence, it is possible to approximately calculate (R² ≥ 0.96) glucose concentration based on online cell concentration measurements using turbidity or Raman spectroscopy. Future approaches will use these online substrate concentration measurements with turbidity and Raman measurements, in combination with the kinetic model, in order to control the bioprocess in terms of feeding strategies, by employing an open platform communication (OPC) network-either in fed-batch or perfusion mode, integrated into a continuous operation of upstream and downstream.

  12. Process Analytical Technology for Advanced Process Control in Biologics Manufacturing with the Aid of Macroscopic Kinetic Modeling

    PubMed Central

    Kornecki, Martin; Strube, Jochen

    2018-01-01

    Productivity improvements of mammalian cell culture in the production of recombinant proteins have been made by optimizing cell lines, media, and process operation. This led to enhanced titers and process robustness without increasing the cost of the upstream processing (USP); however, a downstream bottleneck remains. In terms of process control improvement, the process analytical technology (PAT) initiative, initiated by the American Food and Drug Administration (FDA), aims to measure, analyze, monitor, and ultimately control all important attributes of a bioprocess. Especially, spectroscopic methods such as Raman or near-infrared spectroscopy enable one to meet these analytical requirements, preferably in-situ. In combination with chemometric techniques like partial least square (PLS) or principal component analysis (PCA), it is possible to generate soft sensors, which estimate process variables based on process and measurement models for the enhanced control of bioprocesses. Macroscopic kinetic models can be used to simulate cell metabolism. These models are able to enhance the process understanding by predicting the dynamic of cells during cultivation. In this article, in-situ turbidity (transmission, 880 nm) and ex-situ Raman spectroscopy (785 nm) measurements are combined with an offline macroscopic Monod kinetic model in order to predict substrate concentrations. Experimental data of Chinese hamster ovary cultivations in bioreactors show a sufficiently linear correlation (R2 ≥ 0.97) between turbidity and total cell concentration. PLS regression of Raman spectra generates a prediction model, which was validated via offline viable cell concentration measurement (RMSE ≤ 13.82, R2 ≥ 0.92). Based on these measurements, the macroscopic Monod model can be used to determine different process attributes, e.g., glucose concentration. In consequence, it is possible to approximately calculate (R2 ≥ 0.96) glucose concentration based on online cell concentration measurements using turbidity or Raman spectroscopy. Future approaches will use these online substrate concentration measurements with turbidity and Raman measurements, in combination with the kinetic model, in order to control the bioprocess in terms of feeding strategies, by employing an open platform communication (OPC) network—either in fed-batch or perfusion mode, integrated into a continuous operation of upstream and downstream. PMID:29547557

  13. Measurement of Clozapine, Norclozapine, and Amisulpride in Plasma and in Oral Fluid Obtained Using 2 Different Sampling Systems.

    PubMed

    Fisher, Danielle S; Beyer, Chad; van Schalkwyk, Gerrit; Seedat, Soraya; Flanagan, Robert J

    2017-04-01

    There is a poor correlation between total concentrations of proton-accepting compounds (most basic drugs) in unstimulated oral fluid and in plasma. The aim of this study was to compare clozapine, norclozapine, and amisulpride concentrations in plasma and in oral fluid collected using commercially available collection devices [Thermo Fisher Scientific Oral-Eze and Greiner Bio-One (GBO)]. Oral-Eze and GBO samples and plasma were collected in that order from patients prescribed clozapine. Analyte concentrations were measured by liquid chromatography-tandem mass spectrometry. There were 112 participants [96 men, aged (median, range) 47 (21-65) years and 16 women, aged 44 (21-65) years]: 74 participants provided 2 sets of samples and 7 provided 3 sets (overall 2 GBO samples not collected). Twenty-three patients were co-prescribed amisulpride, of whom 17 provided 2 sets of samples and 1 provided 3 sets. The median (range) oral fluid within the GBO samples was 52 (13%-86%). Nonadherence to clozapine was identified in all 3 samples in one instance. After correction for oral fluid content, analyte concentrations in the GBO and Oral-Eze samples were poorly correlated with plasma clozapine and norclozapine (R = 0.57-0.63) and plasma amisulpride (R = 0.65-0.72). Analyte concentrations in the 2 sets of oral fluid samples were likewise poorly correlated (R = 0.68-0.84). Mean (SD) plasma clozapine and norclozapine were 0.60 (0.46) and 0.25 (0.21) mg/L, respectively. Mean clozapine and norclozapine concentrations in the 2 sets of oral fluid samples were similar to those in plasma (0.9-1.8 times higher), that is, approximately 2- to 3-fold higher than those in unstimulated oral fluid. The mean (±SD) amisulpride concentrations (microgram per liter) in plasma (446 ± 297) and in the Oral-Eze samples (501 ± 461) were comparable and much higher than those in the GBO samples (233 ± 318). Oral fluid collected using either the GBO system or the Oral-Eze system cannot be used for quantitative clozapine and/or amisulpride therapeutic drug monitoring.

  14. Evaluation of FUS-2000 urine analyzer: analytical properties and particle recognition.

    PubMed

    Beňovská, Miroslava; Wiewiorka, Ondřej; Pinkavová, Jana

    This study evaluates the performance of microscopic part of a hybrid analyzer FUS-2000 (Dirui Industrial Co., Changchun, China), its analytical properties and particle recognition. The evaluation of trueness, repeatability, detection limit, carry-over, linearity range and analytical stability was performed according to Dirui protocol guidelines designed by Dirui Company to guarantee the quality of the instrument. Trueness for low, medium and high-value concentrations was calculated with bias of 15.5, 4.7 and -6.6%, respectively. Detection limit of 5 Ery/μl was confirmed. Coefficient of variation of 11.0, 5.2 and 3.8% was measured for within-run repeatability of low, medium and high concentration. Between-run repeatability for daily quality control had coefficient of variation of 3.0%. Carry-over did not exceed 0.05%. Linearity was confirmed for range of 0-16,000 particles/μl (R 2  = 0.9997). The analytical stability had coefficient of variation of 4.3%. Out of 1258 analyzed urine samples, 362 positive were subjected to light microscopy urine sediment analysis and compared to the analyzer results. Cohen's kappa coefficients were calculated to express the concordance. Squared kappa coefficient was 0.927 (red blood cells), 0.888 (white blood cells), 0.908 (squamous epithelia), 0.634 (transitional epithelia), 0.628 (hyaline casts), 0.843 (granular casts) and 0.623 (bacteria). Single kappa coefficients were 0.885 (yeasts) and 0.756 (crystals), respectively. Aforementioned results show good analytical performance of the analyzer and tight agreement with light microscopy of urine sediment.

  15. Simultaneous quantitation of hydroxychloroquine and its metabolites in mouse blood and tissues using LC-ESI-MS/MS: An application for pharmacokinetic studies.

    PubMed

    Chhonker, Yashpal S; Sleightholm, Richard L; Li, Jing; Oupický, David; Murry, Daryl J

    2018-01-01

    Hydroxychloroquine (HCQ) has been shown to disrupt autophagy and sensitize cancer cells to radiation and chemotherapeutic agents. However, the optimal delivery method, dose, and tumor concentrations required for these effects are not known. This is in part due to a lack of sensitive and reproducible analytical methods for HCQ quantitation in small animals. As such, we developed and validated a selective and sensitive liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method for simultaneous quantitation of hydroxychloroquine and its metabolites in mouse blood and tissues. The chromatographic separation and detection of analytes were achieved on a reversed phase Thermo Aquasil C 18 (50×4.6mm, 3μ) column, with gradient elution using 0.2% formic acid and 0.1% formic acid in methanol as mobile phase at a flow rate of 0.5mL/min. Simple protein precipitation was utilized for extraction of analytes from the desired matrix. Analytes were separated and quantitated using MS/MS with an electrospray ionization source in positive multiple reaction monitoring (MRM) mode. The MS/MS response was linear over the concentration range from 1 to 2000ng/mL for all analytes with a correlation coefficient (R 2 ) of 0.998 or better. The within- and between-day precision (relative standard deviation, % RSD) and accuracy were within the acceptable limits per FDA guidelines. The validated method was successfully applied to a preclinical pharmacokinetic mouse study involving low volume blood and tissue samples for hydroxychloroquine and metabolites. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Compensating for Effects of Humidity on Electronic Noses

    NASA Technical Reports Server (NTRS)

    Homer, Margie; Ryan, Margaret A.; Manatt, Kenneth; Zhou, Hanying; Manfreda, Allison

    2004-01-01

    A method of compensating for the effects of humidity on the readouts of electronic noses has been devised and tested. The method is especially appropriate for use in environments in which humidity is not or cannot be controlled for example, in the vicinity of a chemical spill, which can be accompanied by large local changes in humidity. Heretofore, it has been common practice to treat water vapor as merely another analyte, the concentration of which is determined, along with that of the other analytes, in a computational process based on deconvolution. This practice works well, but leaves room for improvement: changes in humidity can give rise to large changes in electronic-nose responses. If corrections for humidity are not made, the large humidity-induced responses may swamp smaller responses associated with low concentrations of analytes. The present method offers an improvement. The underlying concept is simple: One augments an electronic nose with a separate humidity and a separate temperature sensor. The outputs of the humidity and temperature sensors are used to generate values that are subtracted from the readings of the other sensors in an electronic nose to correct for the temperature-dependent contributions of humidity to those readings. Hence, in principle, what remains after corrections are the contributions of the analytes only. Laboratory experiments on a first-generation electronic nose have shown that this method is effective and improves the success rate of identification of analyte/ water mixtures. Work on a second-generation device was in progress at the time of reporting the information for this article.

  17. Multi-analyte profiling of inflammatory mediators in COPD sputum--the effects of processing.

    PubMed

    Pedersen, Frauke; Holz, Olaf; Lauer, Gereon; Quintini, Gianluca; Kiwull-Schöne, Heidrun; Kirsten, Anne-Marie; Magnussen, Helgo; Rabe, Klaus F; Goldmann, Torsten; Watz, Henrik

    2015-02-01

    Prior to using a new multi-analyte platform for the detection of markers in sputum it is advisable to assess whether sputum processing, especially mucus homogenization by dithiothreitol (DTT), affects the analysis. In this study we tested a novel Human Inflammation Multi Analyte Profiling® Kit (v1.0 Luminex platform; xMAP®). Induced sputum samples of 20 patients with stable COPD (mean FEV1, 59.2% pred.) were processed in parallel using standard processing (with DTT) and a more time consuming sputum dispersion method with phosphate buffered saline (PBS) only. A panel of 47 markers was analyzed in these sputum supernatants by the xMAP®. Twenty-five of 47 analytes have been detected in COPD sputum. Interestingly, 7 markers have been detected in sputum processed with DTT only, or significantly higher levels were observed following DTT treatment (VDBP, α-2-Macroglobulin, haptoglobin, α-1-antitrypsin, VCAM-1, and fibrinogen). However, standard DTT-processing resulted in lower detectable concentrations of ferritin, TIMP-1, MCP-1, MIP-1β, ICAM-1, and complement C3. The correlation between processing methods for the different markers indicates that DTT processing does not introduce a bias by affecting individual sputum samples differently. In conclusion, our data demonstrates that the Luminex-based xMAP® panel can be used for multi-analyte profiling of COPD sputum using the routinely applied method of sputum processing with DTT. However, researchers need to be aware that the absolute concentration of selected inflammatory markers can be affected by DTT. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Can cloud point-based enrichment, preservation, and detection methods help to bridge gaps in aquatic nanometrology?

    PubMed

    Duester, Lars; Fabricius, Anne-Lena; Jakobtorweihen, Sven; Philippe, Allan; Weigl, Florian; Wimmer, Andreas; Schuster, Michael; Nazar, Muhammad Faizan

    2016-11-01

    Coacervate-based techniques are intensively used in environmental analytical chemistry to enrich and extract different kinds of analytes. Most methods focus on the total content or the speciation of inorganic and organic substances. Size fractionation is less commonly addressed. Within coacervate-based techniques, cloud point extraction (CPE) is characterized by a phase separation of non-ionic surfactants dispersed in an aqueous solution when the respective cloud point temperature is exceeded. In this context, the feature article raises the following question: May CPE in future studies serve as a key tool (i) to enrich and extract nanoparticles (NPs) from complex environmental matrices prior to analyses and (ii) to preserve the colloidal status of unstable environmental samples? With respect to engineered NPs, a significant gap between environmental concentrations and size- and element-specific analytical capabilities is still visible. CPE may support efforts to overcome this "concentration gap" via the analyte enrichment. In addition, most environmental colloidal systems are known to be unstable, dynamic, and sensitive to changes of the environmental conditions during sampling and sample preparation. This delivers a so far unsolved "sample preparation dilemma" in the analytical process. The authors are of the opinion that CPE-based methods have the potential to preserve the colloidal status of these instable samples. Focusing on NPs, this feature article aims to support the discussion on the creation of a convention called the "CPE extractable fraction" by connecting current knowledge on CPE mechanisms and on available applications, via the uncertainties visible and modeling approaches available, with potential future benefits from CPE protocols.

  19. Trace analysis of endocrine disrupting compounds in environmental water samples by use of solid-phase extraction and gas chromatography with mass spectrometry detection.

    PubMed

    Azzouz, Abdelmonaim; Ballesteros, Evaristo

    2014-09-19

    A novel analytical method using a continuous solid-phase extraction system in combination with gas chromatography-mass spectrometry for the simultaneous separation and determination of endocrine disrupting compounds (EDCs) is reported. The method was applied to major EDCs of various types including parabens, alkylphenols, phenylphenols, bisphenol A and triclosan in water. Samples were preconcentrated by using an automatic solid-phase extraction module containing a sorbent column, and retained analytes eluted with acetonitrile for derivatization with a mixture of N,O-bis(trimethylsilyl)trifluoroacetamide and trimethylchlorosilane. A number of variables potentially influencing recovery of the target compounds such as the type of SPE sorbent (Silica gel, Florisil, RP-C18, Amberlite XAD-2 and XAD-4, Oasis HLB and LiChrolut EN), eluent and properties of the water including pH and ionic strength, were examined. LiChrolut EN was found to be the most efficient sorbent for retaining the analytes, with ∼100% efficiency. The ensuing method was validated with good analytical results including low limits of detection (0.01-0.08ng/L for 100mL of sample) and good linearity (r(2)>0.997) throughout the studied concentration ranges. The method exhibited good accuracy (recoveries of 90-101%) and precision (relative standard deviations less than 7%) in the determination of EDCs in drinking, river, pond, well, swimming pool and waste water. Waste water samples were found to contain the largest number and highest concentrations of analytes (3.2-390ng/L). Copyright © 2014 Elsevier B.V. All rights reserved.

  20. External quality assurance project report for the National Atmospheric Deposition Program’s National Trends Network and Mercury Deposition Network, 2013–14

    USGS Publications Warehouse

    Wetherbee, Gregory A.; Martin, RoseAnn

    2016-07-05

    The Mercury Deposition Network programs include the system blank program and an interlaboratory comparison program. System blank results indicated that maximum total mercury contamination concentrations in samples were less than the third percentile of all Mercury Deposition Network sample concentrations. The Mercury Analytical Laboratory produced chemical concentration results with low bias and variability compared with other domestic and international laboratories that support atmospheric-deposition monitoring.

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