Spectroscopic chemical analysis methods and apparatus

NASA Technical Reports Server (NTRS)

Hug, William F. (Inventor); Reid, Ray D. (Inventor)

2009-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. Chemical analysis instruments employed in some embodiments include capillary and gel plane electrophoresis, capillary electrochromatography, high performance liquid chromatography, flow cytometry, flow cells for liquids and aerosols, and surface detection instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted simultaneously with native fluorescence spectroscopy to provide high levels of sensitivity and specificity in the same instrument.

Spectroscopic chemical analysis methods and apparatus

NASA Technical Reports Server (NTRS)

Hug, William F. (Inventor); Reid, Ray D. (Inventor); Bhartia, Rohit (Inventor)

2013-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. Chemical analysis instruments employed in some embodiments include capillary and gel plane electrophoresis, capillary electrochromatography, high performance liquid chromatography, flow cytometry, flow cells for liquids and aerosols, and surface detection instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

Spectroscopic chemical analysis methods and apparatus

NASA Technical Reports Server (NTRS)

Reid, Ray D. (Inventor); Hug, William F. (Inventor)

2010-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. Chemical analysis instruments employed in some embodiments include capillary and gel plane electrophoresis, capillary electrochromatography, high performance liquid chromatography, flow cytometry, flow cells for liquids and aerosols, and surface detection instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted simultaneously with native fluorescence spectroscopy to provide high levels of sensitivity and specificity in the same instrument.

Electron Spectroscopy for Chemical Analysis (ESCA) study of atmospheric particles

NASA Technical Reports Server (NTRS)

Dillard, J. G.; Seals, R. D.; Wightman, J. P.

1979-01-01

The results of analyses by ESCA (Electron Spectroscopy for Chemical Analysis) on several Nuclepore filters which were exposed during air pollution studies are presented along with correlative measurements by Neutron Activation Analysis and Scanning Electron Microscopy. Samples were exposed during air pollution studies at Norfolk, Virginia and the NASA Kennedy Space Center (KSC). It was demonstrated that with the ESCA technique it was possible to identify the chemical (bonding) state of elements contained in the atmospheric particulate matter collected on Nuclepore filters. Sulfur, nitrogen, mercury, chlorine, alkali, and alkaline earth metal species were identified in the Norfolk samples. ESCA binding energy data for aluminum indicated that three chemically different types of aluminum are present in the launch and background samples from NASA-KSC.

On the deduction of chemical reaction pathways from measurements of time series of concentrations.

PubMed

Samoilov, Michael; Arkin, Adam; Ross, John

2001-03-01

We discuss the deduction of reaction pathways in complex chemical systems from measurements of time series of chemical concentrations of reacting species. First we review a technique called correlation metric construction (CMC) and show the construction of a reaction pathway from measurements on a part of glycolysis. Then we present two new improved methods for the analysis of time series of concentrations, entropy metric construction (EMC), and entropy reduction method (ERM), and illustrate (EMC) with calculations on a model reaction system. (c) 2001 American Institute of Physics.

Chemical Sensing in Process Analysis.

ERIC Educational Resources Information Center

Hirschfeld, T.; And Others

1984-01-01

Discusses: (1) rationale for chemical sensors in process analysis; (2) existing types of process chemical sensors; (3) sensor limitations, considering lessons of chemometrics; (4) trends in process control sensors; and (5) future prospects. (JN)

Kelvin probe microscopy and electronic transport measurements in reduced graphene oxide chemical sensors

NASA Astrophysics Data System (ADS)

Kehayias, Christopher E.; MacNaughton, Samuel; Sonkusale, Sameer; Staii, Cristian

2013-06-01

Reduced graphene oxide (RGO) is an electronically hybrid material that displays remarkable chemical sensing properties. Here, we present a quantitative analysis of the chemical gating effects in RGO-based chemical sensors. The gas sensing devices are patterned in a field-effect transistor geometry, by dielectrophoretic assembly of RGO platelets between gold electrodes deposited on SiO2/Si substrates. We show that these sensors display highly selective and reversible responses to the measured analytes, as well as fast response and recovery times (tens of seconds). We use combined electronic transport/Kelvin probe microscopy measurements to quantify the amount of charge transferred to RGO due to chemical doping when the device is exposed to electron-acceptor (acetone) and electron-donor (ammonia) analytes. We demonstrate that this method allows us to obtain high-resolution maps of the surface potential and local charge distribution both before and after chemical doping, to identify local gate-susceptible areas on the RGO surface, and to directly extract the contact resistance between the RGO and the metallic electrodes. The method presented is general, suggesting that these results have important implications for building graphene and other nanomaterial-based chemical sensors.

Kelvin probe microscopy and electronic transport measurements in reduced graphene oxide chemical sensors.

PubMed

Kehayias, Christopher E; MacNaughton, Samuel; Sonkusale, Sameer; Staii, Cristian

2013-06-21

Reduced graphene oxide (RGO) is an electronically hybrid material that displays remarkable chemical sensing properties. Here, we present a quantitative analysis of the chemical gating effects in RGO-based chemical sensors. The gas sensing devices are patterned in a field-effect transistor geometry, by dielectrophoretic assembly of RGO platelets between gold electrodes deposited on SiO2/Si substrates. We show that these sensors display highly selective and reversible responses to the measured analytes, as well as fast response and recovery times (tens of seconds). We use combined electronic transport/Kelvin probe microscopy measurements to quantify the amount of charge transferred to RGO due to chemical doping when the device is exposed to electron-acceptor (acetone) and electron-donor (ammonia) analytes. We demonstrate that this method allows us to obtain high-resolution maps of the surface potential and local charge distribution both before and after chemical doping, to identify local gate-susceptible areas on the RGO surface, and to directly extract the contact resistance between the RGO and the metallic electrodes. The method presented is general, suggesting that these results have important implications for building graphene and other nanomaterial-based chemical sensors.

Spectroscopic Chemical Analysis Methods and Apparatus

NASA Technical Reports Server (NTRS)

Hug, William F. (Inventor); Lane, Arthur L. (Inventor); Bhartia, Rohit (Inventor); Reid, Ray D. (Inventor)

2017-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

Spectroscopic Chemical Analysis Methods and Apparatus

NASA Technical Reports Server (NTRS)

Hug, William F. (Inventor); Lane, Arthur L. (Inventor); Reid, Ray D. (Inventor); Bhartia, Rohit (Inventor)

2018-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

Unifying Approach to Analytical Chemistry and Chemical Analysis: Problem-Oriented Role of Chemical Analysis.

ERIC Educational Resources Information Center

Pardue, Harry L.; Woo, Jannie

1984-01-01

Proposes an approach to teaching analytical chemistry and chemical analysis in which a problem to be resolved is the focus of a course. Indicates that this problem-oriented approach is intended to complement detailed discussions of fundamental and applied aspects of chemical determinations and not replace such discussions. (JN)

First satellite measurements of chemical changes in coincidence with sprite activity

NASA Astrophysics Data System (ADS)

Arnone, Enrico; São Sabbas, Fernanda; Kero, Antti; Soula, Serge; Carlotti, Massimo; Chanrion, Olivier; Dinelli, Bianca Maria; Papandrea, Enzo; Castelli, Elisa; Neubert, Torsten

2010-05-01

The last twenty years have seen the discovery of electric discharges in the Earth's atmosphere above thunderstorms, the so-called sprites and jets. It has been suggested that they impact the atmospheric chemistry and possibly affect the ozone layer through their repeated occurrence. Whereas theoretical studies and laboratory experiments suggest enhancement of such gasses as nitrogen oxides by up to hundreds of percent within sprites, a definitive detection of their chemical effects have to date been unsuccessful. In this paper, we report on the first measurements of atmospheric chemical perturbations recorded in coincidence with sprite activity. A striking event occurred on 25 August 2003 when the MIPAS spectrometer onboard the Envisat satellite recorded spectroscopic measurements soon after a sequence of 11 sprites observed above Corsica (France) by Eurosprite ground facilities (details of the convective system are discussed in a companion paper by São Sabbas et al.). The measurements show an enhancement of ambient nitrous oxide by 80% at 52 km altitude in the region above the parent thunderstorm. The recorded chemical changes imply sprites can exert significant modification of the atmospheric chemistry at a regional scale, confirming model and laboratory predictions of sprite-chemistry, and requiring a new estimate of their global impact. The results of the analysis and their implications are discussed.

High resolution Physio-chemical Tissue Analysis: Towards Non-invasive In Vivo Biopsy

NASA Astrophysics Data System (ADS)

Xu, Guan; Meng, Zhuo-Xian; Lin, Jian-Die; Deng, Cheri X.; Carson, Paul L.; Fowlkes, J. Brian; Tao, Chao; Liu, Xiaojun; Wang, Xueding

2016-02-01

Conventional gold standard histopathologic diagnosis requires information of both high resolution structural and chemical changes in tissue. Providing optical information at ultrasonic resolution, photoacoustic (PA) technique could provide highly sensitive and highly accurate tissue characterization noninvasively in the authentic in vivo environment, offering a replacement for histopathology. A two-dimensional (2D) physio-chemical spectrogram (PCS) combining micrometer to centimeter morphology and chemical composition simultaneously can be generated for each biological sample with PA measurements at multiple optical wavelengths. This spectrogram presents a unique 2D “physio-chemical signature” for any specific type of tissue. Comprehensive analysis of PCS, termed PA physio-chemical analysis (PAPCA), can lead to very rich diagnostic information, including the contents of all relevant molecular and chemical components along with their corresponding histological microfeatures, comparable to those accessible by conventional histology. PAPCA could contribute to the diagnosis of many diseases involving diffusive patterns such as fatty liver.

Biological and chemical removal of Cr(VI) from waste water: cost and benefit analysis.

PubMed

Demir, Aynur; Arisoy, Münevver

2007-08-17

The objective of the present study is cost and benefit analysis of biological and chemical removal of hexavalent chromium [Cr(VI)] ions. Cost and benefit analysis were done with refer to two separate studies on removal of Cr(VI), one of heavy metals with a crucial role concerning increase in environmental pollution and disturbance of ecological balance, through biological adsorption and chemical ion-exchange. Methods of biological and chemical removal were compared with regard to their cost and percentage in chrome removal. According to the result of the comparison, cost per unit in chemical removal was calculated 0.24 euros and the ratio of chrome removal was 99.68%, whereas those of biological removal were 0.14 and 59.3% euros. Therefore, it was seen that cost per unit in chemical removal and chrome removal ratio were higher than those of biological removal method. In the current study where chrome removal is seen as immeasurable benefit in terms of human health and the environment, percentages of chrome removal were taken as measurable benefit and cost per unit of the chemicals as measurable cost.

Measurement of chromium VI and chromium III in stainless steel welding fumes with electrom spectroscopy for chemical analysis and neutron activation analysis.

PubMed

Lautner, G M; Carver, J C; Konzen, R B

1978-08-01

Electron Spectroscopy for Chemical Analysis (ESCA) was explored as a means of studying the oxidation state of chromium in SMAC (coated electrode) stainless steel welding fume collected on Nucleopore filters in the laboratory. Chromuim VI and III (as a percent of the total chromium) obtained from ESCA analysis was applied to results from Neutron Activation Analysis (NAA) to yield an average of 69 microgram chromium VI per sample. Diphenylcarbazide/atomic absorption (DPC/AA) results are reported for samples submitted to an industrial laboratory. Possible chemical species and solubility of chromium VI in stainless steel fumes is discussed in light of analogy between the SMAC process and the manufacturing process for chromates.

An Inverse Analysis Approach to the Characterization of Chemical Transport in Paints

PubMed Central

Willis, Matthew P.; Stevenson, Shawn M.; Pearl, Thomas P.; Mantooth, Brent A.

2014-01-01

The ability to directly characterize chemical transport and interactions that occur within a material (i.e., subsurface dynamics) is a vital component in understanding contaminant mass transport and the ability to decontaminate materials. If a material is contaminated, over time, the transport of highly toxic chemicals (such as chemical warfare agent species) out of the material can result in vapor exposure or transfer to the skin, which can result in percutaneous exposure to personnel who interact with the material. Due to the high toxicity of chemical warfare agents, the release of trace chemical quantities is of significant concern. Mapping subsurface concentration distribution and transport characteristics of absorbed agents enables exposure hazards to be assessed in untested conditions. Furthermore, these tools can be used to characterize subsurface reaction dynamics to ultimately design improved decontaminants or decontamination procedures. To achieve this goal, an inverse analysis mass transport modeling approach was developed that utilizes time-resolved mass spectroscopy measurements of vapor emission from contaminated paint coatings as the input parameter for calculation of subsurface concentration profiles. Details are provided on sample preparation, including contaminant and material handling, the application of mass spectrometry for the measurement of emitted contaminant vapor, and the implementation of inverse analysis using a physics-based diffusion model to determine transport properties of live chemical warfare agents including distilled mustard (HD) and the nerve agent VX. PMID:25226346

Multi-wavelength differential absorption measurements of chemical species

NASA Astrophysics Data System (ADS)

Brown, David M.

The probability of accurate detection and quantification of airborne species is enhanced when several optical wavelengths are used to measure the differential absorption of molecular spectral features. Characterization of minor atmospheric constituents, biological hazards, and chemical plumes containing multiple species is difficult when using current approaches because of weak signatures and the use of a limited number of wavelengths used for identification. Current broadband systems such as Differential Optical Absorption Spectroscopy (DOAS) have either limitations for long-range propagation, or require transmitter power levels that are unsafe for operation in urban environments. Passive hyperspectral imaging systems that utilize absorption of solar scatter at visible and infrared wavelengths, or use absorption of background thermal emission, have been employed routinely for detection of airborne chemical species. Passive approaches have operational limitations at various ranges, or under adverse atmospheric conditions because the source intensity and spectrum is often an unknown variable. The work presented here describes a measurement approach that uses a known source of a low transmitted power level for an active system, while retaining the benefits of broadband and extremely long-path absorption operations. An optimized passive imaging system also is described that operates in the 3 to 4 mum window of the mid-infrared. Such active and passive instruments can be configured to optimize the detection of several hydrocarbon gases, as well as many other species of interest. Measurements have provided the incentive to develop algorithms for the calculations of atmospheric species concentrations using multiple wavelengths. These algorithms are used to prepare simulations and make comparisons with experimental results from absorption data of a supercontinuum laser source. The MODTRAN model is used in preparing the simulations, and also in developing additional

pH measurements of FET-based (bio)chemical sensors using portable measurement system.

PubMed

Voitsekhivska, T; Zorgiebel, F; Suthau, E; Wolter, K-J; Bock, K; Cuniberti, G

2015-01-01

In this study we demonstrate the sensing capabilities of a portable multiplex measurement system for FET-based (bio)chemical sensors with an integrated microfluidic interface. We therefore conducted pH measurements with Silicon Nanoribbon FET-based Sensors using different measurement procedures that are suitable for various applications. We have shown multiplexed measurements in aqueous medium for three different modes that are mutually specialized in fast data acquisition (constant drain current), calibration-less sensing (constant gate voltage) and in providing full information content (sweeping mode). Our system therefore allows surface charge sensing for a wide range of applications and is easily adaptable for multiplexed sensing with novel FET-based (bio)chemical sensors.

Component pattern analysis of chemicals using multispectral THz imaging system

NASA Astrophysics Data System (ADS)

Kawase, Kodo; Ogawa, Yuichi; Watanabe, Yuki

2004-04-01

We have developed a novel basic technology for terahertz (THz) imaging, which allows detection and identification of chemicals by introducing the component spatial pattern analysis. The spatial distributions of the chemicals were obtained from terahertz multispectral transillumination images, using absorption spectra previously measured with a widely tunable THz-wave parametric oscillator. Further we have applied this technique to the detection and identification of illicit drugs concealed in envelopes. The samples we used were methamphetamine and MDMA, two of the most widely consumed illegal drugs in Japan, and aspirin as a reference.

Chemical and optical properties of atmospheric aerosols in Phimai, Thailand by intensive surface measurements and satellite data analysis

NASA Astrophysics Data System (ADS)

Tsuruta, H.; Thana, B.; Takamura, T.; Hashimoto, M.; Yabuki, M.; Oikawa, E.; Nakajima, T.

2013-12-01

Atmospheric aerosols were measured at the Observatory of Atmospheric Research, in Phimai, Thailand, a key station of SKYNET, during 2006-2008. In the surface measurement, mass concentrations and major chemical components in fine and coarse aerosols were analyzed, and the optical properties such as AOT and SSA were measured by skyradiometer. Analysis of MODIS and CALIPSO satellite data was made for wild fire activities and aerosol distribution, respectively. In this paper, the following topics are summarized. The surface wind pattern in dry season was divided into the three periods as follows; D1 (Oct.-Nov.) with northeasterly monsoon, D3 (middle March-April) with southerly wind, and D2 (Dec.-early March) with a transit stage between D1 and D3. Wet season in southwesterly monsoon was from May to September. The concentration ratio of BC/nss-SO4 showed that the dominant PM2.5 aerosols in D1 were due to long-range transport of air pollutants emitted from urban/industrial area of east Asia. In contrast, most of aerosols in D3 were derived from biomass burning in Indochina, because the activity of biomass burning was highest in the latter D2 and early D3 period, by the analysis of the fire database in MODIS and of BC/nss-SO4. The mass concentration in PM2.5 showed a clear seasonal variation with the maximum in D2. On the contrary, AOT showed the maximum in D3, and which could be attributed to an increase in the vertical thickness of high aerosol concentration in the boundary layer by the CALIOP data analysis. Dust particles in D1 were directly transported from east Asia, and re-suspension of soil dusts was dominant in D2 because the surface soil became dry. In D3, soil dusts were re-suspended with the thermal plume caused by biomass burning. In contrast, high dust particles measured in the wet season was due to long range transport of dust aerosols from western desert area by the CALIOP data analysis.

Continuous-flow centrifugation to collect suspended sediment for chemical analysis

USGS Publications Warehouse

Conn, Kathleen E.; Dinicola, Richard S.; Black, Robert W.; Cox, Stephen E.; Sheibley, Richard W.; Foreman, James R.; Senter, Craig A.; Peterson, Norman T.

2016-12-22

Recent advances in suspended-sediment monitoring tools and surrogate technologies have greatly improved the ability to quantify suspended-sediment concentrations and to estimate daily, seasonal, and annual suspended-sediment fluxes from rivers to coastal waters. However, little is known about the chemical composition of suspended sediment, and how it may vary spatially between water bodies and temporally within a single system owing to climate, seasonality, land use, and other natural and anthropogenic drivers. Many water-quality contaminants, such as organic and inorganic chemicals, nutrients, and pathogens, preferentially partition in sediment rather than water. Suspended sediment-bound chemical concentrations may be undetected during analysis of unfiltered water samples, owing to small water sample volumes and analytical limitations. Quantification of suspended sediment‑bound chemical concentrations is needed to improve estimates of total chemical concentrations, chemical fluxes, and exposure levels of aquatic organisms and humans in receiving environments. Despite these needs, few studies or monitoring programs measure the chemical composition of suspended sediment, largely owing to the difficulty in consistently obtaining samples of sufficient quality and quantity for laboratory analysis.A field protocol is described here utilizing continuous‑flow centrifugation for the collection of suspended sediment for chemical analysis. The centrifuge used for development of this method is small, lightweight, and portable for the field applications described in this protocol. Project scoping considerations, deployment of equipment and system layout options, and results from various field and laboratory quality control experiments are described. The testing confirmed the applicability of the protocol for the determination of many inorganic and organic chemicals sorbed on suspended sediment, including metals, pesticides, polycyclic aromatic hydrocarbons, and

Chemical and Thermal Analysis

NASA Technical Reports Server (NTRS)

Bulluck, J. W.; Rushing, R. A.; Thornton, C. P.

1996-01-01

Work has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-Ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted changes in the molecular weight distribution of the Coflon material using a dual detector Gel Permeation Analysis. Again these changes may result in variation in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-Ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, Thermogravimetric Analysis, and Differential Scanning Calorimetry. We investigated a number of aged samples of both Tefzel and Coflon that were forwarded from MERL. Pressurized tests were performed in a modified Fluid G, which we will call G2. In this case the ethylene diamine concentration was increased to 3 percent in methanol. Coflon pipe sections and powdered Coflon were exposed in pressure cells at 1700 psi at three separate test temperatures, 70 C, 110 C, and 130 C. The primary purpose of the pressure tests in Fluid G2 was to further elucidate the aging mechanism of PVDF degradation.

ANALYSIS OF SAMPLES FROM TANK 5F CHEMICAL CLEANING

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

Poirier, M.; Fink, S.

2011-03-07

The Savannah River Site (SRS) is preparing Tank 5F for closure. The first step in preparing the tank for closure is mechanical sludge removal. Following mechanical sludge removal, SRS performed chemical cleaning with oxalic acid to remove the sludge heel. Personnel are currently assessing the effectiveness of the chemical cleaning. SRS personnel collected liquid samples during chemical cleaning and submitted them to Savannah River National Laboratory (SRNL) for analysis. Following chemical cleaning, they collected a solid sample (also known as 'process sample') and submitted it to SRNL for analysis. The authors analyzed these samples to assess the effectiveness of themore » chemical cleaning process. The conclusions from this work are: (1) With the exception of iron, the dissolution of sludge components from Tank 5F agreed with results from the actual waste demonstration performed in 2007. The fraction of iron removed from Tank 5F by chemical cleaning was significantly less than the fraction removed in the SRNL demonstrations. The likely cause of this difference is the high pH following the first oxalic acid strike. (2) Most of the sludge mass remaining in the tank is iron and nickel. (3) The remaining sludge contains approximately 26 kg of barium, 37 kg of chromium, and 37 kg of mercury. (4) Most of the radioactivity remaining in the residual material is beta emitters and {sup 90}Sr. (5) The chemical cleaning removed more than {approx} 90% of the uranium isotopes and {sup 137}Cs. (6) The chemical cleaning removed {approx} 70% of the neptunium, {approx} 83% of the {sup 90}Sr, and {approx} 21% of the {sup 60}Co. (7) The chemical cleaning removed less than 10% of the plutonium, americium, and curium isotopes. (8) The chemical cleaning removed more than 90% of the aluminium, calcium, and sodium from the tank. (9) The cleaning operations removed 61% of lithium, 88% of non-radioactive strontium, and 65% of zirconium. The {sup 90}Sr and non-radioactive strontium were

Estimating air chemical emissions from research activities using stack measurement data.

PubMed

Ballinger, Marcel Y; Duchsherer, Cheryl J; Woodruff, Rodger K; Larson, Timothy V

2013-03-01

&D facilities using chemical inventory data. Air emissions from research operations are difficult to estimate because of the changing nature of research processes and the small quantity and wide variety of chemicals used. Analysis of stack measurements taken over multiple facilities and a 10-year period using a Monte Carlo technique provided a method to quantify the low emissions and to estimate release fractions based on chemical inventories. The variation in release fractions did not correlate well with factors investigated, confirming the complexities in estimating R&D emissions.

40 CFR 761.253 - Chemical analysis.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Chemical analysis. 761.253 Section 761.253 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Sample Sites, Collecting Surface Samples, and Analyzing Standard PCB Wipe Samples § 761.253 Chemical...

40 CFR 761.253 - Chemical analysis.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Chemical analysis. 761.253 Section 761.253 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Sample Sites, Collecting Surface Samples, and Analyzing Standard PCB Wipe Samples § 761.253 Chemical...

40 CFR 761.253 - Chemical analysis.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Chemical analysis. 761.253 Section 761.253 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Sample Sites, Collecting Surface Samples, and Analyzing Standard PCB Wipe Samples § 761.253 Chemical...

40 CFR 761.253 - Chemical analysis.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Chemical analysis. 761.253 Section 761.253 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Sample Sites, Collecting Surface Samples, and Analyzing Standard PCB Wipe Samples § 761.253 Chemical...

40 CFR 761.253 - Chemical analysis.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Chemical analysis. 761.253 Section 761.253 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Sample Sites, Collecting Surface Samples, and Analyzing Standard PCB Wipe Samples § 761.253 Chemical...

Review of chemical separation techniques applicable to alpha spectrometric measurements

NASA Astrophysics Data System (ADS)

de Regge, P.; Boden, R.

1984-06-01

Prior to alpha-spectrometric measurements several chemical manipulations are usually required to obtain alpha-radiating sources with the desired radiochemical and chemical purity. These include sampling, dissolution or leaching of the elements of interest, conditioning of the solution, chemical separation and preparation of the alpha-emitting source. The choice of a particular method is dependent on different criteria but always involves aspects of the selectivity or the quantitative nature of the separations. The availability of suitable tracers or spikes and modern high resolution instruments resulted in the wide-spread application of isotopic dilution techniques to the problems associated with quantitative chemical separations. This enhanced the development of highly elective methods and reagents which led to important simplifications in the separation schemes. The chemical separation methods commonly used in connection with alpha-spectrometric measurements involve precipitation with selected scavenger elements, solvent extraction, ion exchange and electrodeposition techniques or any combination of them. Depending on the purpose of the final measurement and the type of sample available the chemical separation methods have to be adapted to the particular needs of environment monitoring, nuclear chemistry and metrology, safeguards and safety, waste management and requirements in the nuclear fuel cycle. Against the background of separation methods available in the literature the present paper highlights the current developments and trends in the chemical techniques applicable to alpha spectrometry.

An extended chemical analysis of gallstone.

PubMed

Chandran, P; Kuchhal, N K; Garg, P; Pundir, C S

2007-09-01

Chemical composition of gall stones is essential for aetiopathogensis of gallstone disease. We have reported quantitative chemical analysis of total cholesterol bilirubin, calcium, iron and inorganic phosphate in 120 gallstones from haryana. To extend this chemical analysis of gall stones by studying more cases and by analyzing more chemical constituents. A quantitative chemical analysis of total cholesterol, total bilirubin, fatty acids, triglycerides, phospholipids, bile acids, soluble proteins, sodium potassium, magnesium, copper, oxalate and chlorides of biliary calculi (52 cholesterol, 76 mixed and 72 pigment) retrieved from surgical operation of 200 patients from Haryana state was carried out. Total cholesterol as the major component and total bilirubin, phospholipids, triglycerides, bile acids, fatty acids (esterified), soluble protein, calcium, magnesium, iron, copper, sodium, potassium, inorganic phosphate, oxalate and chloride as minor components were found in all types of calculi. The cholesterol stones had higher content of total cholesterol, phospholipids, fatty acids (esterified), inorganic phosphate and copper compared to mixed and pigment stones. The mixed stones had higher content of iron and triglycerides than to cholesterol and pigment stones. The pigment stones were richer in total bilirubin, bile acids, calcium, oxalate, magnesium, sodium, potassium, chloride and soluble protein compared to cholesterol and mixed stones. Although total cholesterol was a major component of cholesterol, mixed and pigment gall stone in Haryana, the content of most of the other lipids, cations and anions was different in different gall stones indicating their different mechanism of formation.

Chemical and Thermal Analysis

NASA Technical Reports Server (NTRS)

Bulluck, J. W.; Rushing, R. A.

1997-01-01

Work during the past three years has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-Ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted changes in the molecular weight distribution and the increased crosslinking of the Coflon material using Gel Permeation Chromatographic Analysis. Again these changes may result in variations in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, and Differential Scanning Calorimetry. We investigated a plethora of aged samples of both Tefzel and Coflon that were forwarded from MERL. Pressurized tests were performed on powdered PVDF in a modified Fluid A, which we will call A-2. In this case the ethylene diamine concentration was increased to 3 percent in methanol. Coflon pipe sections and powdered Coflon were exposed in pressure cells at 1700 psi at three separate test temperatures.

Chemical, Biological, and Explosive Sensors for Field Measurements

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

Kevin Kyle, Manuel Manard, Stephan Weeks

Special Technologies Laboratory (STL) is developing handheld chemical, biological, and explosive (CBE) detection systems and sensor motes for wireless networked field operations. The CBE sensors are capable of detecting and identifying multiple targeted toxic industrial chemicals (TICs) and high-explosive vapor components. The CBE devices are based on differential mobility spectrometry (DMS) coupled with fast gas chromatography (GC) or mass spectrometry. The systems all include the concepts of: 1. Direct air/particulate “smart” sampling 2. Selective, continuous real-time (~1 sec) alert monitoring using DMS 3. Highly selective, rapid dual technology separation/verification analysis The biosensor technology is based on Raman aerosol particle flowmore » cytometry for target detection and identification. Monitoring and identifying trace level chemical vapors directly from ambient air will allow First Responders to quickly adapt situational response strategies and personal protective equipment needs to the specific response scenario being encountered. First Responders require great confidence in the measurements and ability of a given system to detect CBE below threshold levels without interferences. The concept of determining the background matrix in near real-time to allow subsequent automated field-programmable method selection and cueing of high-value assets in a wide range of environs will be presented. This provides CBE information for decisions prior to First Responders entering the response site or sending a portable mobile unit for a remote site survey of the hazards. The focus is on real-time information needed by those responsible for emergency response and national security.« less

Chemical processing and shampooing impact cortisol measured in human hair.

PubMed

Hoffman, M Camille; Karban, Laura V; Benitez, Patrick; Goodteacher, Angela; Laudenslager, Mark L

2014-08-01

The assessment of cortisol in hair has gained popularity as a means to measure retrospective hypothalamic-pituitary-adrenal activity in a number of species; however, cortisol levels from human hair subjected to typical chemicals for cosmetic or hygienic purposes may be altered by the chemicals used. The purposed of this study was to determine if exposure of hair to chemical processing or shampooing impacts cortisol values. Human hair not exposed to prior chemical processing was cut from the posterior vertex region of the head of 106 human subjects as close to the scalp as possible. The hair sample was divided into 4-6 full-length clusters depending on quantity of hair available. Each hair sample was processed for baseline (native) cortisol and remaining clusters were exposed to five standard chemical hair treatments (Experiment 1) or were shampooed 15 or 30 times (Experiment 2). Hair was ground and cortisol levels were determined by enzyme immunoassay (EIA). Comparisons were made between native hair and processed hair using paired t-tests and Pearson correlation. Hair cortisol as assessed by EIA was significantly altered by chemical processing but in somewhat different ways. Exposure to bleach (harshest exposure), demi-perm (least exposure) or 15-30 shampoos resulted in a significant decrease in cortisol level while exposure to varying percentages of peroxides increased cortisol measured. There were no differences in cortisol levels associated with sex, age or tobacco use in the native hair for this particular group. Chemical processing and frequent shampooing affect cortisol levels measured in hair. Chemically processed or excessively shampooed hair should be avoided when recruiting subjects for hair cortisol studies.

Chemical processing and shampooing impact cortisol measured in human hair

PubMed Central

Hoffman, M. Camille; Karban, Laura V.; Benitez, Patrick; Goodteacher, Angela; Laudenslager, Mark L.

2015-01-01

Purpose The assessment of cortisol in hair has gained popularity as a means to measure retrospective hypothalamic-pituitary-adrenal activity in a number of species; however, cortisol levels from human hair subjected to typical chemicals for cosmetic or hygienic purposes may be altered by the chemicals used. The purposed of this study was to determine if exposure of hair to chemical processing or shampooing impacts cortisol values. Methods Human hair not exposed to prior chemical processing was cut from the posterior vertex region of the head of 106 human subjects as close to the scalp as possible. The hair sample was divided into 4-6 full-length clusters depending on quantity of hair available. Each hair sample was processed for baseline (native) cortisol and remaining clusters were exposed to five standard chemical hair treatments (Experiment 1) or were shampooed 15 or 30 times (Experiment 2). Hair was ground and cortisol levels were determined by enzyme immunoassay (EIA). Comparisons were made between native hair and processed hair using paired t-tests and Pearson correlation. Results Hair cortisol as assessed by EIA was significantly altered by chemical processing but in somewhat different ways. Exposure to bleach (harshest exposure), demi-perm (least exposure) or 15-30 shampoos resulted in a significant decrease in cortisol level while exposure to varying percentages of peroxides increased cortisol measured. There were no differences in cortisol levels associated with sex, age or tobacco use in the native hair for this particular group. Conclusion Chemical processing and frequent shampooing affect cortisol levels measured in hair. Chemically processed or excessively shampooed hair should be avoided when recruiting subjects for hair cortisol studies. PMID:25090265

Nature and Analysis of Chemical Species.

ERIC Educational Resources Information Center

Shuman, Mark S.; Fogleman, Wavell W.

1978-01-01

Presents a literature review of the nature and analysis of chemical species in water, covering publications of 1976-77. This review is concerned with inorganics, and it covers: (1) electrochemical analysis; (2) spectroscopy; (3) neutron activation, radiochemical analysis, and isotope dilution. A list of 262 references is also presented. (HM)

Odor and odorous chemical emissions from animal buildings: part 4-correlations between sensory and chemical measurements

USDA-ARS?s Scientific Manuscript database

This study supplemented the National Air Emissions Monitoring Study (NAEMS) with one year of comprehensive measurements of odor emission at five swine and four dairy buildings. The measurements included both standard human sensory measurements using dynamic forced-choice olfactometry and chemical an...

An infrared measurement of chemical desorption from interstellar ice analogues

NASA Astrophysics Data System (ADS)

Oba, Y.; Tomaru, T.; Lamberts, T.; Kouchi, A.; Watanabe, N.

2018-03-01

In molecular clouds at temperatures as low as 10 K, all species except hydrogen and helium should be locked in the heterogeneous ice on dust grain surfaces. Nevertheless, astronomical observations have detected over 150 different species in the gas phase in these clouds. The mechanism by which molecules are released from the dust surface below thermal desorption temperatures to be detectable in the gas phase is crucial for understanding the chemical evolution in such cold clouds. Chemical desorption, caused by the excess energy of an exothermic reaction, was first proposed as a key molecular release mechanism almost 50 years ago1. Chemical desorption can, in principle, take place at any temperature, even below the thermal desorption temperature. Therefore, astrochemical network models commonly include this process2,3. Although there have been a few previous experimental efforts4-6, no infrared measurement of the surface (which has a strong advantage to quantify chemical desorption) has been performed. Here, we report the first infrared in situ measurement of chemical desorption during the reactions H + H2S → HS + H2 (reaction 1) and HS + H → H2S (reaction 2), which are key to interstellar sulphur chemistry2,3. The present study clearly demonstrates that chemical desorption is a more efficient process for releasing H2S into the gas phase than was previously believed. The obtained effective cross-section for chemical desorption indicates that the chemical desorption rate exceeds the photodesorption rate in typical interstellar environments.

A benchmarking method to measure dietary absorption efficiency of chemicals by fish.

PubMed

Xiao, Ruiyang; Adolfsson-Erici, Margaretha; Åkerman, Gun; McLachlan, Michael S; MacLeod, Matthew

2013-12-01

Understanding the dietary absorption efficiency of chemicals in the gastrointestinal tract of fish is important from both a scientific and a regulatory point of view. However, reported fish absorption efficiencies for well-studied chemicals are highly variable. In the present study, the authors developed and exploited an internal chemical benchmarking method that has the potential to reduce uncertainty and variability and, thus, to improve the precision of measurements of fish absorption efficiency. The authors applied the benchmarking method to measure the gross absorption efficiency for 15 chemicals with a wide range of physicochemical properties and structures. They selected 2,2',5,6'-tetrachlorobiphenyl (PCB53) and decabromodiphenyl ethane as absorbable and nonabsorbable benchmarks, respectively. Quantities of chemicals determined in fish were benchmarked to the fraction of PCB53 recovered in fish, and quantities of chemicals determined in feces were benchmarked to the fraction of decabromodiphenyl ethane recovered in feces. The performance of the benchmarking procedure was evaluated based on the recovery of the test chemicals and precision of absorption efficiency from repeated tests. Benchmarking did not improve the precision of the measurements; after benchmarking, however, the median recovery for 15 chemicals was 106%, and variability of recoveries was reduced compared with before benchmarking, suggesting that benchmarking could account for incomplete extraction of chemical in fish and incomplete collection of feces from different tests. © 2013 SETAC.

Effects of measurement errors on psychometric measurements in ergonomics studies: Implications for correlations, ANOVA, linear regression, factor analysis, and linear discriminant analysis.

PubMed

Liu, Yan; Salvendy, Gavriel

2009-05-01

This paper aims to demonstrate the effects of measurement errors on psychometric measurements in ergonomics studies. A variety of sources can cause random measurement errors in ergonomics studies and these errors can distort virtually every statistic computed and lead investigators to erroneous conclusions. The effects of measurement errors on five most widely used statistical analysis tools have been discussed and illustrated: correlation; ANOVA; linear regression; factor analysis; linear discriminant analysis. It has been shown that measurement errors can greatly attenuate correlations between variables, reduce statistical power of ANOVA, distort (overestimate, underestimate or even change the sign of) regression coefficients, underrate the explanation contributions of the most important factors in factor analysis and depreciate the significance of discriminant function and discrimination abilities of individual variables in discrimination analysis. The discussions will be restricted to subjective scales and survey methods and their reliability estimates. Other methods applied in ergonomics research, such as physical and electrophysiological measurements and chemical and biomedical analysis methods, also have issues of measurement errors, but they are beyond the scope of this paper. As there has been increasing interest in the development and testing of theories in ergonomics research, it has become very important for ergonomics researchers to understand the effects of measurement errors on their experiment results, which the authors believe is very critical to research progress in theory development and cumulative knowledge in the ergonomics field.

Measuring indigenous photosynthetic organisms to detect chemical warefare agents in water

DOEpatents

Greenbaum, Elias; Sanders, Charlene A.

2005-11-15

A method of testing water to detect the presence of a chemical or biological warfare agent is disclosed. The method is carried out by establishing control data by providing control water containing indigenous organisms but substantially free of a chemical and a biological warfare agent. Then measuring photosynthetic activity of the control water with a fluorometer to obtain control data to compare with test data to detect the presence of the chemical or agent. The test data is gathered by providing test water comprising the same indigenous organisms as contained in the control water. Further, the test water is suspected of containing the chemical or agent to be tested for. Photosynthetic activity is also measured by fluorescence induction in the test water using a fluorometer.

Measurements of in situ chemical ozone (oxidant) production rates

NASA Astrophysics Data System (ADS)

Huang, Hao; Faloon, Kate; Najera, Juan; Bloss, William

2013-04-01

Tropospheric ozone is a major air pollutant, harmful to human health, agricultural crops and vegetation, the main precursor to the atmospheric oxidants which initiate the degradation of most reactive gases emitted to the atmosphere, and an important greenhouse gas in its own right. The capacity to understand and predict tropospheric ozone levels is a key goal for atmospheric science - but one which is challenging, as ozone is formed in the atmosphere from the complex oxidation of VOCs in the presence of NOx and sunlight, on a timescale such that in situ chemical processes, deposition and transport all affect ozone levels. Known uncertainties in emissions, chemistry, dynamics and deposition affect the accuracy of predictions of current and future ozone levels, and hinder development of optimal air quality policies to mitigate against ozone exposure. Recently new approaches to directly measure the local chemical ozone production rate, bypassing the many uncertainties in emissions and chemical schemes, have been developed (Cazorla & Brune, AMT 2010). Here, we describe the development of an analogous Ozone Production Rate (OPR) approach: Air is sampled into parallel reactors, within which ozone formation either occurs as in the ambient atmosphere, or is suppressed. Comparisons of ozone levels exiting a pair of such reactors determines the net chemical oxidant production rate, after correction for perturbation of the NOx-O3 photochemical steady state, and when operated under conditions such that wall effects are minimised. We report preliminary measurements of local chemical ozone production made during the UK NERC ClearfLo (Clean Air for London) campaign at an urban background location in London in January and July 2012. The OPR system was used to measure the local chemical oxidant formation rate, which is compared with observed trends in O3 and NOx and the prevailing meteorology, and with the predictions of a detailed zero-dimensional atmospheric chemistry model

Chemical composition measurements of the atmosphere of Jupiter with the Galileo Probe mass spectrometer

NASA Technical Reports Server (NTRS)

Niemann, H. B.; Atreya, S. K.; Carignan, G. R.; Donahue, T. M.; Haberman, J. A.; Harpold, D. N.; Hartle, R. E.; Hunten, D. M.; Kasprzak, W. T.; Mahaffy, P. R.;

Chemical composition measurements of the atmosphere of Jupiter with the Galileo Probe mass spectrometer.

PubMed

Niemann, H B; Atreya, S K; Carignan, G R; Donahue, T M; Haberman, J A; Harpold, D N; Hartle, R E; Hunten, D M; Kasprzak, W T; Mahaffy, P R; Owen, T C; Spencer, N W

1998-01-01

The Galileo Probe entered the atmosphere of Jupiter on December 7, 1995. Measurements of the chemical and isotopic composition of the Jovian atmosphere were obtained by the mass spectrometer during the descent over the 0.5 to 21 bar pressure region over a time period of approximately 1 hour. The sampling was either of atmospheric gases directly introduced into the ion source of the mass spectrometer through capillary leaks or of gas, which had been chemically processed to enhance the sensitivity of the measurement to trace species or noble gases. The analysis of this data set continues to be refined based on supporting laboratory studies on an engineering unit. The mixing ratios of the major constituents of the atmosphere hydrogen and helium have been determined as well as mixing ratios or upper limits for several less abundant species including: methane, water, ammonia, ethane, ethylene, propane, hydrogen sulfide, neon, argon, krypton, and xenon. Analysis also suggests the presence of trace levels of other 3 and 4 carbon hydrocarbons, or carbon and nitrogen containing species, phosphine, hydrogen chloride, and of benzene. The data set also allows upper limits to be set for many species of interest which were not detected. Isotope ratios were measured for 3He/4He, D/H, 13C/12C, 20Ne/22Ne, 38Ar/36Ar and for isotopes of both Kr and Xe.

Chemical composition measurements of the atmosphere of jupiter with the galileo probe mass spectrometer

NASA Astrophysics Data System (ADS)

Niemann, H. B.; Atreya, S. K.; Carignan, G. R.; Donahue, T. M.; Haberman, J. A.; Harpold, D. N.; Hartle, R. E.; Hunten, D. M.; Kasprzak, W. T.; Mahaffy, P. R.; Owen, T. C.; Spencer, N. W.

The Galileo Probe entered the atmosphere of Jupiter on December 7, 1995. Measurements of the chemical and isotopic composition of the Jovian atmosphere were obtained by the mass spectrometer during the descent over the 0.5 to 21 bar pressure region over a time period of approximately 1 hour. The sampling was either of atmospheric gases directly introduced into the ion source of the mass spectrometer through capillary leaks or of gas, which had been chemically processed to enhance the sensitivity of the measurement to trace species or noble gases. The analysis of this data set continues to be refined based on supporting laboratory studies on an engineering unit. The mixing ratios of the major constituents of the atmosphere hydrogen and helium have been determined as well as mixing ratios or upper limits for several less abundant species including: methane, water, ammonia, ethane, ethylene, propane, hydrogen sulfide, neon, argon, krypton, and xenon. Analysis also suggests the presence of trace levels of other 3 and 4 carbon hydrocarbons, or carbon and nitrogen containing species, phosphine, hydrogen chloride, and of benzene. The data set also allows upper limits to be set for many species of interest which were not detected. Isotope ratios were measured for ^3He/^4He, D/H, ^13C/^12C, ^20Ne/^22Ne, ^38Ar/^36Ar and for isotopes of both Kr and Xe.

Sensory assessment and chemical measurement of astringency of Greek wines: Correlations with analytical polyphenolic composition.

PubMed

Kallithraka, S; Kim, D; Tsakiris, A; Paraskevopoulos, I; Soleas, G

2011-06-15

The purpose of this study was to measure the astringency of selected Greek red wines and to assess the relationship between sensory and chemical data. Nine red wines produced by three native Greek grape varieties (agiorgitiko, xinomavro and mavrodafni) were used and their astringency and bitterness was assessed by a trained panel. In addition, their astringency was estimated chemically employing the ovalbumin precipitation method. Their polyphenolic composition was also determined by High Performance Liquid Chromatography (HPLC). The sensory data showed that mandilaria was the most astringent variety whereas agiorgitiko was the least. Statistical analysis of the results indicated that the chemical data obtained for astringency significantly correlated with the sensory determinations. In addition, significant correlations were obtained between the sensory data and the wine polyphenolic composition. Copyright © 2010 Elsevier Ltd. All rights reserved.

LIF measurements and chemical kinetic analysis of methylidyne formation in high-pressure counter-flow partially premixed and non-premixed flames

NASA Astrophysics Data System (ADS)

Naik, S. V.; Laurendeau, N. M.

2004-11-01

We report quantitative, spatially resolved, linear laser-induced fluorescence (LIF) measurements of methylidyne concentration ([CH]) in laminar, methane air, counter-flow partially premixed and non-premixed flames using excitation near 431.5 nm in the A X (0,0) band. For partially premixed flames, fuel-side equivalence ratios (ϕB) of 1.45, 1.6 and 2.0 are studied at pressures of 1, 3, 6, 9 and 12 atm. For non-premixed flames, the fuel-side mixture consists of 25% CH4 and 75% N2; measurements are obtained at pressures of 1, 2, 3, 4, 5, 6, 9 and 12 atm. The quantitative CH measurements are compared with predictions from an opposed-flow flame code utilizing two GRI chemical kinetic mechanisms (versions 2.11 and 3.0). LIF measurements of [CH] are corrected for variations in the quenching rate coefficient by using major species concentrations and temperatures generated by the code along with suitable quenching cross sections for CH available from the literature. A pathway analysis provides relative contributions from important elementary reactions to the total amount of CH produced at various pressures. Key reactions controlling peak CH concentrations are also identified by using a sensitivity analysis. For the partially premixed flames, measured CH profiles are reproduced reasonably well by GRI 3.0, although some quantitative disagreement exists at all pressures. Two CH radical peaks are observed for ϕB=1.45 and ϕB=1.6 at pressures above 3 atm. Peak CH concentrations for the non-premixed flames are significantly underpredicted by GRI 3.0. The latter agrees with previously reported NO concentrations, which are also underpredicted in these same high-pressure counter-flow diffusion flames.

Directly amplified redox sensor for on-chip chemical analysis

NASA Astrophysics Data System (ADS)

Takahashi, Sou; Futagawa, Masato; Ishida, Makoto; Sawada, Kazuaki

2014-03-01

In recent years, many groups have studied redox sensors for chemical analysis. A redox sensor has certain powerful advantages, such as its ability to detect multiple ions inside the sensing area, and its ability to measure concentrations of materials by using voltage and current signals. However, the output current signal of a redox sensor decreases when either concentration or sensing area decreases. Therefore, we propose the use of an amplified redox sensor (ARS) for measuring small current signals. The proposed sensor consists of a working electrode combined with a bipolar transistor. In this study, we fabricated an ARS sensor and performed low-concentration measurements using current signal amplification with an integrated bipolar transistor. The sensor chip successfully detected a potassium ferricyanide (K3[Fe(CN)6]) concentration of as low as 10 µM using cyclic voltammetry.

Electrochemical approaches for chemical and biological analysis on Mars

NASA Technical Reports Server (NTRS)

Kounaves, Samuel P.

2003-01-01

Obtaining in situ chemical data from planetary bodies such as Mars or Europa can present significant challenges. The one analytical technique that has many of the requisite characteristics to meet such a challenge is electroanalysis. Described here are three electroanalytical devices designed for in situ geochemical and biological analysis on Mars. The Mars Environmental Compatibility Assessment (MECA) was built and flight qualified for the now cancelled NASA Mars 2001 Lander. Part of MECA consisted of four "cells" containing arrays of electrochemical based sensors for measuring the ionic species in soil samples. A next-generation MECA, the Robotic Chemical Analysis Laboratory (RCAL), uses a carousel-type system to allow for greater customization of analytical procedures. A second instrument, proposed as part of the 2007 CryoScout mission, consists of a flow-through inorganic chemical analyzer (MICA). CryoScout is a torpedo-like device designed for subsurface investigation of the stratigraphic climate record embedded in Mars' north polar cap. As the CryoScout melts its way through the ice cap, MICA will collect and analyze the meltwater for a variety of inorganics and chemical parameters. By analyzing the chemistry locked in the layers of dust, salt, and ice, geologists will be able to determine the recent history of climate, water, and atmosphere on Mars and link it to the past. Finally, electroanalysis shows its abilities in the detection of possible microorganism on Mars or elsewhere in the solar system. To identify an unknown microorganism, one that may not even use Earth-type biochemistry, requires a detection scheme which makes minimal assumptions and looks for the most general features. Recent work has demonstrated that the use of an array of electrochemical sensors which monitors the changes in a solution via electrical conductivity, pH, and ion selective electrodes, can be used to detect minute chemical perturbations caused by the growth of bacteria and

Electrochemical approaches for chemical and biological analysis on Mars.

PubMed

Kounaves, Samuel P

2003-02-17

Obtaining in situ chemical data from planetary bodies such as Mars or Europa can present significant challenges. The one analytical technique that has many of the requisite characteristics to meet such a challenge is electroanalysis. Described here are three electroanalytical devices designed for in situ geochemical and biological analysis on Mars. The Mars Environmental Compatibility Assessment (MECA) was built and flight qualified for the now cancelled NASA Mars 2001 Lander. Part of MECA consisted of four "cells" containing arrays of electrochemical based sensors for measuring the ionic species in soil samples. A next-generation MECA, the Robotic Chemical Analysis Laboratory (RCAL), uses a carousel-type system to allow for greater customization of analytical procedures. A second instrument, proposed as part of the 2007 CryoScout mission, consists of a flow-through inorganic chemical analyzer (MICA). CryoScout is a torpedo-like device designed for subsurface investigation of the stratigraphic climate record embedded in Mars' north polar cap. As the CryoScout melts its way through the ice cap, MICA will collect and analyze the meltwater for a variety of inorganics and chemical parameters. By analyzing the chemistry locked in the layers of dust, salt, and ice, geologists will be able to determine the recent history of climate, water, and atmosphere on Mars and link it to the past. Finally, electroanalysis shows its abilities in the detection of possible microorganism on Mars or elsewhere in the solar system. To identify an unknown microorganism, one that may not even use Earth-type biochemistry, requires a detection scheme which makes minimal assumptions and looks for the most general features. Recent work has demonstrated that the use of an array of electrochemical sensors which monitors the changes in a solution via electrical conductivity, pH, and ion selective electrodes, can be used to detect minute chemical perturbations caused by the growth of bacteria and

Good Chemical Measurements, Good Public Policies

NASA Astrophysics Data System (ADS)

Faulkner, Larry R.

2005-02-01

At every turn now, one encounters sharply debated issues and important public policies that rest on chemical information. This is true in practically any arena where public interest intersects with the material world: health care practice and public health; energy; quality of air, water, and food; manufacturing standards and product liability; criminal justice; national and international security, including the defense against terrorism. The scale can be truly global, as in the case of the current debate over climate change, which extends into international efforts to regulate gaseous emissions. Sometimes the relevant chemical measurements and applicable theory are sound and their scope is appropriate to the policy; often they are inadequate and a policy or debate overreaches the analytical capability needed to support it. In the decades ahead, the issues with us today will become even more pressing and will drive a still greater reliance on analytical chemistry. This presentation will have four parts covering (a) illustrations of the impact of analytical chemistry on public debate and public policy, including instances where analytical capabilities actually gave rise to new issues and policies, (b) the manner in which chemical information is handled and understood in public debates, (c) areas of analytical chemistry that will be critical to sound public policy in the future, and (d) implications for the education of leaders and general citizens of modern societies.

[Preventive measures against health damage due to chemicals in household products].

PubMed

Kaniwa, Masa-aki

2010-01-01

Chemicals in household products have been paid much attention as the main cause of health damage in consumers, such as allergic contact dermatitis. Preventive measures against health damage due to chemicals in fabrics, plastics and rubber products for household use, are reviewed, focusing on 1) the incidence of health damage due to household products, 2) causative product-chemical investigation, and 3) case studies on skin damage.

VALIDATION GUIDELINES FOR LABORATORIES PERFORMING FORENSIC ANALYSIS OF CHEMICAL TERRORISM

EPA Science Inventory

The Scientific Working Group on Forensic Analysis of Chemical Terrorism (SWGFACT) has developed the following guidelines for laboratories engaged in the forensic analysis of chemical evidence associated with terrorism. This document provides a baseline framework and guidance for...

Direct measurements of intermolecular forces by chemical force microscopy

NASA Astrophysics Data System (ADS)

Vezenov, Dmitri Vitalievich

1999-12-01

Detailed description of intermolecular forces is key to understanding a wide range of phenomena from molecular recognition to materials failure. The unique features of atomic force microscopy (AFM) to make point contact force measurements with ultra high sensitivity and to generate spatial maps of surface topography and forces have been extended to include measurements between well-defined organic molecular groups. Chemical modification of AFM probes with self-assembled monolayers (SAMs) was used to make them sensitive to specific molecular interactions. This novel chemical force microscopy (CFM) technique was used to probe forces between different molecular groups in a range of environments (vacuum, organic liquids and aqueous solutions); measure surface energetics on a nanometer scale; determine pK values of the surface acid and base groups; measure forces to stretch and unbind a short synthetic DNA duplex and map the spatial distribution of specific functional groups and their ionization state. Studies of adhesion forces demonstrated the important contribution of hydrogen bonding to interactions between simple organic functionalities. The chemical identity of the tip and substrate surfaces as well as the medium had a dramatic effect on adhesion between model monolayers. A direct correlation between surface free energy and adhesion forces was established. The adhesion between epoxy polymer and model mixed SAMs varied with the amount of hydrogen bonding component in the monolayers. A consistent interpretation of CFM measurements in polar solvents was provided by contact mechanics models and intermolecular force components theory. Forces between tips and surfaces functionalized with SAMs terminating in acid or base groups depended on their ionization state. A novel method of force titration was introduced for highly local characterization of the pK's of surface functional groups. The pH-dependent changes in friction forces were exploited to map spatially the

Thermally emissive sensing materials for chemical spectroscopy analysis

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

Poole, Zsolt; Ohodnicki, Paul R.

A sensor using thermally emissive materials for chemical spectroscopy analysis includes an emissive material, wherein the emissive material includes the thermally emissive materials which emit electromagnetic radiation, wherein the electromagnetic radiation is modified due to chemical composition in an environment; and a detector adapted to detect the electromagnetic radiation, wherein the electromagnetic radiation is indicative of the chemical interaction changes and hence chemical composition and/or chemical composition changes of the environment. The emissive material can be utilized with an optical fiber sensor, with the optical fiber sensor operating without the emissive material probed with a light source external to themore » material.« less

Measurement of Fluorine Atom Concentrations and Reaction Rates in Chemical Laser Systems.

DTIC Science & Technology

1981-09-01

AD-A1RA 070 AERODYNEERESEARCHUINC BEDFORDM MA F/6_20/5 MEASURE MENT OF FLUORINE ATOM CONCENTRATIONS AND REACTION RATFS -ETC(U) SEP_ A A C STANT ON...0772 LEVELIg 00 ~ARI-RR-272 cO0 MEASUREMENT OF FLUORINE ATOM CONCENTRATIONS AND REACTION RATES IN CHEMICAL LASER SYSTEMS ANNUAL TECHNICAL REPORT by...MEASUREMENT OF FLUORINE ATOM CONCENTRATIONS AND Annual Report REACTION RATES IN CHEMICAL LASER SYSTEMS 23 July 1980 - 23 July 1981 S. PERFORMING ORG. REPORT

Chemical Engineering Data Analysis Made Easy with DataFit

ERIC Educational Resources Information Center

Brenner, James R.

2006-01-01

The outline for half of a one-credit-hour course in analysis of chemical engineering data is presented, along with a range of typical problems encountered later on in the chemical engineering curriculum that can be used to reinforce the data analysis skills learned in the course. This mini course allows students to be exposed to a variety of ChE…

Measurement of residual chemical shift anisotropies in compressed polymethylmethacrylate gels. Automatic compensation of gel isotropic shift contribution.

PubMed

Hallwass, Fernando; Teles, Rubens R; Hellemann, Erich; Griesinger, Christian; Gil, Roberto R; Navarro-Vázquez, Armando

2018-05-01

Mechanical compression of polymer gels provides a simple way for the measurement of residual chemical shift anisotropies, which then can be employed, on its own, or in combination with residual dipolar couplings, for structural elucidation purposes. Residual chemical shift anisotropies measured using compression devices needed a posteriori correction to account for the increase of the polymer to solvent ratio inside the swollen gel. This correction has been cast before in terms of a single-free parameter which, as shown here, can be simultaneously optimized along with the components of the alignment tensor while still retaining discriminating power of the different relative configurations as illustrated in the stereochemical analysis of α-santonin and 10-epi-8-deoxycumambrin B. Copyright © 2018 John Wiley & Sons, Ltd.

Gas- and particle-phase chemical composition measurements onboard the G-1 research aircraft during the GoAmazon campaign.

NASA Astrophysics Data System (ADS)

Shilling, J.; Pekour, M. S.; Fortner, E.; Hubbe, J. M.; Longo, K.; Martin, S. T.; Mei, F.; Springston, S. R.; Tomlinson, J. M.; Wang, J.

2014-12-01

The Green Ocean Amazon (GoAmazon) campaign conducted from January 2014 - December 2015 in the vicinity of Manaus, Brazil, was designed to study the aerosol lifecycle and aerosol-cloud interactions in both pristine and anthropogenically influenced conditions. As part of this campaign, the DOE G-1 research aircraft was deployed from February 17th - March 25th 2014 and September 6th - October 5th 2014 to investigate aerosol and cloud properties aloft. An Aerodyne High Resolution Aerosol Mass Spectrometer (AMS) and an Ionicon Proton Transfer Reaction Mass Spectrometer (PTRMS) were part of the G-1 research aircraft payload and were used to investigate aerosol gas- and particle-phase chemical composition. Here we present preliminary analysis of the aerosol and gas phase chemical composition. PTR-MS measurements show that isoprene and its oxidation products are the dominant VOCs during research flights. HR-AMS measurements reveal that the particle phase is dominated by organic material with smaller concentrations of sulfate and nitrate observed. Organic particle concentrations are enhanced when encountering the urban plume from Manaus. During the wet season, we observe increased concentrations of organic particle when passing through low-altitude clouds. PMF analysis of the organic mass spectra shows that the chemical composition of the particles observed in-cloud is distinctly different from particles observed outside clouds. We will also compare measurements made during the wet and dry seasons.

Measuring in vitro biotransformation rates of super hydrophobic chemicals in rat liver s9 fractions using thin-film sorbent-phase dosing.

PubMed

Lee, Yung-Shan; Otton, S Victoria; Campbell, David A; Moore, Margo M; Kennedy, Chris J; Gobas, Frank A P C

2012-01-03

Methods for rapid and cost-effective assessment of the biotransformation potential of very hydrophobic and potentially bioaccumulative chemicals in mammals are urgently needed for the ongoing global evaluation of the environmental behavior of commercial chemicals. We developed and tested a novel solvent-free, thin-film sorbent-phase in vitro dosing system to measure the in vitro biotransformation rates of very hydrophobic chemicals in male Sprague-Dawley rat liver S9 homogenates and compared the rates to those measured by conventional solvent-delivery dosing. The thin-film sorbent-phase dosing system using ethylene vinyl acetate coated vials was developed to eliminate the incomplete dissolution of very hydrophobic substances in largely aqueous liver homogenates, to determine biotransformation rates at low substrate concentrations, to measure the unbound fraction of substrate in solution, and to simplify chemical analysis by avoiding the difficult extraction of test chemicals from complex biological matrices. Biotransformation rates using sorbent-phase dosing were 2-fold greater than those measured using solvent-delivery dosing. Unbound concentrations of very hydrophobic test chemicals were found to decline with increasing S9 and protein concentrations, causing measured biotransformation rates to be independent of S9 or protein concentrations. The results emphasize the importance of specifying both protein content and unbound substrate fraction in the measurement and reporting of in vitro biotransformation rates of very hydrophobic substances, which can be achieved in a thin-film sorbent-phase dosing system.

[Preventive measures against health damage due to chemicals in household products].

PubMed

Kaniwa, Masa-aki

2006-01-01

Chemicals in household products have been paid much attention as main cause of health damage on consumers, such as allergic contact dermatitis. Preventive measures against health damage due to chemicals in fabric, plastic and rubber products for household uses, are reviewed, focusing on (1) regulation and voluntary control by manufacturers, (2) incidence of health damage from household products, (3) causative product-chemical investigation, (4) case studies on skin damage and respiratory tract damage.

Proposed minimum reporting standards for chemical analysis Chemical Analysis Working Group (CAWG) Metabolomics Standards Initiative (MSI)

PubMed Central

Amberg, Alexander; Barrett, Dave; Beale, Michael H.; Beger, Richard; Daykin, Clare A.; Fan, Teresa W.-M.; Fiehn, Oliver; Goodacre, Royston; Griffin, Julian L.; Hankemeier, Thomas; Hardy, Nigel; Harnly, James; Higashi, Richard; Kopka, Joachim; Lane, Andrew N.; Lindon, John C.; Marriott, Philip; Nicholls, Andrew W.; Reily, Michael D.; Thaden, John J.; Viant, Mark R.

2013-01-01

There is a general consensus that supports the need for standardized reporting of metadata or information describing large-scale metabolomics and other functional genomics data sets. Reporting of standard metadata provides a biological and empirical context for the data, facilitates experimental replication, and enables the re-interrogation and comparison of data by others. Accordingly, the Metabolomics Standards Initiative is building a general consensus concerning the minimum reporting standards for metabolomics experiments of which the Chemical Analysis Working Group (CAWG) is a member of this community effort. This article proposes the minimum reporting standards related to the chemical analysis aspects of metabolomics experiments including: sample preparation, experimental analysis, quality control, metabolite identification, and data pre-processing. These minimum standards currently focus mostly upon mass spectrometry and nuclear magnetic resonance spectroscopy due to the popularity of these techniques in metabolomics. However, additional input concerning other techniques is welcomed and can be provided via the CAWG on-line discussion forum at http://msi-workgroups.sourceforge.net/ or http://Msi-workgroups-feedback@lists.sourceforge.net. Further, community input related to this document can also be provided via this electronic forum. PMID:24039616

Physical and Chemical Analytical Analysis: A key component of Bioforensics

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

Velsko, S P

The anthrax letters event of 2001 has raised our awareness of the potential importance of non-biological measurements on samples of biological agents used in a terrorism incident. Such measurements include a variety of mass spectral, spectroscopic, and other instrumental techniques that are part of the current armamentarium of the modern materials analysis or analytical chemistry laboratory. They can provide morphological, trace element, isotopic, and other molecular ''fingerprints'' of the agent that may be key pieces of evidence, supplementing that obtained from genetic analysis or other biological properties. The generation and interpretation of such data represents a new domain of forensicmore » science, closely aligned with other areas of ''microbial forensics''. This paper describes some major elements of the R&D agenda that will define this sub-field in the immediate future and provide the foundations for a coherent national capability. Data from chemical and physical analysis of BW materials can be useful to an investigation of a bio-terror event in two ways. First, it can be used to compare evidence samples collected at different locations where such incidents have occurred (e.g. between the powders in the New York and Washington letters in the Amerithrax investigation) or between the attack samples and those seized during the investigation of sites where it is suspected the material was manufactured (if such samples exist). Matching of sample properties can help establish the relatedness of disparate incidents, and mis-matches might exclude certain scenarios, or signify a more complex etiology of the events under investigation. Chemical and morphological analysis for sample matching has a long history in forensics, and is likely to be acceptable in principle in court, assuming that match criteria are well defined and derived from known limits of precision of the measurement techniques in question. Thus, apart from certain operational issues (such as how

Optical and chemical analysis of iron in Luna 20 plagioclase.

NASA Technical Reports Server (NTRS)

Bell, P. M.; Mao, H. K.

1973-01-01

Review of analytical data on the iron content of Luna 20 anorthitic plagioclase, obtained by a highly sensitive technique for measuring polarized absorption related to crystal-field splittings and by automated electron microprobe analysis of oriented single crystals. The iron content is found to range from a few hundredths to a few tenths of a weight per cent from crystal to crystal. The optical and chemical properties of the iron appear to be caused by postcrystallization migration and exsolution. Postcrystallization effects may obscure evidence of the original oxidation state and iron concentration of these crystals.

Microarray technology for major chemical contaminants analysis in food: current status and prospects.

PubMed

Zhang, Zhaowei; Li, Peiwu; Hu, Xiaofeng; Zhang, Qi; Ding, Xiaoxia; Zhang, Wen

2012-01-01

Chemical contaminants in food have caused serious health issues in both humans and animals. Microarray technology is an advanced technique suitable for the analysis of chemical contaminates. In particular, immuno-microarray approach is one of the most promising methods for chemical contaminants analysis. The use of microarrays for the analysis of chemical contaminants is the subject of this review. Fabrication strategies and detection methods for chemical contaminants are discussed in detail. Application to the analysis of mycotoxins, biotoxins, pesticide residues, and pharmaceutical residues is also described. Finally, future challenges and opportunities are discussed.

Systematic chemical-genetic and chemical-chemical interaction datasets for prediction of compound synergism

PubMed Central

Wildenhain, Jan; Spitzer, Michaela; Dolma, Sonam; Jarvik, Nick; White, Rachel; Roy, Marcia; Griffiths, Emma; Bellows, David S.; Wright, Gerard D.; Tyers, Mike

2016-01-01

The network structure of biological systems suggests that effective therapeutic intervention may require combinations of agents that act synergistically. However, a dearth of systematic chemical combination datasets have limited the development of predictive algorithms for chemical synergism. Here, we report two large datasets of linked chemical-genetic and chemical-chemical interactions in the budding yeast Saccharomyces cerevisiae. We screened 5,518 unique compounds against 242 diverse yeast gene deletion strains to generate an extended chemical-genetic matrix (CGM) of 492,126 chemical-gene interaction measurements. This CGM dataset contained 1,434 genotype-specific inhibitors, termed cryptagens. We selected 128 structurally diverse cryptagens and tested all pairwise combinations to generate a benchmark dataset of 8,128 pairwise chemical-chemical interaction tests for synergy prediction, termed the cryptagen matrix (CM). An accompanying database resource called ChemGRID was developed to enable analysis, visualisation and downloads of all data. The CGM and CM datasets will facilitate the benchmarking of computational approaches for synergy prediction, as well as chemical structure-activity relationship models for anti-fungal drug discovery. PMID:27874849

Exploration of ToxCast/Tox21 bioassays as candidate bioanalytical tools for measuring groups of chemicals in water.

PubMed

Louisse, Jochem; Dingemans, Milou M L; Baken, Kirsten A; van Wezel, Annemarie P; Schriks, Merijn

2018-06-14

The present study explores the ToxCast/Tox21 database to select candidate bioassays as bioanalytical tools for measuring groups of chemicals in water. To this aim, the ToxCast/Tox21 database was explored for bioassays that detect polycyclic aromatic hydrocarbons (PAHs), aromatic amines (AAs), (chloro)phenols ((C)Ps) and halogenated aliphatic hydrocarbons (HAliHs), which are included in the European and/or Dutch Drinking Water Directives. Based on the analysis of the availability and performance of bioassays included in the database, we concluded that several bioassays are suitable as bioanalytical tools for assessing the presence of PAHs and (C)Ps in drinking water sources. No bioassays were identified for AAs and HAliHs, due to the limited activity of these chemicals and/or the limited amount of data on these chemicals in the database. A series of bioassays was selected that measure molecular or cellular effects that are covered by bioassays currently in use for chemical water quality monitoring. Interestingly, also bioassays were selected that represent molecular or cellular effects that are not covered by bioassays currently applied. The usefulness of these newly identified bioassays as bioanalytical tools should be further evaluated in follow-up studies. Altogether, this study shows how exploration of the ToxCast/Tox21 database provides a series of candidate bioassays as bioanalytical tools for measuring groups of chemicals in water. This assessment can be performed for any group of chemicals of interest (if represented in the database), and may provide candidate bioassays that can be used to complement the currently applied bioassays for chemical water quality assessment. Copyright © 2018. Published by Elsevier Ltd.

Theory, Image Simulation, and Data Analysis of Chemical Release Experiments

NASA Technical Reports Server (NTRS)

Wescott, Eugene M.

1994-01-01

The final phase of Grant NAG6-1 involved analysis of physics of chemical releases in the upper atmosphere and analysis of data obtained on previous NASA sponsored chemical release rocket experiments. Several lines of investigation of past chemical release experiments and computer simulations have been proceeding in parallel. This report summarizes the work performed and the resulting publications. The following topics are addressed: analysis of the 1987 Greenland rocket experiments; calculation of emission rates for barium, strontium, and calcium; the CRIT 1 and 2 experiments (Collisional Ionization Cross Section experiments); image calibration using background stars; rapid ray motions in ionospheric plasma clouds; and the NOONCUSP rocket experiments.

Recent Development in Optical Chemical Sensors Coupling with Flow Injection Analysis

PubMed Central

Ojeda, Catalina Bosch; Rojas, Fuensanta Sánchez

2006-01-01

Optical techniques for chemical analysis are well established and sensors based on these techniques are now attracting considerable attention because of their importance in applications such as environmental monitoring, biomedical sensing, and industrial process control. On the other hand, flow injection analysis (FIA) is advisable for the rapid analysis of microliter volume samples and can be interfaced directly to the chemical process. The FIA has become a widespread automatic analytical method for more reasons; mainly due to the simplicity and low cost of the setups, their versatility, and ease of assembling. In this paper, an overview of flow injection determinations by using optical chemical sensors is provided, and instrumentation, sensor design, and applications are discussed. This work summarizes the most relevant manuscripts from 1980 to date referred to analysis using optical chemical sensors in FIA.

Material Cycles and Chemicals: Dynamic Material Flow Analysis of Contaminants in Paper Recycling.

PubMed

Pivnenko, Kostyantyn; Laner, David; Astrup, Thomas F

2016-11-15

This study provides a systematic approach for assessment of contaminants in materials for recycling. Paper recycling is used as an illustrative example. Three selected chemicals, bisphenol A (BPA), diethylhexyl phthalate (DEHP) and mineral oil hydrocarbons (MOHs), are evaluated within the paper cycle. The approach combines static material flow analysis (MFA) with dynamic material and substance flow modeling. The results indicate that phasing out of chemicals is the most effective measure for reducing chemical contamination. However, this scenario was also associated with a considerable lag phase (between approximately one and three decades) before the presence of chemicals in paper products could be considered insignificant. While improved decontamination may appear to be an effective way of minimizing chemicals in products, this may also result in lower production yields. Optimized waste material source-segregation and collection was the least effective strategy for reducing chemical contamination, if the overall recycling rates should be maintained at the current level (approximately 70% for Europe). The study provides a consistent approach for evaluating contaminant levels in material cycles. The results clearly indicate that mass-based recycling targets are not sufficient to ensure high quality material recycling.

X-ray texture analysis of paper coating pigments and the correlation with chemical composition analysis

NASA Astrophysics Data System (ADS)

Roine, J.; Tenho, M.; Murtomaa, M.; Lehto, V.-P.; Kansanaho, R.

2007-10-01

The present research experiments the applicability of x-ray texture analysis in investigating the properties of paper coatings. The preferred orientations of kaolin, talc, ground calcium carbonate, and precipitated calcium carbonate particles used in four different paper coatings were determined qualitatively based on the measured crystal orientation data. The extent of the orientation, namely, the degree of the texture of each pigment, was characterized quantitatively using a single parameter. As a result, the effect of paper calendering is clearly seen as an increase on the degree of texture of the coating pigments. The effect of calendering on the preferred orientation of kaolin was also evident in an independent energy dispersive spectrometer analysis on micrometer scale and an electron spectroscopy for chemical analysis on nanometer scale. Thus, the present work proves x-ray texture analysis to be a potential research tool for characterizing the properties of paper coating layers.

A novel inlet system for online chemical analysis of semi-volatile submicron particulate matter

NASA Astrophysics Data System (ADS)

Eichler, P.; Müller, M.; D'Anna, B.; Wisthaler, A.

2015-03-01

We herein present a novel modular inlet system designed to be coupled to low-pressure gas analyzers for online chemical characterization of semi-volatile submicron particles. The "chemical analysis of aerosol online" (CHARON) inlet consists of a gas-phase denuder for stripping off gas-phase analytes, an aerodynamic lens for particle collimation combined with an inertial sampler for the particle-enriched flow and a thermodesorption unit for particle volatilization prior to chemical analysis. The denuder was measured to remove gas-phase organics with an efficiency > 99.999% and to transmit particles in the 100-750 nm size range with a 75-90% efficiency. The measured average particle enrichment factor in the subsampling flow from the aerodynamic lens was 25.6, which is a factor of 3 lower than the calculated theoretical optimum. We coupled the CHARON inlet to a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) which quantitatively detects most organic analytes and ammonia. The combined CHARON-PTR-ToF-MS setup is thus capable of measuring both the organic and the ammonium fraction in submicron particles in real time. Individual organic compounds can be detected down to levels of 10-20 ng m-3. Two proof-of-principle studies were carried out for demonstrating the analytical power of this new instrumental setup: (i) oxygenated organics and their partitioning between the gas and the particulate phase were observed from the reaction of limonene with ozone and (ii) nicotine was measured in cigarette smoke particles demonstrating that selected organic target compounds can be detected in submicron particles in real time.

A new technique to assess dermal absorption of volatile chemicals in vitro by thermal gravimetric analysis.

PubMed

Rauma, Matias; Isaksson, Tina S; Johanson, Gunnar

2006-10-01

Potential health hazards of dermal exposure, variability in reported dermal absorption rates and potential losses from the skin by evaporation indicate a need for a simple, inexpensive and standardized procedure to measure dermal absorption and desorption of chemical substances. The aim of this study was to explore the possibility to measure dermal absorption and desorption of volatile chemicals using a new gravimetric technique, namely thermal gravimetric analysis (TGA), and trypsinated stratum corneum from pig. Changes in skin weight were readily detected before, during and after exposure to vapours of water, 2-propanol, methanol and toluene. The shape and height of the weight curves differed between the four chemicals, reflecting differences in diffusivity and partial pressure and skin:air partitioning, respectively. As the skin weight is highly sensitive to the partial pressure of volatile chemicals, including water, this technique requires carefully controlled conditions with respect to air flow, temperature, chemical vapour generation and humidity. This new technique may help in the assessment of dermal uptake of volatile chemicals. Only a small piece of skin is needed and skin integrity is not necessary, facilitating the use of human samples. The high resolution weight-time curves obtained may also help to elucidate the characteristics of absorption, desorption and diffusion of chemicals in skin.

Chemical Imaging and Stable Isotope Analysis of Atmospheric Particles by NanoSIMS (Invited)

NASA Astrophysics Data System (ADS)

Sinha, B.; Harris, E. J.; Pöhlker, C.; Wiedemann, K. T.; van Pinxteren, D.; Tilgner, A.; Fomba, K. W.; Schneider, J.; Roth, A.; Gnauk, T.; Fahlbusch, B.; Mertes, S.; Lee, T.; Collett, J. L.; Shiraiwa, M.; Gunthe, S. S.; Smith, M.; Artaxo, P. P.; Gilles, M.; Kilcoyne, A. L.; Moffet, R.; Weigand, M.; Martin, S. T.; Poeschl, U.; Andreae, M. O.; Hoppe, P.; Herrmann, H.; Borrmann, S.

2013-12-01

Chemical imaging analysis of the internal distribution of chemical compounds by a combination of SEM-EDX, and NanoSIMS allows investigating the physico-chemical properties and isotopic composition of individual aerosol particles. Stable sulphur isotope analysis provides insight into the sources, sinks and oxidation pathways of SO2 in the environment. Oxidation by OH radicals, O3 and H2O2 enriches the heavier isotope in the product sulphate, whereas oxidation by transition metal ions (TMI), hypohalites and hypohalous acids depletes the heavier isotope in the product sulphate. The isotope fractionation during SO2 oxidation by stabilized Criegee Intermediate radicals is unknown. We studied the relationship between aerosol chemical composition and predominant sulphate formation pathways in continental clouds in Central Europe and during the wet season in the Amazon rain forest. Sulphate formation in continental clouds in Central Europe was studied during HCCT-2010, a lagrangian-type field experiment, during which an orographic cloud was used as a natural flow-through reactor to study in-cloud aerosol processing (Harris et al. 2013). Sulphur isotopic compositions in SO2 and H2SO4 gas and particulate sulphate were measured and changes in the sulphur isotope composition of SO2 between the upwind and downwind measurement sites were used to determine the dominant SO2 chemical removal process occurring in the cloud. Changes in the isotopic composition of particulate sulphate revealed that transition metal catalysis pathway was the dominant SO2 oxidation pathway. This reaction occurred primarily on coarse mineral dust particles. Thus, sulphate produced due to in-cloud SO2 oxidation is removed relatively quickly from the atmosphere and has a minor climatic effect. The aerosol samples from the Amazonian rainforest, a pristine tropical environment, were collected during the rainy season. The samples were found to be dominated by SOA particles in the fine mode and primary

Chemical properties and methods of analysis of refractory compounds

NASA Technical Reports Server (NTRS)

Samsonov, G. V. (Editor); Frantsevich, I. N. (Editor); Yeremenko, V. N. (Editor); Nazarchuk, T. N. (Editor); Popova, O. I. (Editor)

1978-01-01

Reactions involving refractory metals and the alloys based on them are discussed. Chemical, electrochemical, photometric, spectrophotometric, and X-ray analysis are among the methods described for analyzing the results of the reactions and for determining the chemical properties of these materials.

QUALITY ASSURANCE GUIDELINES FOR LABORATORIES PERFORMING FORENSIC ANALYSIS OF CHEMICAL TERRORISM

EPA Science Inventory

The Scientific Working Group on Forensic Analysis of Chemical Terrorism (SWGFACT) has developed the following quality assurance guidelines to provide laboratories engaged in forensic analysis of chemical evidence associated with terrorism a framework to implement a quality assura...

Accelerator-based chemical and elemental analysis of atmospheric aerosols

NASA Astrophysics Data System (ADS)

Mentes, Besim

Aerosol particles have always been present in the atmosphere, arising from natural sources. But it was not until recently when emissions from anthropogenic (man made) sources began to dominate, that atmospheric aerosols came into focus and the aerosol science in the environmental perspective started to grow. These sources emit or produce particles with different elemental and chemical compositions, as well as different sizes of the individual aerosols. The effects of increased pollution of the atmosphere are many, and have different time scales. One of the effects known today is acid rain, which causes problems for vegetation. Pollution is also a direct human health risk, in many cities where traffic driven by combustion engines is forbidden at certain times when the meteorological conditions are unfavourable. Aerosols play an important role in the climate, and may have both direct and indirect effect which cause cooling of the planet surface, in contrast to the so-called greenhouse gases. During this work a technique for chemical and elemental analysis of atmospheric aerosols and an elemental analysis methodology for upper tropospheric aerosols have been developed. The elemental analysis is performed by the ion beam analysis (IBA) techniques, PIXE (elements heavier than Al). PESA (C, N and O), cPESA (H) and pNRA (Mg and Na). The chemical speciation of atmospheric aerosols is obtained by ion beam thermography (IBT). During thermography the sample temperature is stepwise increased and the IBA techniques are used to continuously monitor the elemental concentration. A thermogram is obtained for each element. The vaporisation of the compounds in the sample appears as a concentration decrease in the thermograms at characteristic vaporisation temperatures (CVTs). Different aspects of IBT have been examined in Paper I to IV. The features of IBT are: almost total elemental speciation of the aerosol mass, chemical speciation of the inorganic compounds, carbon content

Gas chromatograph-mass spectrometer (GC/MS) system for quantitative analysis of reactive chemical compounds

DOEpatents

Grindstaff, Quirinus G.

1992-01-01

Described is a new gas chromatograph-mass spectrometer (GC/MS) system and method for quantitative analysis of reactive chemical compounds. All components of such a GC/MS system external to the oven of the gas chromatograph are programmably temperature controlled to operate at a volatilization temperature specific to the compound(s) sought to be separated and measured.

Chemical analysis of bleach and hydroxide-based solutions after decontamination of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX).

PubMed

Hopkins, F B; Gravett, M R; Self, A J; Wang, M; Chua, Hoe-Chee; Hoe-Chee, C; Lee, H S Nancy; Sim, N Lee Hoi; Jones, J T A; Timperley, C M; Riches, J R

2014-08-01

Detailed chemical analysis of solutions used to decontaminate chemical warfare agents can be used to support verification and forensic attribution. Decontamination solutions are amongst the most difficult matrices for chemical analysis because of their corrosive and potentially emulsion-based nature. Consequently, there are relatively few publications that report their detailed chemical analysis. This paper describes the application of modern analytical techniques to the analysis of decontamination solutions following decontamination of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX). We confirm the formation of N,N-diisopropylformamide and N,N-diisopropylamine following decontamination of VX with hypochlorite-based solution, whereas they were not detected in extracts of hydroxide-based decontamination solutions by nuclear magnetic resonance (NMR) spectroscopy or gas chromatography-mass spectrometry. We report the electron ionisation and chemical ionisation mass spectroscopic details, retention indices, and NMR spectra of N,N-diisopropylformamide and N,N-diisopropylamine, as well as analytical methods suitable for their analysis and identification in solvent extracts and decontamination residues.

Investigation of Chemically Treated Test-Strips for Ozone Measurement

NASA Technical Reports Server (NTRS)

Bush, Linda C.

1997-01-01

A colorimetric passive ozone monitoring system is currently in use in the GLOBE project, as well as several other environmental studies, as commercially supplied as Eco-Badge by Vistanomics. This simple, but effective, system consists of papers treated with a chemical preparation, tin(II) diphenylcarbazidel that reacts with ozone to change them from white to purple. The intensity of the purple coloration is dependent on the concentration of ozone. Our previous contributions to that method of analysis involved modest modifications to the chemical substrate employed. The new formulation improved the reproducibility and linearity of the color change of treated papers.

Electron Probe MicroAnalysis (EPMA) Standards. Issues Related to Measurement and Accuracy Evaluation in EPMA

NASA Technical Reports Server (NTRS)

Carpenter, Paul

2003-01-01

Electron-probe microanalysis standards and issues related to measurement and accuracy of microanalysis will be discussed. Critical evaluation of standards based on homogeneity and comparison with wet-chemical analysis will be made. Measurement problems such as spectrometer dead-time will be discussed. Analytical accuracy issues will be evaluated for systems by alpha-factor analysis and comparison with experimental k-ratio databases.

An Inventory for Measuring Student Teachers' Knowledge of Chemical Representations: Design, Validation, and Psychometric Analysis

ERIC Educational Resources Information Center

Taskin, V.; Bernholt, S.; Parchmann, I.

2015-01-01

Chemical representations play an important role in helping learners to understand chemical contents. Thus, dealing with chemical representations is a necessity for learning chemistry, but at the same time, it presents a great challenge to learners. Due to this great challenge, it is not surprising that numerous national and international studies…

Probabilistic Exposure Analysis for Chemical Risk Characterization

PubMed Central

Bogen, Kenneth T.; Cullen, Alison C.; Frey, H. Christopher; Price, Paul S.

2009-01-01

This paper summarizes the state of the science of probabilistic exposure assessment (PEA) as applied to chemical risk characterization. Current probabilistic risk analysis methods applied to PEA are reviewed. PEA within the context of risk-based decision making is discussed, including probabilistic treatment of related uncertainty, interindividual heterogeneity, and other sources of variability. Key examples of recent experience gained in assessing human exposures to chemicals in the environment, and other applications to chemical risk characterization and assessment, are presented. It is concluded that, although improvements continue to be made, existing methods suffice for effective application of PEA to support quantitative analyses of the risk of chemically induced toxicity that play an increasing role in key decision-making objectives involving health protection, triage, civil justice, and criminal justice. Different types of information required to apply PEA to these different decision contexts are identified, and specific PEA methods are highlighted that are best suited to exposure assessment in these separate contexts. PMID:19223660

Spectroscopic Chemical Analysis Methods and Apparatus

NASA Technical Reports Server (NTRS)

Hug, William F.; Reid, Ray D.

2012-01-01

This invention relates to non-contact spectroscopic methods and apparatus for performing chemical analysis and the ideal wavelengths and sources needed for this analysis. It employs deep ultraviolet (200- to 300-nm spectral range) electron-beam-pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor lightemitting devices, and hollow cathode metal ion lasers. Three achieved goals for this innovation are to reduce the size (under 20 L), reduce the weight [under 100 lb (.45 kg)], and reduce the power consumption (under 100 W). This method can be used in microscope or macroscope to provide measurement of Raman and/or native fluorescence emission spectra either by point-by-point measurement, or by global imaging of emissions within specific ultraviolet spectral bands. In other embodiments, the method can be used in analytical instruments such as capillary electrophoresis, capillary electro-chromatography, high-performance liquid chromatography, flow cytometry, and related instruments for detection and identification of unknown analytes using a combination of native fluorescence and/or Raman spectroscopic methods. This design provides an electron-beampumped semiconductor radiation-producing method, or source, that can emit at a wavelength (or wavelengths) below 300 nm, e.g. in the deep ultraviolet between about 200 and 300 nm, and more preferably less than 260 nm. In some variations, the method is to produce incoherent radiation, while in other implementations it produces laser radiation. In some variations, this object is achieved by using an AlGaN emission medium, while in other implementations a diamond emission medium may be used. This instrument irradiates a sample with deep UV radiation, and then uses an improved filter for separating wavelengths to be detected. This provides a multi-stage analysis of the sample. To avoid the difficulties related to producing deep UV semiconductor sources, a pumping approach has been developed that uses

Device for high spatial resolution chemical analysis of a sample and method of high spatial resolution chemical analysis

DOEpatents

Van Berkel, Gary J.

2015-10-06

A system and method for analyzing a chemical composition of a specimen are described. The system can include at least one pin; a sampling device configured to contact a liquid with a specimen on the at least one pin to form a testing solution; and a stepper mechanism configured to move the at least one pin and the sampling device relative to one another. The system can also include an analytical instrument for determining a chemical composition of the specimen from the testing solution. In particular, the systems and methods described herein enable chemical analysis of specimens, such as tissue, to be evaluated in a manner that the spatial-resolution is limited by the size of the pins used to obtain tissue samples, not the size of the sampling device used to solubilize the samples coupled to the pins.

Chemical Abundance Measurements of Ultra-Faint Dwarf Galaxies Discovered by the Dark Energy Survey

NASA Astrophysics Data System (ADS)

Nagasawa, Daniel; Marshall, Jennifer L.; Simon, Joshua D.; Hansen, Terese; Li, Ting; Bernstein, Rebecca; Balbinot, Eduardo; Drlica-Wagner, Alex; Pace, Andrew; Strigari, Louis; Pellegrino, Craig; DePoy, Darren L.; Suntzeff, Nicholas; Bechtol, Keith; Dark Energy Suvey

2018-01-01

We present chemical abundance analysis results derived from high-resolution spectroscopy of ultra-faint dwarfs discovered by the Dark Energy Survey. Ultra-faint dwarf galaxies preserve a fossil record of the chemical abundance patterns imprinted by the first stars in the Universe. High-resolution spectroscopic observations of member stars in several recently discovered Milky Way satellites reveal a range of abundance patterns among ultra-faint dwarfs suggesting that star formation processes in the early Universe were quite diverse. The chemical content provides a glimpse not only of the varied nucleosynthetic processes and chemical history of the dwarfs themselves, but also the environment in which they were formed. We present the chemical abundance analysis of these objects and discuss possible explanations for the observed abundance patterns.

Single particle measurements of the chemical composition of cirrus ice residue during CRYSTAL-FACE

NASA Astrophysics Data System (ADS)

Cziczo, D. J.; Murphy, D. M.; Hudson, P. K.; Thomson, D. S.

2004-02-01

The first real-time, in situ, investigation of the chemical composition of the residue of cirrus ice crystals was performed during July 2002. This study was undertaken on a NASA WB-57F high-altitude research aircraft as part of CRYSTAL-FACE, a field campaign which sought to further our understanding of the relation of clouds, water vapor, and climate by characterizing, among other parameters, anvil cirrus formed about the Florida peninsula. A counter flow virtual impactor (CVI) was used to separate cirrus ice from the unactivated interstitial aerosol particles and evaporate condensed-phase water. Residual material, on a crystal-by-crystal basis, was subsequently analyzed using the NOAA Aeronomy Laboratory's Particle Analysis by Laser Mass Spectrometry (PALMS) instrument. Sampling was performed from 5 to 15 km altitude and from 12° to 28° north latitude within cirrus originating over land and ocean. Chemical composition measurements provided several important results. Sea salt was often incorporated into cirrus, consistent with homogeneous ice formation by aerosol particles from the marine boundary layer. Size measurements showed that large particles preferentially froze over smaller ones. Meteoritic material was found within ice crystals, indicative of a relation between stratospheric aerosol particles and tropospheric clouds. Mineral dust was the dominant residue observed in clouds formed during a dust transport event from the Sahara, consistent with a heterogeneous freezing mechanism. These results show that chemical composition and size are important determinants of which aerosol particles form cirrus ice crystals.

Nonradiological chemical pathway analysis and identification of chemicals of concern for environmental monitoring at the Hanford Site

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

Blanton, M.L.; Cooper, A.T.; Castleton, K.J.

1995-11-01

Pacific Northwest`s Surface Environmental Surveillance Project (SESP) is an ongoing effort tot design, review, and conducted monitoring on and off the Hanford site. Chemicals of concern that were selected are listed. Using modeled exposure pathways, the offsite cancer incidence and hazard quotient were calculated and a retrospective pathway analysis performed to estimate what onsite concentrations would be required in the soil for each chemical of concern and other detected chemicals that would be required to obtain an estimated offsite human-health risk of 1.0E-06 cancer incidence or 1.0 hazard quotient. This analysis indicates that current nonradiological chemical contamination occurring on themore » site does not pose a significant offsite human-health risk; the highest cancer incidence to the offsite maximally exposed individual was from arsenic (1.76E-10); the highest hazard quotient was chromium(VI) (1.48E-04). The most sensitive pathways of exposure were surfacewater and aquatic food consumption. Combined total offsite excess cancer incidence was 2.09E-10 and estimated hazard quotient was 2.40E-04. Of the 17 identified chemicals of concern, the SESP does not currently (routinely) monitor arsenic, benzo(a)pyrene, bis(2- ethylhexyl)phthalate (BEHP), and chrysene. Only 3 of the chemicals of concern (arsenic, BEHP, chloroform) could actually occur in onsite soil at concern high enough to cause a 1.0E-06 excess cancer incidence or a 1.0 hazard index for a given offsite exposure pathway. During the retrospective analysis, 20 other chemicals were also evaluated; only vinyl chloride and thallium could reach targeted offsite risk values.« less

Method for combined biometric and chemical analysis of human fingerprints.

PubMed

Staymates, Jessica L; Orandi, Shahram; Staymates, Matthew E; Gillen, Greg

This paper describes a method for combining direct chemical analysis of latent fingerprints with subsequent biometric analysis within a single sample. The method described here uses ion mobility spectrometry (IMS) as a chemical detection method for explosives and narcotics trace contamination. A collection swab coated with a high-temperature adhesive has been developed to lift latent fingerprints from various surfaces. The swab is then directly inserted into an IMS instrument for a quick chemical analysis. After the IMS analysis, the lifted print remains intact for subsequent biometric scanning and analysis using matching algorithms. Several samples of explosive-laden fingerprints were successfully lifted and the explosives detected with IMS. Following explosive detection, the lifted fingerprints remained of sufficient quality for positive match scores using a prepared gallery consisting of 60 fingerprints. Based on our results ( n  = 1200), there was no significant decrease in the quality of the lifted print post IMS analysis. In fact, for a small subset of lifted prints, the quality was improved after IMS analysis. The described method can be readily applied to domestic criminal investigations, transportation security, terrorist and bombing threats, and military in-theatre settings.

Chemical structure of wood charcoal by infrared spectroscopy and multivariate analysis

Treesearch

Nicole Labbe; David Harper; Timothy Rials; Thomas Elder

2006-01-01

In this work, the effect of temperature on charcoal structure and chemical composition is investigated for four tree species. Wood charcoal carbonized at various temperatures is analyzed by mid infrared spectroscopy coupled with multivariate analysis and by thermogravimetric analysis to characterize the chemical composition during the carbonization process. The...

Fixation and chemical analysis of single fog and rain droplets

NASA Astrophysics Data System (ADS)

Kasahara, M.; Akashi, S.; Ma, C.-J.; Tohno, S.

Last decade, the importance of global environmental problems has been recognized worldwide. Acid rain is one of the most important global environmental problems as well as the global warming. The grasp of physical and chemical properties of fog and rain droplets is essential to make clear the physical and chemical processes of acid rain and also their effects on forests, materials and ecosystems. We examined the physical and chemical properties of single fog and raindrops by applying fixation technique. The sampling method and treatment procedure to fix the liquid droplets as a solid particle were investigated. Small liquid particles like fog droplet could be easily fixed within few minutes by exposure to cyanoacrylate vapor. The large liquid particles like raindrops were also fixed successively, but some of them were not perfect. Freezing method was applied to fix the large raindrops. Frozen liquid particles existed stably by exposure to cyanoacrylate vapor after freezing. The particle size measurement and the elemental analysis of the fixed particle were performed in individual base using microscope, and SEX-EDX, particle-induced X-ray emission (PIXE) and micro-PIXE analyses, respectively. The concentration in raindrops was dependent upon the droplet size and the elapsed time from the beginning of rainfall.

LSENS - GENERAL CHEMICAL KINETICS AND SENSITIVITY ANALYSIS CODE

NASA Technical Reports Server (NTRS)

Bittker, D. A.

1994-01-01

LSENS has been developed for solving complex, homogeneous, gas-phase, chemical kinetics problems. The motivation for the development of this program is the continuing interest in developing detailed chemical reaction mechanisms for complex reactions such as the combustion of fuels and pollutant formation and destruction. A reaction mechanism is the set of all elementary chemical reactions that are required to describe the process of interest. Mathematical descriptions of chemical kinetics problems constitute sets of coupled, nonlinear, first-order ordinary differential equations (ODEs). The number of ODEs can be very large because of the numerous chemical species involved in the reaction mechanism. Further complicating the situation are the many simultaneous reactions needed to describe the chemical kinetics of practical fuels. For example, the mechanism describing the oxidation of the simplest hydrocarbon fuel, methane, involves over 25 species participating in nearly 100 elementary reaction steps. Validating a chemical reaction mechanism requires repetitive solutions of the governing ODEs for a variety of reaction conditions. Analytical solutions to the systems of ODEs describing chemistry are not possible, except for the simplest cases, which are of little or no practical value. Consequently, there is a need for fast and reliable numerical solution techniques for chemical kinetics problems. In addition to solving the ODEs describing chemical kinetics, it is often necessary to know what effects variations in either initial condition values or chemical reaction mechanism parameters have on the solution. Such a need arises in the development of reaction mechanisms from experimental data. The rate coefficients are often not known with great precision and in general, the experimental data are not sufficiently detailed to accurately estimate the rate coefficient parameters. The development of a reaction mechanism is facilitated by a systematic sensitivity analysis

The bioavailability of chemicals in soil for earthworms

USGS Publications Warehouse

Lanno, R.; Wells, J.; Conder, Jason M.; Bradham, K.; Basta, N.

2004-01-01

The bioavailability of chemicals to earthworms can be modified dramatically by soil physical/chemical characteristics, yet expressing exposure as total chemical concentrations does not address this problem. In order to understand the effects of modifying factors on bioavailability, one must measure and express chemical bioavailability to earthworms in a consistent, logical manner. This can be accomplished by direct biological measures of bioavailability (e.g., bioaccumulation, critical body residues), indirect biological measures of bioavailability (e.g., biomarkers, reproduction), or indirect chemical measures of bioavailability (e.g., chemical or solid-phase extracts of soil). If indirect chemical measures of bioavailability are to be used, they must be correlated with some biological response. Bioavailability can be incorporated into ecological risk assessment during risk analysis, primarily in the estimation of exposure. However, in order to be used in the site-specific ecological risk assessment of chemicals, effects concentrations must be developed from laboratory toxicity tests based on exposure estimates utilizing techniques that measure the bioavailable fraction of chemicals in soil, not total chemical concentrations. ?? 2003 Elsevier Inc. All rights reserved.

Measurement of volatile organic chemicals at selected sites in California

NASA Technical Reports Server (NTRS)

Singh, Hanwant B.; Salas, L.; Viezee, W.; Sitton, B.; Ferek, R.

1992-01-01

Urban air concentrations of 24 selected volatile organic chemicals that may be potentially hazardous to human health and environment were measured during field experiments conducted at two California locations, at Houston, and at Denver. Chemicals measured included chlorofluorocarbons, halomethanes, haloethanes, halopropanes, chloroethylenes, and aromatic hydrocarbons. With emphasis on California sites, data from these studies are analyzed and interpreted with respect to variabilities in ambient air concentrations, diurnal changes, relation to prevailing meteorology, sources and trends. Except in a few instances, mean concentrations are typically between 0 and 5 ppb. Significant variabilities in atmospheric concentrations associated with intense sources and adverse meteorological conditions are shown to exist. In addition to short-term variability, there is evidence of systematic diurnal and seasonal trends. In some instances it is possible to detect declining trends resulting from the effectiveness of control strategies.

Spectral Reflectance Measurement of Evaporating Chemical Films: Initial Results and Application to Skin Permeation.

PubMed

Frasch, H Frederick; Lee, Larry; Barbero, Ana M

2018-04-27

The current study has two aims. First the method of spectral reflectance was used to measure evaporation rates of thin (∼25-300 μm) films of neat liquid volatile organic chemicals exposed to a well-regulated wind speed u. Gas phase evaporation mass transfer coefficient (k evap ) measurements of 10 chemicals, 9 of which were measured at similar u, are predicted (slope of log-log data = 1.01; intercept = 0.08; R 2 = 0.996) by a previously proposed mass transfer correlation. For one chemical, isoamyl alcohol, the dependence of k evap on u 0.52 was measured, in support of the predicted exponent value of ½. Second, measured k evap of nicotine was used as an input in analytical models based on diffusion theory to estimate the absorbed fraction (F abs ) of a small dose (5 μL/cm 2 ) applied to human epidermis in vitro. The measured F abs was 0.062 ± 0.023. Model-estimated values are 0.066 and 0.115. Spectral reflectance is a precise method of measuring k evap of liquid chemicals and the data are well-described by a simple gas phase mass transfer coefficient. For nicotine under the single exposure condition measured herein, F abs is well-predicted from a theoretical model that requires knowledge of k evap , maximal dermal flux and membrane lag time. Copyright © 2018. Published by Elsevier Inc.

Measurement system analysis of viscometers used for drilling mud characterization

NASA Astrophysics Data System (ADS)

Mat-Shayuti, M. S.; Adzhar, S. N.

2017-07-01

Viscometers in the Faculty of Chemical Engineering, University Teknologi MARA, are subject to heavy utilization from the members of the faculty. Due to doubts surrounding their result integrity and maintenance management, Measurement System Analysis was executed. 5 samples of drilling muds with varied barite content from 5 - 25 weight% were prepared and their rheological properties determined in 3 trials by 3 operators using the viscometers. Gage Linearity and Bias Study were performed using Minitab software and the result shows high biases in the range of 19.2% to 38.7%, with non-linear trend along the span of measurements. Gage Repeatability & Reproducibility (Nested) analysis later produces Percent Repeatability & Reproducibility more than 7.7% and Percent Tolerance above 30%. Lastly, good and marginal Distinct Categories output are seen among the results. Despite acceptable performance of the measurement system in Distinct Categories, the poor results in accuracy, linearity, and Percent Repeatability & Reproducibility render the gage generally not capable. Improvement to the measurement system is imminent.

Thermal decomposition in thermal desorption instruments: importance of thermogram measurements for analysis of secondary organic aerosol

NASA Astrophysics Data System (ADS)

Stark, H.; Yatavelli, R. L. N.; Thompson, S.; Kang, H.; Krechmer, J. E.; Kimmel, J.; Palm, B. B.; Hu, W.; Hayes, P.; Day, D. A.; Campuzano Jost, P.; Ye, P.; Canagaratna, M. R.; Jayne, J. T.; Worsnop, D. R.; Jimenez, J. L.

2017-12-01

Understanding the chemical composition of secondary organic aerosol (SOA) is crucial for explaining sources and fate of this important aerosol class in tropospheric chemistry. Further, determining SOA volatility is key in predicting its atmospheric lifetime and fate, due to partitioning from and to the gas phase. We present three analysis approaches to determine SOA volatility distributions from two field campaigns in areas with strong biogenic emissions, a Ponderosa pine forest in Colorado, USA, from the BEACHON-RoMBAS campaign, and a mixed forest in Alabama, USA, from the SOAS campaign. We used a high-resolution-time-of-flight chemical ionization mass spectrometer (CIMS) for both campaigns, equipped with a micro-orifice volatilization impactor (MOVI) inlet for BEACHON and a filter inlet for gases and aerosols (FIGAERO) for SOAS. These inlets allow near simultaneous analysis of particle and gas-phase species by the CIMS. While gas-phase species are directly measured without heating, particles undergo thermal desorption prior to analysis. Volatility distributions can be estimated in three ways: (1) analysis of the thermograms (signal vs. temperature); (2) via partitioning theory using the gas- and particle-phase measurements; (3) from measured chemical formulas via a group contribution model. Comparison of the SOA volatility distributions from the three methods shows large discrepancies for both campaigns. Results from the thermogram method are the most consistent of the methods when compared with independent AMS-thermal denuder measurements. The volatility distributions estimated from partitioning measurements are very narrow, likely due to signal-to-noise limits in the measurements. The discrepancy between the formula and the thermogram methods indicates large-scale thermal decomposition of the SOA species. We will also show results of citric acid thermal decomposition, where, in addition to the mass spectra, measurements of CO, CO2 and H2O were made, showing

Pretest uncertainty analysis for chemical rocket engine tests

NASA Technical Reports Server (NTRS)

Davidian, Kenneth J.

1987-01-01

A parametric pretest uncertainty analysis has been performed for a chemical rocket engine test at a unique 1000:1 area ratio altitude test facility. Results from the parametric study provide the error limits required in order to maintain a maximum uncertainty of 1 percent on specific impulse. Equations used in the uncertainty analysis are presented.

Chemical Applications for Enhanced World Security

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

Leibman, Christopher Patrick

The purpose of this project is to reduce complexity of chemical analysis by combining chemical and physical processing steps into on package; develop instrumentation that cost less and is easy to use in a field laboratory by non-experts; and develop this "chemical application" so uranium enrichment can be measured onsite, eliminating the need for radioactive sample transport.

Tox21 Enricher: Web-based Chemical/Biological Functional Annotation Analysis Tool Based on Tox21 Toxicity Screening Platform.

PubMed

Hur, Junguk; Danes, Larson; Hsieh, Jui-Hua; McGregor, Brett; Krout, Dakota; Auerbach, Scott

2018-05-01

The US Toxicology Testing in the 21st Century (Tox21) program was established to develop more efficient and human-relevant toxicity assessment methods. The Tox21 program screens >10,000 chemicals using quantitative high-throughput screening (qHTS) of assays that measure effects on toxicity pathways. To date, more than 70 assays have yielded >12 million concentration-response curves. The patterns of activity across assays can be used to define similarity between chemicals. Assuming chemicals with similar activity profiles have similar toxicological properties, we may infer toxicological properties based on its neighbourhood. One approach to inference is chemical/biological annotation enrichment analysis. Here, we present Tox21 Enricher, a web-based chemical annotation enrichment tool for the Tox21 toxicity screening platform. Tox21 Enricher identifies over-represented chemical/biological annotations among lists of chemicals (neighbourhoods), facilitating the identification of the toxicological properties and mechanisms in the chemical set. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sampling and physico-chemical analysis of precipitation: a review.

PubMed

Krupa, Sagar V

2002-01-01

Wet deposition is one of two processes governing the transfer of beneficial and toxic chemicals from the atmosphere on to surfaces. Since the early 1970s, numerous investigators have sampled and analyzed precipitation for their chemical constituents, in the context of "acidic rain" and related atmospheric processes. Since then, significant advances have been made in our understanding of how to sample rain, cloud and fog water to preserve their physico-chemical integrity prior to analyses. Since the 1970s large-scale precipitation sampling networks have been in operation to broadly address regional and multi-regional issues. However, in examining the results from such efforts at a site-specific level, concerns have been raised about the accuracy and precision of the information gathered. There is mounting evidence to demonstrate the instability of precipitation samples (e.g. with N species) that have been subjected to prolonged ambient or field conditions. At the present time precipitation sampling procedures allow unrefrigerated or refrigerated collection of wet deposition from individual events, sequential fractions within events, in situ continuous chemical analyses in the field and even sampling of single or individual rain, cloud and fog droplets. Similarly analytical procedures of precipitation composition have advanced from time-consuming methods to rapid and simultaneous analyses of major anions and cations, from bulk samples to single droplets. For example, analytical techniques have evolved from colorimetry to ion chromatography to capillary electrophoresis. Overall, these advances allow a better understanding of heterogeneous reactions and atmospheric pollutant scavenging processes by precipitation. In addition, from an environmental perspective, these advances allow better quantification of semi-labile (e.g. NH4+, frequently its deposition values are underestimated) or labile species [e.g. S (IV)] in precipitation and measurements of toxic chemicals such

Depleted Uranium Program: Repository and Chemical Analysis of Biological Samples

DTIC Science & Technology

2010-11-01

Chemical Samples • Chemical Pathology and Analytical Assessment of U and DU in: • Tissues • Urine • Whole blood • Semen • Embedded fragments...preparation for determination of total uranium and isotopic uranium ratios  Semen – Total Uranium – dry ashed by concentrated nitric acid in muffle...Total uranium and DU measurements in blood 0.0 50.0 100.0 150.0 200.0 250.0 ng U in s am pl e Sample Number Semen Measured U Theortical U Uranium

Real time chemical exposure and risk monitor

DOEpatents

Thrall, Karla D.; Kenny, Donald V.; Endres, George W. R.; Sisk, Daniel R.

1997-01-01

The apparatus of the present invention is a combination of a breath interface and an external exposure dosimeter interface to a chemical analysis device, all controlled by an electronic processor for quantitatively analyzing chemical analysis data from both the breath interface and the external exposure dosimeter for determining internal tissue dose. The method of the present invention is a combination of steps of measuring an external dose, measuring breath content, then analyzing the external dose and breath content and determining internal tissue dose.

Antioxidant Micronutrients: Therapeutic Counter Measures for Chemical Agents

DTIC Science & Technology

2011-03-01

ANSI Std. Z39.18 W81XWH-08-2-0007 1 Mar 2010 - 28 Feb 2011Annual01-03-2011 Antioxidant Micronutrients : Therapeutic Counter Measures for Chemical...Agents Kedar Prasad, Ph.D. Premier Micronutrient Corporation Novato, CA 94949 The results of the first phase of HD study suggested that exposure to...Hypothesis of HD study: For the first phase of the study, our hypothesis is that oral supplementation with a mixture of dietary and endogenous

SALI chemical analysis of provided samples

NASA Technical Reports Server (NTRS)

Becker, Christopher H.

1993-01-01

SRI has completed the chemical analysis of all the samples supplied by NASA. The final batch of four samples consisted of: one inch diameter MgF2 mirror, control 1200-ID-FL3; one inch diameter neat resin, PMR-15, AO171-IV-55, half exposed and half unexposed; one inch diameter chromic acid anodized, EOIM-3 120-47 aluminum disc; and AO-exposed and unexposed samples of fullerene extract material in powdered form, pressed into In foil for analysis. Chemical analyses of the surfaces were performed by the surface analysis by laser ionization (SALI) method. The analyses emphasize surface contamination or general organic composition. SALI uses nonselective photoionization of sputtered or desorbed atoms and molecules above but close (approximately one mm) to the surface, followed by time-of-flight (TOF) mass spectrometry. In these studies, we used laser-induced desorption by 5-ns pulse-width 355-nm light (10-100 mJ/sq cm) and single-photon ionization (SPI) by coherent 118-nm radiation (at approximately 5 x 10(exp 5) W/sq cm). SPI was chosen primarily for its ability to obtain molecular information, whereas multiphoton ionization (not used in the present studies) is intended primarily for elemental and small molecule information. In addition to these four samples, the Au mirror (EOIM-3 200-11, sample four) was depth profiled again. Argon ion sputtering was used together with photoionization with intense 355-nm radiation (35-ps pulsewidths). Depth profiles are similar to those reported earlier, showing reproducibility. No chromium was found in the sample above noise level; its presence could at most be at the trace level. Somewhat more Ni appears to be present in the Au layer in the unexposed side, indicating thermal diffusion without chemical enhancement. The result of the presence of oxygen is apparently to tie-up/draw out the Ni as an oxide at the surface. The exposed region has a brownish tint appearance to the naked eye.

Manual or automated measuring of antipsychotics' chemical oxygen demand.

PubMed

Pereira, Sarah A P; Costa, Susana P F; Cunha, Edite; Passos, Marieta L C; Araújo, André R S T; Saraiva, M Lúcia M F S

2018-05-15

Antipsychotic (AP) drugs are becoming accumulated in terrestrial and aqueous resources due to their actual consumption. Thus, the search of methods for assessing the contamination load of these drugs is mandatory. The COD is a key parameter used for monitoring water quality upon the assessment of the effect of polluting agents on the oxygen level. Thus, the present work aims to assess the chemical oxygen demand (COD) levels of several typical and atypical antipsychotic drugs in order to obtain structure-activity relationships. It was implemented the titrimetric method with potassium dichromate as oxidant and a digestion step of 2h, followed by the measurement of remained unreduced dichromate by titration. After that, an automated sequential injection analysis (SIA) method was, also, used aiming to overcome some drawbacks of the titrimetric method. The results obtained showed a relationship between the chemical structures of antipsychotic drugs and their COD values, where the presence of aromatic rings and oxidable groups give higher COD values. It was obtained a good compliance between the results of the reference batch procedure and the SIA system, and the APs were clustered in two groups, with the values ratio between the methodologies, of 2 or 4, in the case of lower or higher COD values, respectively. The SIA methodology is capable of operating as a screening method, in any stage of a synthetic process, being also more environmentally friendly, and cost-effective. Besides, the studies presented open promising perspectives for the improvement of the effectiveness of pharmaceutical removal from the waste effluents, by assessing COD values. Copyright © 2018 Elsevier Inc. All rights reserved.

Chemical Discrimination of Cortex Phellodendri amurensis and Cortex Phellodendri chinensis by Multivariate Analysis Approach.

PubMed

Sun, Hui; Wang, Huiyu; Zhang, Aihua; Yan, Guangli; Han, Ying; Li, Yuan; Wu, Xiuhong; Meng, Xiangcai; Wang, Xijun

2016-01-01

As herbal medicines have an important position in health care systems worldwide, their current assessment, and quality control are a major bottleneck. Cortex Phellodendri chinensis (CPC) and Cortex Phellodendri amurensis (CPA) are widely used in China, however, how to identify species of CPA and CPC has become urgent. In this study, multivariate analysis approach was performed to the investigation of chemical discrimination of CPA and CPC. Principal component analysis showed that two herbs could be separated clearly. The chemical markers such as berberine, palmatine, phellodendrine, magnoflorine, obacunone, and obaculactone were identified through the orthogonal partial least squared discriminant analysis, and were identified tentatively by the accurate mass of quadruple-time-of-flight mass spectrometry. A total of 29 components can be used as the chemical markers for discrimination of CPA and CPC. Of them, phellodenrine is significantly higher in CPC than that of CPA, whereas obacunone and obaculactone are significantly higher in CPA than that of CPC. The present study proves that multivariate analysis approach based chemical analysis greatly contributes to the investigation of CPA and CPC, and showed that the identified chemical markers as a whole should be used to discriminate the two herbal medicines, and simultaneously the results also provided chemical information for their quality assessment. Multivariate analysis approach was performed to the investigate the herbal medicineThe chemical markers were identified through multivariate analysis approachA total of 29 components can be used as the chemical markers. UPLC-Q/TOF-MS-based multivariate analysis method for the herbal medicine samples Abbreviations used: CPC: Cortex Phellodendri chinensis, CPA: Cortex Phellodendri amurensis, PCA: Principal component analysis, OPLS-DA: Orthogonal partial least squares discriminant analysis, BPI: Base peaks ion intensity.

In vivo ultrasound and biometric measurements predict the empty body chemical composition in Nellore cattle.

PubMed

Castilhos, A M; Francisco, C L; Branco, R H; Bonilha, S F M; Mercadante, M E Z; Meirelles, P R L; Pariz, C M; Jorge, A M

2018-05-04

Evaluation of the body chemical composition of beef cattle can only be measured postmortem and those data cannot be used in real production scenarios to adjust nutritional plans. The objective of this study was to develop multiple linear regression equations from in vivo measurements, such as ultrasound parameters [backfat thickness (uBFT, mm), rump fat thickness (uRF, mm), and ribeye area (uLMA, cm2)], shrunk body weight (SBW, kg), age (AG, d), hip height (HH, m), as well as from postmortem measurements (composition of the 9th to 11th rib section) to predict the empty body and carcass chemical composition for Nellore cattle. Thirty-three young bulls were used (339 ± 36.15 kg and 448 ± 17.78 d for initial weight and age, respectively). Empty body chemical composition (protein, fat, water, and ash in kg) was obtained by combining noncarcass and carcass components. Data were analyzed using the PROC REG procedure of SAS software. Mallows' Cp values were close to the ideal value of number of independent variables in the prediction equations plus one. Equations to predict chemical components of both empty body and carcass using in vivo measurements presented higher R2 values than those determined by postmortem measurements. Chemical composition of the empty body using in vivo measurements was predicted with R2 > 0.73. Equations to predict chemical composition of the carcass from in vivo measurements showed R2 lower (R2< 0.68) than observed for empty body, except for the water (R2 = 0.84). The independent variables SBW, uRF, and AG were sufficient to predict the fat, water, energy components of the empty body, whereas for estimation of protein content the uRF, HH, and SBW were satisfactory. For the calculation of the ash, the SBW variable in the equation was sufficient. Chemical compounds from components of the empty body of Nellore cattle can be calculated by the following equations: protein (kg) = 47.92 + 0.18 × SBW - 1.46 × uRF - 30.72 × HH (R2 = 0.94, RMSPE = 1

Coupling passive sampling with in vitro bioassays and chemical analysis to understand combined effects of bioaccumulative chemicals in blood of marine turtles.

PubMed

Jin, Ling; Escher, Beate I; Limpus, Colin J; Gaus, Caroline

2015-11-01

Conventional target analysis of biological samples such as blood limits our ability to understand mixture effects of chemicals. This study aimed to establish a rapid passive sampling technique using the polymer polydimethylsiloxane (PDMS) for exhaustive extraction of mixtures of neutral organic chemicals accumulated in blood of green turtles, in preparation for screening in in vitro bioassays. We designed a PDMS-blood partitioning system based on the partition coefficients of chemicals between PDMS and major blood components. The sampling kinetics of hydrophobic test chemicals (polychlorinated dibenzo-p-dioxins; PCDDs) from blood into PDMS were reasonably fast reaching steady state in <96 h. The geometric mean of the measured PDMS-blood partition coefficients for PCDDs, polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) was 14 L blood kg PDMS(-1) and showed little variability (95% confidence interval from 8.4 to 29) across a wide range of hydrophobicity (logKow 5.7-8.3). The mass transfer of these chemicals from 5 mL blood into 0.94 g PDMS was 62-84%, which is similar to analytical recoveries in conventional solvent extraction methods. The validated method was applied to 15 blood samples from green turtles with known concentrations of PCDD/Fs, dioxin-like PCBs, PBDEs and organochlorine pesticides. The quantified chemicals explained most of the dioxin-like activity (69-98%), but less than 0.4% of the oxidative stress response. The results demonstrate the applicability of PDMS-based passive sampling to extract bioaccumulative chemicals from blood as well as the value of in vitro bioassays for capturing the combined effects of unknown and known chemicals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Micropyrolyzer for chemical analysis of liquid and solid samples

DOEpatents

Mowry, Curtis D.; Morgan, Catherine H.; Manginell, Ronald P.; Frye-Mason, Gregory C.

2006-07-18

A micropyrolyzer has applications to pyrolysis, heated chemistry, and thermal desorption from liquid or solid samples. The micropyrolyzer can be fabricated from semiconductor materials and metals using standard integrated circuit technologies. The micropyrolyzer enables very small volume samples of less than 3 microliters and high sample heating rates of greater than 20.degree. C. per millisecond. A portable analyzer for the field analysis of liquid and solid samples can be realized when the micropyrolyzer is combined with a chemical preconcentrator, chemical separator, and chemical detector. Such a portable analyzer can be used in a variety of government and industrial applications, such as non-proliferation monitoring, chemical and biological warfare detection, industrial process control, water and air quality monitoring, and industrial hygiene.

Nanophotonic Atomic Force Microscope Transducers Enable Chemical Composition and Thermal Conductivity Measurements at the Nanoscale [Nanophotonic AFM Transducers Enable Chemical Composition and Thermal Conductivity Measurements at the Nanoscale

DOE PAGES

Chae, Jungseok; An, Sangmin; Ramer, Georg; ...

2017-08-03

The atomic force microscope (AFM) offers a rich observation window on the nanoscale, yet many dynamic phenomena are too fast and too weak for direct AFM detection. Integrated cavity-optomechanics is revolutionizing micromechanical sensing; however, it has not yet impacted AFM. Here, we make a groundbreaking advance by fabricating picogram-scale probes integrated with photonic resonators to realize functional AFM detection that achieve high temporal resolution (<10 ns) and picometer vertical displacement uncertainty simultaneously. The ability to capture fast events with high precision is leveraged to measure the thermal conductivity (η), for the first time, concurrently with chemical composition at the nanoscalemore » in photothermal induced resonance experiments. The intrinsic η of metal–organic-framework individual microcrystals, not measurable by macroscale techniques, is obtained with a small measurement uncertainty (8%). The improved sensitivity (50×) increases the measurement throughput 2500-fold and enables chemical composition measurement of molecular monolayer-thin samples. In conclusion, our paradigm-shifting photonic readout for small probes breaks the common trade-off between AFM measurement precision and ability to capture transient events, thus transforming the ability to observe nanoscale dynamics in materials.« less

Nanophotonic Atomic Force Microscope Transducers Enable Chemical Composition and Thermal Conductivity Measurements at the Nanoscale [Nanophotonic AFM Transducers Enable Chemical Composition and Thermal Conductivity Measurements at the Nanoscale

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

Chae, Jungseok; An, Sangmin; Ramer, Georg

The atomic force microscope (AFM) offers a rich observation window on the nanoscale, yet many dynamic phenomena are too fast and too weak for direct AFM detection. Integrated cavity-optomechanics is revolutionizing micromechanical sensing; however, it has not yet impacted AFM. Here, we make a groundbreaking advance by fabricating picogram-scale probes integrated with photonic resonators to realize functional AFM detection that achieve high temporal resolution (<10 ns) and picometer vertical displacement uncertainty simultaneously. The ability to capture fast events with high precision is leveraged to measure the thermal conductivity (η), for the first time, concurrently with chemical composition at the nanoscalemore » in photothermal induced resonance experiments. The intrinsic η of metal–organic-framework individual microcrystals, not measurable by macroscale techniques, is obtained with a small measurement uncertainty (8%). The improved sensitivity (50×) increases the measurement throughput 2500-fold and enables chemical composition measurement of molecular monolayer-thin samples. In conclusion, our paradigm-shifting photonic readout for small probes breaks the common trade-off between AFM measurement precision and ability to capture transient events, thus transforming the ability to observe nanoscale dynamics in materials.« less

Real time chemical exposure and risk monitor

DOEpatents

Thrall, K.D.; Kenny, D.V.; Endres, G.W.R.; Sisk, D.R.

1997-07-08

The apparatus of the present invention is a combination of a breath interface and an external exposure dosimeter interface to a chemical analysis device, all controlled by an electronic processor for quantitatively analyzing chemical analysis data from both the breath interface and the external exposure dosimeter for determining internal tissue dose. The method of the present invention is a combination of steps of measuring an external dose, measuring breath content, then analyzing the external dose and breath content and determining internal tissue dose. 7 figs.

Environmental analysis of the chemical release module. [space shuttle payload

NASA Technical Reports Server (NTRS)

Heppner, J. P.; Dubin, M.

1980-01-01

The environmental analysis of the Chemical Release Module (a free flying spacecraft deployed from the space shuttle to perform chemical release experiments) is reviewed. Considerations of possible effects of the injectants on human health, ionosphere, weather, ground based optical astronomical observations, and satellite operations are included. It is concluded that no deleterious environmental effects of widespread or long lasting nature are anticipated from chemical releases in the upper atmosphere of the type indicated for the program.

[Validation of measurement methods and estimation of uncertainty of measurement of chemical agents in the air at workstations].

PubMed

Dobecki, Marek

2012-01-01

This paper reviews the requirements for measurement methods of chemical agents in the air at workstations. European standards, which have a status of Polish standards, comprise some requirements and information on sampling strategy, measuring techniques, type of samplers, sampling pumps and methods of occupational exposure evaluation at a given technological process. Measurement methods, including air sampling and analytical procedure in a laboratory, should be appropriately validated before intended use. In the validation process, selected methods are tested and budget of uncertainty is set up. The validation procedure that should be implemented in the laboratory together with suitable statistical tools and major components of uncertainity to be taken into consideration, were presented in this paper. Methods of quality control, including sampling and laboratory analyses were discussed. Relative expanded uncertainty for each measurement expressed as a percentage, should not exceed the limit of values set depending on the type of occupational exposure (short-term or long-term) and the magnitude of exposure to chemical agents in the work environment.

Chemical Analysis of the Dyes Used in Navy Green and Yellow Colored Smokes .

DTIC Science & Technology

1986-01-31

RD-RI69 478 CHEMICAL ANALYSIS OF THE DYES USED IN NAVY OREEN AND 11 YELLOW COLORED SNOKES(U) NAVAL WEAPONS SUP POR T CENTER CRANE IN APPLIED SCIENCES...NWSC/CR/RDTR-271 00 CHEMICAL ANALYSIS OF THE DYES USED IN NAVY GREEN AND YELLOW COLORED SMOKES Anton Chin Naval Weapons Support Center Applied Sciences...62765 SF65-559 559-691 20392 TITLE (Iint/ude Sec uritE C/assitication) CHEMICAL ANALYSIS OF THE DYES USED IN NAVY GREEN AND YELLOW COLORED SMOKES 1.1

CERENA: ChEmical REaction Network Analyzer--A Toolbox for the Simulation and Analysis of Stochastic Chemical Kinetics.

PubMed

Kazeroonian, Atefeh; Fröhlich, Fabian; Raue, Andreas; Theis, Fabian J; Hasenauer, Jan

2016-01-01

Gene expression, signal transduction and many other cellular processes are subject to stochastic fluctuations. The analysis of these stochastic chemical kinetics is important for understanding cell-to-cell variability and its functional implications, but it is also challenging. A multitude of exact and approximate descriptions of stochastic chemical kinetics have been developed, however, tools to automatically generate the descriptions and compare their accuracy and computational efficiency are missing. In this manuscript we introduced CERENA, a toolbox for the analysis of stochastic chemical kinetics using Approximations of the Chemical Master Equation solution statistics. CERENA implements stochastic simulation algorithms and the finite state projection for microscopic descriptions of processes, the system size expansion and moment equations for meso- and macroscopic descriptions, as well as the novel conditional moment equations for a hybrid description. This unique collection of descriptions in a single toolbox facilitates the selection of appropriate modeling approaches. Unlike other software packages, the implementation of CERENA is completely general and allows, e.g., for time-dependent propensities and non-mass action kinetics. By providing SBML import, symbolic model generation and simulation using MEX-files, CERENA is user-friendly and computationally efficient. The availability of forward and adjoint sensitivity analyses allows for further studies such as parameter estimation and uncertainty analysis. The MATLAB code implementing CERENA is freely available from http://cerenadevelopers.github.io/CERENA/.

CERENA: ChEmical REaction Network Analyzer—A Toolbox for the Simulation and Analysis of Stochastic Chemical Kinetics

PubMed Central

Kazeroonian, Atefeh; Fröhlich, Fabian; Raue, Andreas; Theis, Fabian J.; Hasenauer, Jan

2016-01-01

Gene expression, signal transduction and many other cellular processes are subject to stochastic fluctuations. The analysis of these stochastic chemical kinetics is important for understanding cell-to-cell variability and its functional implications, but it is also challenging. A multitude of exact and approximate descriptions of stochastic chemical kinetics have been developed, however, tools to automatically generate the descriptions and compare their accuracy and computational efficiency are missing. In this manuscript we introduced CERENA, a toolbox for the analysis of stochastic chemical kinetics using Approximations of the Chemical Master Equation solution statistics. CERENA implements stochastic simulation algorithms and the finite state projection for microscopic descriptions of processes, the system size expansion and moment equations for meso- and macroscopic descriptions, as well as the novel conditional moment equations for a hybrid description. This unique collection of descriptions in a single toolbox facilitates the selection of appropriate modeling approaches. Unlike other software packages, the implementation of CERENA is completely general and allows, e.g., for time-dependent propensities and non-mass action kinetics. By providing SBML import, symbolic model generation and simulation using MEX-files, CERENA is user-friendly and computationally efficient. The availability of forward and adjoint sensitivity analyses allows for further studies such as parameter estimation and uncertainty analysis. The MATLAB code implementing CERENA is freely available from http://cerenadevelopers.github.io/CERENA/. PMID:26807911

Methodology for national risk analysis and prioritization of toxic industrial chemicals.

PubMed

Taxell, Piia; Engström, Kerstin; Tuovila, Juha; Söderström, Martin; Kiljunen, Harri; Vanninen, Paula; Santonen, Tiina

2013-01-01

The identification of chemicals that pose the greatest threat to human health from incidental releases is a cornerstone in public health preparedness for chemical threats. The present study developed and applied a methodology for the risk analysis and prioritization of industrial chemicals to identify the most significant chemicals that pose a threat to public health in Finland. The prioritization criteria included acute and chronic health hazards, physicochemical and environmental hazards, national production and use quantities, the physicochemical properties of the substances, and the history of substance-related incidents. The presented methodology enabled a systematic review and prioritization of industrial chemicals for the purpose of national public health preparedness for chemical incidents.

Approaches to Measuring Entanglement in Chemical Magnetometers

PubMed Central

2013-01-01

Chemical magnetometers are radical pair systems such as solutions of pyrene and N,N-dimethylaniline (Py–DMA) that show magnetic field effects in their spin dynamics and their fluorescence. We investigate the existence and decay of quantum entanglement in free geminate Py–DMA radical pairs and discuss how entanglement can be assessed in these systems. We provide an entanglement witness and propose possible observables for experimentally estimating entanglement in radical pair systems with isotropic hyperfine couplings. As an application, we analyze how the field dependence of the entanglement lifetime in Py–DMA could in principle be used for magnetometry and illustrate the propagation of measurement errors in this approach. PMID:24372396

Analysis of Pfizer compounds in EPA's ToxCast chemicals-assay space.

PubMed

Shah, Falgun; Greene, Nigel

2014-01-21

The U.S. Environmental Protection Agency (EPA) launched the ToxCast program in 2007 with the goal of evaluating high-throughput in vitro assays to prioritize chemicals that need toxicity testing. Their goal was to develop predictive bioactivity signatures for toxic compounds using a set of in vitro assays and/or in silico properties. In 2009, Pfizer joined the ToxCast initiative by contributing 52 compounds with preclinical and clinical data for profiling across the multiple assay platforms available. Here, we describe the initial analysis of the Pfizer subset of compounds within the ToxCast chemical (n = 1814) and in vitro assay (n = 486) space. An analysis of the hit rate of Pfizer compounds in the ToxCast assay panel allowed us to focus our mining of assays potentially most relevant to the attrition of our compounds. We compared the bioactivity profile of Pfizer compounds to other compounds in the ToxCast chemical space to gain insights into common toxicity pathways. Additionally, we explored the similarity in the chemical and biological spaces between drug-like compounds and environmental chemicals in ToxCast and compared the in vivo profiles of a subset of failed pharmaceuticals having high similarity in both spaces. We found differences in the chemical and biological spaces of pharmaceuticals compared to environmental chemicals, which may question the applicability of bioactivity signatures developed exclusively based on the latter to drug-like compounds if used without prior validation with the ToxCast Phase-II chemicals. Finally, our analysis has allowed us to identify novel interactions for our compounds in particular with multiple nuclear receptors that were previously not known. This insight may help us to identify potential liabilities with future novel compounds.

Updated Chemical Kinetics and Sensitivity Analysis Code

NASA Technical Reports Server (NTRS)

Radhakrishnan, Krishnan

2005-01-01

An updated version of the General Chemical Kinetics and Sensitivity Analysis (LSENS) computer code has become available. A prior version of LSENS was described in "Program Helps to Determine Chemical-Reaction Mechanisms" (LEW-15758), NASA Tech Briefs, Vol. 19, No. 5 (May 1995), page 66. To recapitulate: LSENS solves complex, homogeneous, gas-phase, chemical-kinetics problems (e.g., combustion of fuels) that are represented by sets of many coupled, nonlinear, first-order ordinary differential equations. LSENS has been designed for flexibility, convenience, and computational efficiency. The present version of LSENS incorporates mathematical models for (1) a static system; (2) steady, one-dimensional inviscid flow; (3) reaction behind an incident shock wave, including boundary layer correction; (4) a perfectly stirred reactor; and (5) a perfectly stirred reactor followed by a plug-flow reactor. In addition, LSENS can compute equilibrium properties for the following assigned states: enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. For static and one-dimensional-flow problems, including those behind an incident shock wave and following a perfectly stirred reactor calculation, LSENS can compute sensitivity coefficients of dependent variables and their derivatives, with respect to the initial values of dependent variables and/or the rate-coefficient parameters of the chemical reactions.

Measuring the Chemical Potential of the Martian Regolith to Generate and Sustain Life

NASA Technical Reports Server (NTRS)

Kounaves, S. P.; Buehler, M. G.; Kuhlman, K. R.

1999-01-01

A critical component for identifying chemical biosignatures is the ability to assess in-situ the potential of an aqueous geochemical environment to generate and sustain life. On Mars or other solar bodies, in-situ chemical characterization could provide evidence as to whether the chemical composition of the regolith or evaporites in suspected ancient water bodies have been biologically influenced or possess the chemical parameters within which life may have existed, or may still exist. A variety of analytical techniques have been proposed for use in detecting and identify signatures of past or present life. These techniques fall into two groups; visual observation with instruments such as cameras or optical/atomic-force microscopes; or elemental chemical analysis with such instruments as X-ray fluorescence (XRF) and diffraction (XRD), a-proton backscatter (APX), y-ray, Mossbauer, Raman, IR, UV/VIS spectroscopies, gas chromatography (GC), or mass spectrometry (MS). Direct observation of an identifiable lifeform by the first set of instruments in a single sample is highly unlikely, especially for extinct organisms or on the surface. The later instruments can provide vital data as to the elemental mineralogy and geological history of the planet, but are highly inadequate for understanding the chemistry of the planet in terms of indigenous life or interactions with human explorers. Techniques such as XRD, XRF, and APX, provide elemental composition at high limits of detection. Some of this data can be extrapolated or interpolated to provide chemical parameters such as oxidation state or composition. Gas chromatography (GC) without standards and non-specific detectors, has little chance of identifying a mixture of unknown components. Combined with GC or by itself, mass spectrometry (MS) can provide identification of compounds, but in both cases the sample must be appropriately prepared for accurate and reliable analysis. Life as we know it, and probably identify it as

Confocal detection of Rayleigh scattering for residual stress measurement in chemically tempered glass

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

Hödemann, S., E-mail: siim.hodemann@ut.ee; Möls, P.; Kiisk, V.

2015-12-28

A new optical method is presented for evaluation of the stress profile in chemically tempered (chemically strengthened) glass based on confocal detection of scattered laser beam. Theoretically, a lateral resolution of 0.2 μm and a depth resolution of 0.6 μm could be achieved by using a confocal microscope with high-NA immersion objective. The stress profile in the 250 μm thick surface layer of chemically tempered lithium aluminosilicate glass was measured with a high spatial resolution to illustrate the capability of the method. The confocal method is validated using transmission photoelastic and Na{sup +} ion concentration profile measurement. Compositional influence on the stress-optic coefficientmore » is calculated and discussed. Our method opens up new possibilities for three-dimensional scattered light tomography of mechanical imaging in birefringent materials.« less

Conformational analysis, spectroscopic, structure-activity relations and quantum chemical simulation studies of 4-(trifluoromethyl)benzylamine

NASA Astrophysics Data System (ADS)

Arjunan, V.; Devi, L.; Mohan, S.

2018-05-01

The FT-IR and FT-Raman spectra of 4-trifluoromethylbenzylamine (TFMBA) have been recorded in the range 4000-450 and 4000-100 cm-1 respectively. The conformational analysis of the compound has been carried out to attain stable geometry of the compound. The complete vibrational assignment and analysis of the fundamental modes of the compound are carried out using the experimental FTIR and FT-Raman data and quantum chemical studies. The experimental vibrational frequencies are compared with the wavenumbers obtained theoretically from the B3LYP gradient calculations employing the standard high level 6-311++G** and cc-pVTZ basis sets for the optimised geometry of the compound. The structural parameters, thermodynamic properties and vibrational frequencies of the normal modes obtained from the B3LYP methods are in good agreement with the experimental data. The 1H (400 MHz; CDCl3) and 13C (100 MHz; CDCl3) nuclear magnetic resonance (NMR) spectra were also recorded. The electronic properties, highest occupied molecular orbital and lowest unoccupied molecular orbital energies are measured by DFT approach. The charges of the atoms by natural bond orbital (NBO) analysis are determined by B3LYP/cc-pVTZ method. The structure-chemical reactivity relations of the compound are determined through chemical potential, global hardness, global softness, electronegativity, electrophilicity and local reactivity descriptors by conceptual DFT methods.

Comparison of bioactive chemical space networks generated using substructure- and fingerprint-based measures of molecular similarity

NASA Astrophysics Data System (ADS)

Zhang, Bijun; Vogt, Martin; Maggiora, Gerald M.; Bajorath, Jürgen

2015-07-01

Chemical space networks (CSNs) have recently been introduced as a conceptual alternative to coordinate-based representations of chemical space. CSNs were initially designed as threshold networks using the Tanimoto coefficient as a continuous similarity measure. The analysis of CSNs generated from sets of bioactive compounds revealed that many statistical properties were strongly dependent on their edge density. While it was difficult to compare CSNs at pre-defined similarity threshold values, CSNs with constant edge density were directly comparable. In the current study, alternative CSN representations were constructed by applying the matched molecular pair (MMP) formalism as a substructure-based similarity criterion. For more than 150 compound activity classes, MMP-based CSNs (MMP-CSNs) were compared to corresponding threshold CSNs (THR-CSNs) at a constant edge density by applying different parameters from network science, measures of community structure distributions, and indicators of structure-activity relationship (SAR) information content. MMP-CSNs were found to be an attractive alternative to THR-CSNs, yielding low edge densities and well-resolved topologies. MMP-CSNs and corresponding THR-CSNs often had similar topology and closely corresponding community structures, although there was only limited overlap in similarity relationships. The homophily principle from network science was shown to affect MMP-CSNs and THR-CSNs in different ways, despite the presence of conserved topological features. Moreover, activity cliff distributions in alternative CSN designs markedly differed, which has important implications for SAR analysis.

Inter-laboratory comparison study on measuring semi-volatile organic chemicals in standards and air samples.

PubMed

Su, Yushan; Hung, Hayley

2010-11-01

Measurements of semi-volatile organic chemicals (SVOCs) were compared among 21 laboratories from 7 countries through the analysis of standards, a blind sample, an air extract, and an atmospheric dust sample. Measurement accuracy strongly depended on analytes, laboratories, and types of standards and samples. Intra-laboratory precision was generally good with relative standard deviations (RSDs) of triplicate injections <10% and with median differences of duplicate samples between 2.1 and 22%. Inter-laboratory variability, measured by RSDs of all measurements, was in the range of 2.8-58% in analyzing standards, and 6.9-190% in analyzing blind sample and air extract. Inter-laboratory precision was poorer when samples were subject to cleanup processes, or when SVOCs were quantified at low concentrations. In general, inter-laboratory differences up to a factor of 2 can be expected to analyze atmospheric SVOCs. When comparing air measurements from different laboratories, caution should be exercised if the data variability is less than the inter-laboratory differences. 2010. Published by Elsevier Ltd. All rights reserved.

Analysis of LDEF experiment AO187-2 chemical and isotopic measurements of micrometeoroids by secondary ion mass spectrometry

NASA Technical Reports Server (NTRS)

Zinner, Ernst

1995-01-01

#Experiment AO187-2, that was flown on board the Long Duration Exposure Facility(LDEF), was designed to measure the chemical and isotopic compositions of interplanetary dust impinging on the spacecraft from outer space. Information on the nature and composition of orbital debris was also anticipated. The spacecraft maintained a constant orientation with respect to its velocity vector thereby defining leading and trailing edges that faced respectively into and away from the direction of motion. Arrays of individual capture cells each 80.8 sq cm in size and totaling 237 in number were exposed on both the leading and trailing edges of LDEF. Each cell consisted of a pure Ge target surface slightly separated from a thin (2.5 micrometers) metallized plastic 'entrance foil.' The basic concept was that incoming projectiles would penetrate the foil, strike the Ge target plate at high velocity producing a vapor-liquid cloud that would re-deposit material on the underside of the plastic foil. This material would then be analyzed using the sensitive surface analysis technique of Secondary Ion Mass Spectrometry (SIMS). In practice, most of the plastic entrance foils failed during the extended period of orbital exposure probably due to a combination of UV embrittlement, large densities of impact events and (for the leading edge) the effects of atomic oxygen erosion in orbit. However the foils failed gradually and most remained in place on the capture cells for a significant fraction of the duration of the flight . Because most of the impactors were small (less than 10 micrometers) they were heated and dispersed in traversing the entrance foils producing clouds of molten droplets and vapor that produced easily identifiable 'extended impacts' on the Ge target plates. Fortunately, it proved possible to make ion probe measurements of projectile compositions from material deposited on the Ge in the extended impact structures.

To measure the chemical composition of a Near Earth Object

NASA Astrophysics Data System (ADS)

Gasnault, 0.; Ball, A.; Biele, J.; D'Uston, C.; Forni, O.; Klingelhofer, G.; Maurice, S.; Ulamec, S.

Introduction. Scenarios for a Near Earth Object (NEO) rendezvous mission were discussed recently in Europe. Such a mission would address scientific questions about the initial conditions and evolutionary history of the solar nebula, as well as mitigation considerations to prevent impact with the Earth. In our opinion the measurement of the elemental composition and the distribution of volatiles in the shallow sub-surface are two of the key observations to be conducted, either from an orbiter or a lander. These measurements are also valuable for documentation (landing site candidates and sample context). This report is limited to the chemical composition, but we assume that remote and/or in-situ observations of physical characteristics, interior, morphology, mineralogy, and organic compounds will also be made as essential complements to achieve the mission scientific objectives. Scientific Interest. The analysis of the bulk composition addresses three fundamental aspects of the scientific mission: (1) the formation of the asteroid or the comet; (2) the evolution of the object; (3) the relation between the parent body and collected meteorites on Earth. Classification of an asteroid/comet can be based on its global composition (abundances of Mg, Si, Fe, Al, Ca, etc. along with its mineralogy), which bears the signature of the feeding zone where it formed. For example the K/U and K/Th ratios seem to increase with distance from the Sun (decreasing temperature). The hydrogen content is another measurable to study the distribution of volatiles in the Solar System. The surface composition is also the result of the degree of evolution of the object and of the interactions with its environment. Building a compositional map of the major elements is necessary to identify and characterize the processes that influenced the asteroid along its history. Finally, knowing the chemical composition will obviously help to relate the parent 1 body to meteorites. Ideally the measurement

Ultrasonic, needle, and carcass measurements for predicting chemical composition of lamb carcasses.

PubMed

Ramsey, C B; Kirton, A H; Hogg, B; Dobbie, J L

1991-09-01

Three groups (n = 147) of New Zealand mixed breed lambs averaging 170 d of age and 31.7 kg in weight were killed after a diet of pasture to determine whether the total depth of soft tissues over the 12th rib 11 cm from the dorsal midline (GR) could be measured in live lambs with sufficient accuracy to warrant its use as a selection tool for breeding flock replacements. Relationships among live and carcass measurements and carcass chemical composition also were determined. An ultrasonic measurement of GR in the live lambs was a more accurate predictor of carcass GR (r = .87) and percentage carcass fat (r = .80) than was a measurement of GR made with a needle (r = .80 and .67, respectively). Both measurements were sufficiently accurate to permit culling of over-fat lambs from breeding flock replacement prospects. The best single indicator of percentage carcass fat (r = .87) was a shoulder fat measurement, followed closely by carcass GR (r = .85). Both were superior to USDA yield grade for estimating carcass chemical composition in these young, lightweight lambs. These two measurements also were most highly related to percentage carcass protein (r = -.78 and r = -.77, respectively). These results indicate possibilities for improving the method of evaluating the composition of U. S. lamb carcasses.

Application of Solid Phase Microextraction Coupled with Gas Chromatography/Mass Spectrometry as a Rapid Method for Field Sampling and Analysis of Chemical Warfare Agents and Toxic Industrial Chemicals

DTIC Science & Technology

2003-01-01

PHASE MICROEXTRACTION COUPLED WITH GAS CHROMATOGRAPHY/MASS SPECTROMETRY AS A RAPID METHOD FOR FIELD SAMPLING AND ANALYSIS OF CHEMICAL WARFARE AGENTS...SAMPLING AND ANALYSIS OF CHEMICAL WARFARE AGENTS AND TOXIC INDUSTRIAL CHEMICALS 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6...GAS CHROMATOGRAPHY/MASS SPECTROMETRY AS A RAPID METHOD FOR FIELD SAMPLING AND ANALYSIS OF CHEMICAL WARFARE AGENTS AND TOXIC INDUSTRIAL CHEMICALS

Uses of NHANES biomarker data for chemical risk ...

EPA Pesticide Factsheets

Background. Each year, the US NHANES measures hundreds of chemical biomarkers in samples from thousands of study participants. These biomarker measurements are meant to track trends and identify subsets of the US population with elevated exposures. There is now interest in further utilizing the NHANES data to inform chemical risk assessments. Objectives. This article highlights: 1) the extent to which NHANES chemical biomarker data have been evaluated, 2) groups of chemicals that have been studied, 3) data analysis approaches, and 4) opportunities for using these data to inform chemical risk assessments.Methods. A literature search (1999-2013) was performed to identify publications in which NHANES data were reported. Manual curation identified only the subset of publications that clearly utilized chemical biomarker data. This subset was evaluated for chemical groupings, data analysis approaches, and overall trends.Results. A small percentage of yearly NHANES-related publications reported on chemical biomarkers (8% yearly average). Of eleven chemical groups, metals/metalloids were most frequently evaluated (49%), followed by pesticides (9%) and environmental phenols (7%). Studies of multiple chemical groups were also common (8%). Publications linking chemical biomarkers to health metrics have increased dramatically in recent years. New studies are addressing challenges related to NHANES data interpretation in health risk contexts.Conclusions. This articl

Use of thermal neutron reflection method for chemical analysis of bulk samples

NASA Astrophysics Data System (ADS)

Papp, A.; Csikai, J.

2014-09-01

Microscopic, σβ, and macroscopic, Σβ, reflection cross-sections of thermal neutrons averaged over bulk samples as a function of thickness (z) are given. The σβ values are additive even for bulk samples in the z=0.5-8 cm interval and so the σβmol(z) function could be given for hydrogenous substances, including some illicit drugs, explosives and hiding materials of ~1000 cm3 dimensions. The calculated excess counts agree with the measured R(z) values. For the identification of concealed objects and chemical analysis of bulky samples, different neutron methods need to be used simultaneously.

An Analysis of Chemical Ingredients Network of Chinese Herbal Formulae for the Treatment of Coronary Heart Disease

PubMed Central

Ding, Fan; Zhang, Qianru; Ung, Carolina Oi Lam; Wang, Yitao; Han, Yifan; Hu, Yuanjia; Qi, Jin

2015-01-01

As a complex system, the complicated interactions between chemical ingredients, as well as the potential rules of interactive associations among chemical ingredients of traditional Chinese herbal formulae are not yet fully understood by modern science. On the other hand, network analysis is emerging as a powerful approach focusing on processing complex interactive data. By employing network approach in selected Chinese herbal formulae for the treatment of coronary heart disease (CHD), this article aims to construct and analyze chemical ingredients network of herbal formulae, and provide candidate herbs, chemical constituents, and ingredient groups for further investigation. As a result, chemical ingredients network composed of 1588 ingredients from 36 herbs used in 8 core formulae for the treatment of CHD was produced based on combination associations in herbal formulae. In this network, 9 communities with relative dense internal connections are significantly associated with 14 kinds of chemical structures with P<0.001. Moreover, chemical structural fingerprints of network communities were detected, while specific centralities of chemical ingredients indicating different levels of importance in the network were also measured. Finally, several distinct herbs, chemical ingredients, and ingredient groups with essential position in the network or high centrality value are recommended for further pharmacology study in the context of new drug development. PMID:25658855

Chemical probes for analysis of carbonylated proteins: a review

PubMed Central

Yan, Liang-Jun; Forster, Michael J.

2010-01-01

Protein carbonylation is a major form of protein oxidation and is widely used as an indicator of oxidative stress. Carbonyl groups do not have distinguishing UV or visible, spectrophotometric absorbance/fluorescence characteristics and thus their detection and quantification can only be achieved using specific chemical probes. In this paper, we review the advantages and disadvantages of several chemical probes that have been and are still being used for protein carbonyl analysis. These probes include 2, 4-dinitrophenylhydazine (DNPH), tritiated sodium borohydride ([3H]NaBH4), biotin-containing probes, and fluorescence probes. As our discussions lean toward gel-based approaches, utilizations of these probes in 2D gel-based proteomic analysis of carbonylated proteins are illustrated where applicable. Analysis of carbonylated proteins by ELISA, immunofluorescent imaging, near infrared fluorescence detection, and gel-free proteomic approaches are also discussed where appropriate. Additionally, potential applications of blue native gel electrophoresis as a tool for first dimensional separation in 2D gel-based analysis of carbonylated proteins are discussed as well. PMID:20732835

Fatty acid composition and its association with chemical and sensory analysis of boar taint.

PubMed

Liu, Xiaoye; Trautmann, Johanna; Wigger, Ruth; Zhou, Guanghong; Mörlein, Daniel

2017-09-15

A certain level of disagreement between the chemical analysis of androstenone and skatole and the human perception of boar taint has been found in many studies. Here we analyze whether the fatty acid composition can explain such inconsistency between sensory evaluation and chemical analysis of boar taint compounds. Therefore, back fat samples (n=143) were selected according to their sensory evaluation by a 10-person sensory panel, and the chemical analysis (stable isotope dilution analysis with headspace solid-phase microextraction and gas chromatography-mass spectrometry) of androstenone and skatole. Subsequently a quantification of fatty acids using gas chromatography-flame ionization detection was conducted. The correlation analyses revealed that several fatty acids are significantly correlated with androstenone, skatole, and the sensory rating. However, multivariate analyses (principal component analysis) revealed no explanation of the fatty acid composition with respect to the (dis-)agreement between sensory and chemical analysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

METHOD OF CHEMICAL ANALYSIS FOR OIL SHALE WASTES

EPA Science Inventory

Several methods of chemical analysis are described for oil shale wastewaters and retort gases. These methods are designed to support the field testing of various pollution control systems. As such, emphasis has been placed on methods which are rapid and sufficiently rugged to per...

Measurement uncertainty analysis techniques applied to PV performance measurements

NASA Astrophysics Data System (ADS)

Wells, C.

1992-10-01

The purpose of this presentation is to provide a brief introduction to measurement uncertainty analysis, outline how it is done, and illustrate uncertainty analysis with examples drawn from the PV field, with particular emphasis toward its use in PV performance measurements. The uncertainty information we know and state concerning a PV performance measurement or a module test result determines, to a significant extent, the value and quality of that result. What is measurement uncertainty analysis? It is an outgrowth of what has commonly been called error analysis. But uncertainty analysis, a more recent development, gives greater insight into measurement processes and tests, experiments, or calibration results. Uncertainty analysis gives us an estimate of the interval about a measured value or an experiment's final result within which we believe the true value of that quantity will lie. Why should we take the time to perform an uncertainty analysis? A rigorous measurement uncertainty analysis: Increases the credibility and value of research results; allows comparisons of results from different labs; helps improve experiment design and identifies where changes are needed to achieve stated objectives (through use of the pre-test analysis); plays a significant role in validating measurements and experimental results, and in demonstrating (through the post-test analysis) that valid data have been acquired; reduces the risk of making erroneous decisions; demonstrates quality assurance and quality control measures have been accomplished; define Valid Data as data having known and documented paths of: Origin, including theory; measurements; traceability to measurement standards; computations; uncertainty analysis of results.

Measurement of chemical composition and optical properties of PM2.5 at Rudong, China

NASA Astrophysics Data System (ADS)

Taketani, F.; Kanaya, Y.; Pan, X.; Irie, H.; Takashima, H.; Tanimoto, H.; Saito, S.; Akimoto, H.; Wang, Z.

2013-12-01

Intensive field campaign in Rudong(32.26 deg N, 121.37 deg E), located 100 km north of the city center of Shanghai, China, in May and June 2010 was carried out. To investigate chemical and optical property of aerosol particles, in this study, 9 or 14-hours PM2.5 samples were collected on the quartz filters using High-volume(500L/min) samplers. Using these filters, EC (elemental carbon) and OC(organic carbon), water-soluble ions(SO42-, NO3-, NH4+, Cl-, Ca2+, Mg2+, K+, and Na+) and metals(Al, Fe, Cu, Mn, Zn, Pb) were measured by Sunset lab EC/OC instrument, ion-chromatography, and ICP-AES, respectively. Furthermore, to monitor PM2.5 total mass, we employed SHARP monitor. During the campaign, total mass concentration monitored by SHARP instrument ranged from 3.2 to 172.1 ug/m3 with a mean of 55.3 ug/m3, and major components were sulfate, nitrate, and organics. The total mass concentration of PM2.5 monitored by the SHARP instrument was overestimated with sum of observed mass concentrations of each species. By taking into account the water amount in the particles measured by the SHARP instrument using thermodynamics model with the compositions on the filter and measured RH, we found mass closure should be achieved. We also performed particle source apportionment analysis using Positive Matrix Factorization (PMF) to investigate the source categories. Furthermore, scattering coefficient was reconstructed in an empirical manner by summing the contributions from various chemical species, which were calculated by multiplying observed mass concentrations of each species with empirical mass scattering coefficient. The reconstructed scattering coefficient had good correlation with directly measured coefficients by nephelometer at RH < 40%. We found the importance of ammonium sulfate and organics in determining the ambient scattering coefficient.

SWOT analysis for safer carriage of bulk liquid chemicals in tankers.

PubMed

Arslan, Ozcan; Er, Ismail Deha

2008-06-15

The application of strengths, weaknesses, opportunities and threats (SWOT) analysis to formulation of strategy concerned with the safe carriage of bulk liquid chemicals in maritime tankers was examined in this study. A qualitative investigation using SWOT analysis has been implemented successfully for ships that are designed to carry liquid chemicals in bulk. The originality of this study lies in the use of SWOT analysis as a management tool to formulate strategic action plans for ship management companies, ship masters and officers for the carriage of dangerous goods in bulk. With this transportation-based SWOT analysis, efforts were made to explore the ways and means of converting possible threats into opportunities, and changing weaknesses into strengths; and strategic plans of action were developed for safer tanker operation.

[Relativity of commercial specification of Menthae Herba based on chemical analysis].

PubMed

Ye, Dan; Zhao, Ming; Shao, Yang; Ouyang, Zhen; Peng, Hua-sheng; Han Bang-xing; Zhang, Wei-wan-qi; Gu, Xue-mei

2015-01-01

In order to compare the differences of 35 Menthae Herba samples collected on the market and at producing areas, the contents of six total terpenoids, the essential oil and chromatographic fingerprints were analyzed, which provided evidences for drawing up the commodity specifications and grading criteria of Menthae Herba. GC-MS method was used to analyze the chemical constituents of 35 different samples. The chromatographic fingerprints obtained by using GC were then evaluated by similarity analysis, hierarchical clustering analysis and principal component analysis. The relativity between the content of six terpenoids and the essential oil were studied. In this study, the chemical profiles of 35 samples from different producing areas had significant disparity. All samples collected in the report could be categorized into four chemical types, L-menthol, pulegone, carvone and L-menthone, but the chemical profiles had no relationship with the areas. The chromatographic fingerprints of the samples from different types were dissimilar, while the different producing areas were difficult to be separated. It was indicated that the content of volatile oil was positively correlated with the content of L-menthol and the sum of six total terpenoids. The content of the essential oil, L-menthol and the sum of six total terpenoids of Menthae Herba were considered as one of the commercial specifications and grading criteria. These results in the research could be helpful to draw up the commercial specification and grading criteria of Menthae Herba from a view of chemical information.

Binary similarity measures for fingerprint analysis of qualitative metabolomic profiles.

PubMed

Rácz, Anita; Andrić, Filip; Bajusz, Dávid; Héberger, Károly

2018-01-01

Contemporary metabolomic fingerprinting is based on multiple spectrometric and chromatographic signals, used either alone or combined with structural and chemical information of metabolic markers at the qualitative and semiquantitative level. However, signal shifting, convolution, and matrix effects may compromise metabolomic patterns. Recent increase in the use of qualitative metabolomic data, described by the presence (1) or absence (0) of particular metabolites, demonstrates great potential in the field of metabolomic profiling and fingerprint analysis. The aim of this study is a comprehensive evaluation of binary similarity measures for the elucidation of patterns among samples of different botanical origin and various metabolomic profiles. Nine qualitative metabolomic data sets covering a wide range of natural products and metabolomic profiles were applied to assess 44 binary similarity measures for the fingerprinting of plant extracts and natural products. The measures were analyzed by the novel sum of ranking differences method (SRD), searching for the most promising candidates. Baroni-Urbani-Buser (BUB) and Hawkins-Dotson (HD) similarity coefficients were selected as the best measures by SRD and analysis of variance (ANOVA), while Dice (Di1), Yule, Russel-Rao, and Consonni-Todeschini 3 ranked the worst. ANOVA revealed that concordantly and intermediately symmetric similarity coefficients are better candidates for metabolomic fingerprinting than the asymmetric and correlation based ones. The fingerprint analysis based on the BUB and HD coefficients and qualitative metabolomic data performed equally well as the quantitative metabolomic profile analysis. Fingerprint analysis based on the qualitative metabolomic profiles and binary similarity measures proved to be a reliable way in finding the same/similar patterns in metabolomic data as that extracted from quantitative data.

CHEERS: Chemical enrichment of clusters of galaxies measured using a large XMM-Newton sample

NASA Astrophysics Data System (ADS)

de Plaa, J.; Mernier, F.; Kaastra, J.; Pinto, C.

2017-10-01

The Chemical Enrichment RGS Sample (CHEERS) is aimed to be a sample of the most optimal clusters of galaxies for observation with the Reflection Grating Spectrometer (RGS) aboard XMM-Newton. It consists of 5 Ms of deep cluster observations of 44 objects obtained through a very large program and archival observations. The main goal is to measure chemical abundances in the hot Intra-Cluster Medium (ICM) of clusters to provide constraints on chemical evolution models. Especially the origin and evolution of type Ia supernovae is still poorly known and X-ray observations could contribute to constrain models regarding the SNIa explosion mechanism. Due to the high quality of the data, the uncertainties on the abundances are dominated by systematic effects. By carefully treating each systematic effect, we increase the accuracy or estimate the remaining uncertainty on the measurement. The resulting abundances are then compared to supernova models. In addition, also radial abundance profiles are derived. In the talk, we present an overview of the results that the CHEERS collaboration obtained based on the CHEERS data. We focus on the abundance measurements. The other topics range from turbulence measurements through line broadening to cool gas in groups.

Chemical Industry Analysis Brief

EIA Publications

2005-01-01

The chemical industries are a cornerstone of the U.S. economy, converting raw materials such as oil, natural gas, air, water, metals, and minerals into thousands of various products. Chemicals are key materials for producing an extensive assortment of consumer goods.

FBX aqueous chemical dosimeter for measurement of virtual wedge profiles.

PubMed

Semwal, Manoj K; Bansal, Anil K; Thakur, Pradeep K; Vidyasagar, Pandit B

2008-10-24

We investigated the ferrous sulfate-benzoic acid-xylenol orange (FBX) aqueous chemical dosimeter for measurement of virtual (dynamic) wedge profiles on a linear accelerator. The layout for irradiation of the FBX-filled tubes mimicked a conventional linear detector array geometry. A comparison of the resulting measurements with film-measured profiles showed that, in the main beam region, the difference between the FBX system and the film system was within +/-2% and that, in the penumbra region, the difference varied from +/-1 mm to +/-2.5 mm in terms of positional equivalence, depending on the size of the dosimeter tubes. We thus believe that the energy-independent FBX dosimetry system can measure virtual wedge profiles with reasonable accuracy at reasonable cost. However, efficiency improvement is required before this dosimetry system can be accepted into routine practice.

Computational singular perturbation analysis of stochastic chemical systems with stiffness

NASA Astrophysics Data System (ADS)

Wang, Lijin; Han, Xiaoying; Cao, Yanzhao; Najm, Habib N.

2017-04-01

Computational singular perturbation (CSP) is a useful method for analysis, reduction, and time integration of stiff ordinary differential equation systems. It has found dominant utility, in particular, in chemical reaction systems with a large range of time scales at continuum and deterministic level. On the other hand, CSP is not directly applicable to chemical reaction systems at micro or meso-scale, where stochasticity plays an non-negligible role and thus has to be taken into account. In this work we develop a novel stochastic computational singular perturbation (SCSP) analysis and time integration framework, and associated algorithm, that can be used to not only construct accurately and efficiently the numerical solutions to stiff stochastic chemical reaction systems, but also analyze the dynamics of the reduced stochastic reaction systems. The algorithm is illustrated by an application to a benchmark stochastic differential equation model, and numerical experiments are carried out to demonstrate the effectiveness of the construction.

Computational singular perturbation analysis of stochastic chemical systems with stiffness

DOE PAGES

Wang, Lijin; Han, Xiaoying; Cao, Yanzhao; ...

2017-01-25

Computational singular perturbation (CSP) is a useful method for analysis, reduction, and time integration of stiff ordinary differential equation systems. It has found dominant utility, in particular, in chemical reaction systems with a large range of time scales at continuum and deterministic level. On the other hand, CSP is not directly applicable to chemical reaction systems at micro or meso-scale, where stochasticity plays an non-negligible role and thus has to be taken into account. In this work we develop a novel stochastic computational singular perturbation (SCSP) analysis and time integration framework, and associated algorithm, that can be used to notmore » only construct accurately and efficiently the numerical solutions to stiff stochastic chemical reaction systems, but also analyze the dynamics of the reduced stochastic reaction systems. Furthermore, the algorithm is illustrated by an application to a benchmark stochastic differential equation model, and numerical experiments are carried out to demonstrate the effectiveness of the construction.« less

Stochastic flux analysis of chemical reaction networks

PubMed Central

2013-01-01

Background Chemical reaction networks provide an abstraction scheme for a broad range of models in biology and ecology. The two common means for simulating these networks are the deterministic and the stochastic approaches. The traditional deterministic approach, based on differential equations, enjoys a rich set of analysis techniques, including a treatment of reaction fluxes. However, the discrete stochastic simulations, which provide advantages in some cases, lack a quantitative treatment of network fluxes. Results We describe a method for flux analysis of chemical reaction networks, where flux is given by the flow of species between reactions in stochastic simulations of the network. Extending discrete event simulation algorithms, our method constructs several data structures, and thereby reveals a variety of statistics about resource creation and consumption during the simulation. We use these structures to quantify the causal interdependence and relative importance of the reactions at arbitrary time intervals with respect to the network fluxes. This allows us to construct reduced networks that have the same flux-behavior, and compare these networks, also with respect to their time series. We demonstrate our approach on an extended example based on a published ODE model of the same network, that is, Rho GTP-binding proteins, and on other models from biology and ecology. Conclusions We provide a fully stochastic treatment of flux analysis. As in deterministic analysis, our method delivers the network behavior in terms of species transformations. Moreover, our stochastic analysis can be applied, not only at steady state, but at arbitrary time intervals, and used to identify the flow of specific species between specific reactions. Our cases study of Rho GTP-binding proteins reveals the role played by the cyclic reverse fluxes in tuning the behavior of this network. PMID:24314153

Stochastic flux analysis of chemical reaction networks.

PubMed

Kahramanoğulları, Ozan; Lynch, James F

2013-12-07

Chemical reaction networks provide an abstraction scheme for a broad range of models in biology and ecology. The two common means for simulating these networks are the deterministic and the stochastic approaches. The traditional deterministic approach, based on differential equations, enjoys a rich set of analysis techniques, including a treatment of reaction fluxes. However, the discrete stochastic simulations, which provide advantages in some cases, lack a quantitative treatment of network fluxes. We describe a method for flux analysis of chemical reaction networks, where flux is given by the flow of species between reactions in stochastic simulations of the network. Extending discrete event simulation algorithms, our method constructs several data structures, and thereby reveals a variety of statistics about resource creation and consumption during the simulation. We use these structures to quantify the causal interdependence and relative importance of the reactions at arbitrary time intervals with respect to the network fluxes. This allows us to construct reduced networks that have the same flux-behavior, and compare these networks, also with respect to their time series. We demonstrate our approach on an extended example based on a published ODE model of the same network, that is, Rho GTP-binding proteins, and on other models from biology and ecology. We provide a fully stochastic treatment of flux analysis. As in deterministic analysis, our method delivers the network behavior in terms of species transformations. Moreover, our stochastic analysis can be applied, not only at steady state, but at arbitrary time intervals, and used to identify the flow of specific species between specific reactions. Our cases study of Rho GTP-binding proteins reveals the role played by the cyclic reverse fluxes in tuning the behavior of this network.

Strontium-90 measurement after the Chernobyl accident in Romanian samples without chemical separation

NASA Astrophysics Data System (ADS)

Cosma, C.

2000-07-01

This paper presents a method for measuring 90Sr from soil and sediments without a preliminary chemical separation of strontium from samples. The measurements were done using a Geiger-Müller proportional radiation detector of VA-Z-520 type, an RFT-20026 monochannel analyser and aluminium plates of two thicknesses determined in this way to select the 1500-2281-keV energy range for the 90Y measurement and to avoid the 106Rh interference. The results obtained with this method were compared with those using chemical separation. This method was used to determine the strontium content in four samples, which were collected in Cluj-Napoca and three other Romanian towns (Transylvania region) after the Chernobyl disaster. The obtained values for these samples are in the 40-75-Bq/g range for 90Sr. The 90Sr/ 137Cs ratio is approximately 1:8, close to the ratio 1:10 determined in samples from Bucharest area and Japanese samples measured during 1988.

Chemical composition of wildland and agricultural biomass burning particles measured downwind during the BBOP study

NASA Astrophysics Data System (ADS)

Onasch, T. B.; Shilling, J. E.; Wormhoudt, J.; Sedlacek, A. J., III; Fortner, E.; Pekour, M. S.; Chand, D.; Zhou, S.; Collier, S.; Zhang, Q.; Kleinman, L. I.; Lewis, E. R.; Yokelson, R. J.; Adachi, K.; Buseck, P. R.; Freedman, A.; Williams, L. R.

2017-12-01

The Biomass Burning Observation Project (BBOP), a Department of Energy (DOE) sponsored study, measured emissions from wildland fires in the Pacific Northwest and agricultural burns in the Central Southeastern US from the DOE Gulfstream-1 airborne platform over a four month period in 2013. Rapid physical, chemical and optical changes in biomass burning particles were measured downwind (< 3 hours temporally) from wildland fires. The chemical composition of the particulate emissions was characterized using an Aerodyne Soot Particle Aerosol Mass Spectrometer (SP-AMS) and a Single Particle Soot Photometer (SP2) and the measurement results will be presented in the context of the fire location, combustion conditions, and optical property measurements, including extinction and single scattering albedos. The SP-AMS was operated with both laser and resistively heated tungsten vaporizers, alternating between laser on and off. With the laser vaporizer off, the instrument operated as a standard high resolution AMS. Under these sampling conditions, the non-refractory chemical composition, including the level of oxidation (i.e., O:C, H:C, and organic mass/organic carbon ratios, OM:OC), of the biomass burning particles was characterized as a function of the fuel type burned, modified combustion efficiency, and degree of oxidation during downwind transport. With the laser vaporizer on, the SP-AMS was also sensitive to the refractory black carbon (rBC) content, in addition to the non-refractory components. The chemical measurements will be correlated with simultaneous optical measurements. We will also present preliminary results from laboratory studies on tar balls and SP-AMS OA quantification while operating with both laser and tungsten vaporizers.

Software for analysis of chemical mixtures--composition, occurrence, distribution, and possible toxicity

USGS Publications Warehouse

Scott, Jonathon C.; Skach, Kenneth A.; Toccalino, Patricia L.

2013-01-01

The composition, occurrence, distribution, and possible toxicity of chemical mixtures in the environment are research concerns of the U.S. Geological Survey and others. The presence of specific chemical mixtures may serve as indicators of natural phenomena or human-caused events. Chemical mixtures may also have ecological, industrial, geochemical, or toxicological effects. Chemical-mixture occurrences vary by analyte composition and concentration. Four related computer programs have been developed by the National Water-Quality Assessment Program of the U.S. Geological Survey for research of chemical-mixture compositions, occurrences, distributions, and possible toxicities. The compositions and occurrences are identified for the user-supplied data, and therefore the resultant counts are constrained by the user’s choices for the selection of chemicals, reporting limits for the analytical methods, spatial coverage, and time span for the data supplied. The distribution of chemical mixtures may be spatial, temporal, and (or) related to some other variable, such as chemical usage. Possible toxicities optionally are estimated from user-supplied benchmark data. The software for the analysis of chemical mixtures described in this report is designed to work with chemical-analysis data files retrieved from the U.S. Geological Survey National Water Information System but can also be used with appropriately formatted data from other sources. Installation and usage of the mixture software are documented. This mixture software was designed to function with minimal changes on a variety of computer-operating systems. To obtain the software described herein and other U.S. Geological Survey software, visit http://water.usgs.gov/software/.

Chemical Analysis of Plants that Poison Livestock: Successes, Challenges, and Opportunities.

PubMed

Welch, Kevin D; Lee, Stephen T; Cook, Daniel; Gardner, Dale R; Pfister, James A

2018-04-04

Poisonous plants have a devastating impact on the livestock industry as well as human health. To fully understand the effects of poisonous plants, multiple scientific disciplines are required. Chemical analysis of plant secondary compounds is key to identifying the responsible toxins, characterizing their metabolism, and understanding their effects on animals and humans. In this review, we highlight some of the successes in studying poisonous plants and mitigating their toxic effects. We also highlight some of the remaining challenges and opportunities with regards to the chemical analysis of poisonous plants.

Optical and chemical properties of wildland biomass burning particles measured downwind during the BBOP study

NASA Astrophysics Data System (ADS)

Onasch, Timothy; Wormhoudt, Jody; Sedlacek, Arthur; Chand, Duli; Freedman, Andrew

2017-04-01

Rapid physical, chemical and optical changes in biomass burning particles were measured downwind (< 3 hours temporally) from wildland fires. The Biomass Burning Observation Project (BBOP), sponsored by the U.S. Department of Energy (DOE), involved the measurement of emissions from wildland fires in the Pacific Northwest and agricultural burns in the Central Southeastern United States observed from the DOE Gulfstream-1 airborne platform over a four month period in 2013. Optical instrumentation included a CAPS PMex particle extinction monitor operating at 630 nm (Aerodyne Research), a photothermal interferometer (Brookhaven National Laboratory) measuring particle absorption at 632 nm and a 3 wavelength nephelometer (TSI). Information about the chemical evolution of the plumes was obtained primarily using a SP-AMS (Aerodyne Research) and a Single Particle Soot Photometer (SP2, Droplet Measurements). The chemical composition of the particulate emissions were characterized in the context of the fire location, combustion conditions, and optical property measurements, including extinction and single scattering albedos. The chemical composition of organic aerosol was found to be rapidly changing as a function of downwind location, with oxygen to carbon ratios increasing as a results of atmospheric aging processes (e.g., dilution, photochemistry). The single scattering albedo, (SSA) of plume aerosols increases downwind as the ratio of total particle extinction to carbon monoxide concentration (a marker for the plume dilution) increases, a finding that is related to changes in organic aerosol chemistry.

The Exposure Data Landscape for Manufactured Chemicals ...

EPA Pesticide Factsheets

The U.S. Environmental Protection Agency is developing chemical screening and prioritization programs to evaluate environmental chemicals for potential risk to human health in a rapid and efficient manner. As part of these efforts, it is important to catalog available information on chemical toxicity and exposure from widely dispersed sources. The main objective of this analysis is to define important aspects of the exposure space and to catalog the available exposure information for chemicals being considered for analysis as part of the U.S. EPA ToxCast™ screening and prioritization program. Publicly available exposure data have been extracted into ACToR (Aggregated Computational Toxicology Resource), which combines information for hundreds of thousands of chemicals from >600 public sources. We use data from ACToR to assess the exposure data landscape for environmental chemicals. Of the roughly 100,000 chemicals that have at least limited toxicity information available, less than one-fifth also have exposure information — and for most of these the information is of limited utility (e.g., production volume). Readily accessible data on concentrations in exposure-related media are only available for a much smaller fraction. Among these, the largest number of chemicals is measured in water with over 1150 unique compounds, followed by 788 substances measured in soil, and 670 in air. These small numbers clearly reflect a focus of resources on those substances pre

Indoor air quality in two French hospitals: Measurement of chemical and microbiological contaminants.

PubMed

Baurès, Estelle; Blanchard, Olivier; Mercier, Fabien; Surget, Emilie; le Cann, Pierre; Rivier, Alexandre; Gangneux, Jean-Pierre; Florentin, Arnaud

2018-06-09

In addition to being influenced by the environment, the indoor air pollution in hospitals may be associated with specific compounds emitted from various products used, health care activities and building materials. This study has enabled assessment of the chemical and microbiological concentrations of indoor air in two French hospitals. Based on an integrated approach, the methodology defined aims to measure concentrations of a wide range of chemical compounds (>50 volatile and semi-volatile organic compounds), particle concentrations (PM 10 and PM 2.5 ), microorganisms (fungi, bacteria and viruses) and ambient parameters (temperature, relative humidity, pressure and carbon dioxide). Chemical and microbiological air concentrations were measured during two campaigns (winter and summer) and across seven rooms (for spatial variability). The results have shown that indoor air contains a complex mixture of chemical, physical and microbiological compounds. Concentrations in the same order of magnitude were found in both hospitals. Compared to dwelling indoor air, our study shows low, at least equivalent, contamination for non-hospital specific parameters (aldehydes, limonene, phthalates, aromatic hydrocarbons), which is related to ventilation efficiency. Chemical compounds retrieved at the highest concentration and frequencies are due to healthcare activities, for example alcohol - most commonly ethanol - and hand rubbing (median concentration: ethanol 245.7 μg/m 3 and isopropanol 13.6 μg/m 3 ); toluene and staining in parasitology (highest median concentration in Nancy laboratory: 2.1 μg/m 3 )). Copyright © 2018. Published by Elsevier B.V.

Physical Processes and Real-Time Chemical Measurement of the Insect Olfactory Environment

PubMed Central

Abrell, Leif; Hildebrand, John G.

2009-01-01

Odor-mediated insect navigation in airborne chemical plumes is vital to many ecological interactions, including mate finding, flower nectaring, and host locating (where disease transmission or herbivory may begin). After emission, volatile chemicals become rapidly mixed and diluted through physical processes that create a dynamic olfactory environment. This review examines those physical processes and some of the analytical technologies available to characterize those behavior-inducing chemical signals at temporal scales equivalent to the olfactory processing in insects. In particular, we focus on two areas of research that together may further our understanding of olfactory signal dynamics and its processing and perception by insects. First, measurement of physical atmospheric processes in the field can provide insight into the spatiotemporal dynamics of the odor signal available to insects. Field measurements in turn permit aspects of the physical environment to be simulated in the laboratory, thereby allowing careful investigation into the links between odor signal dynamics and insect behavior. Second, emerging analytical technologies with high recording frequencies and field-friendly inlet systems may offer new opportunities to characterize natural odors at spatiotemporal scales relevant to insect perception and behavior. Characterization of the chemical signal environment allows the determination of when and where olfactory-mediated behaviors may control ecological interactions. Finally, we argue that coupling of these two research areas will foster increased understanding of the physicochemical environment and enable researchers to determine how olfactory environments shape insect behaviors and sensory systems. PMID:18548311

Flow Injection Analysis and Liquid Chromatography for Multifunctional Chemical Analysis (MCA) Systems

ERIC Educational Resources Information Center

Mayo, Ana V.; Loegel, Thomas N.; Bretz, Stacey Lowery; Danielson, Neil D.

2013-01-01

The large class sizes of first-year chemistry labs makes it challenging to provide students with hands-on access to instrumentation because the number of students typically far exceeds the number of research-grade instruments available to collect data. Multifunctional chemical analysis (MCA) systems provide a viable alternative for large-scale…

Evolutionary toxicology: Meta-analysis of evolutionary events in response to chemical stressors.

PubMed

M Oziolor, Elias; De Schamphelaere, Karel; Matson, Cole W

2016-12-01

The regulatory decision-making process regarding chemical safety is most often informed by evidence based on ecotoxicity tests that consider growth, reproduction and survival as end-points, which can be quantitatively linked to short-term population outcomes. Changes in these end-points resulting from chemical exposure can cause alterations in micro-evolutionary forces (mutation, drift, selection and gene flow) that control the genetic composition of populations. With multi-generation exposures, anthropogenic contamination can lead to a population with an altered genetic composition, which may respond differently to future stressors. These evolutionary changes are rarely discussed in regulatory or risk assessment frameworks, but the growing body of literature that documents their existence suggests that these important population-level impacts should be considered. In this meta-analysis we have compared existing contamination levels of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) that have been documented to be associated with evolutionary changes in resident aquatic organisms to regulatory benchmarks for these contaminants. The original intent of this project was to perform a meta-analysis on evolutionary events associated with PCB and PAH contamination. However, this effort was hindered by a lack of consistency in congener selection for "total" PCB or PAH measurements. We expanded this manuscript to include a discussion of methods used to determine PCB and PAH total contamination in addition to comparing regulatory guidelines and contamination that has caused evolutionary effects. Micro-evolutionary responses often lead populations onto unique and unpredictable trajectories. Therefore, to better understand the risk of population-wide alterations occurring, we need to improve comparisons of chemical contamination between affected locations. In this manuscript we offer several possibilities to unify chemical comparisons for PCBs and

Integrated cost-effectiveness analysis of agri-environmental measures for water quality.

PubMed

Balana, Bedru B; Jackson-Blake, Leah; Martin-Ortega, Julia; Dunn, Sarah

2015-09-15

This paper presents an application of integrated methodological approach for identifying cost-effective combinations of agri-environmental measures to achieve water quality targets. The methodological approach involves linking hydro-chemical modelling with economic costs of mitigation measures. The utility of the approach was explored for the River Dee catchment in North East Scotland, examining the cost-effectiveness of mitigation measures for nitrogen (N) and phosphorus (P) pollutants. In-stream nitrate concentration was modelled using the STREAM-N and phosphorus using INCA-P model. Both models were first run for baseline conditions and then their effectiveness for changes in land management was simulated. Costs were based on farm income foregone, capital and operational expenditures. The costs and effects data were integrated using 'Risk Solver Platform' optimization in excel to produce the most cost-effective combination of measures by which target nutrient reductions could be attained at a minimum economic cost. The analysis identified different combination of measures as most cost-effective for the two pollutants. An important aspect of this paper is integration of model-based effectiveness estimates with economic cost of measures for cost-effectiveness analysis of land and water management options. The methodological approach developed is not limited to the two pollutants and the selected agri-environmental measures considered in the paper; the approach can be adapted to the cost-effectiveness analysis of any catchment-scale environmental management options. Copyright © 2015 Elsevier Ltd. All rights reserved.

Analysis of the multiple system with chemically peculiar component φ Draconis

NASA Astrophysics Data System (ADS)

Liška, J.

2016-09-01

The star ϕ Dra comprises a spectroscopic binary and a third star that together form a visual triple system. It is one of the brightest chemically peculiar stars of the upper main sequence. Despite these facts, no comprehensive study of its multiplicity has been performed yet. In this work, we present a detailed analysis of the triple system based on available measurements. We use radial velocities taken from four sources in the literature in a re-analysis of the inner spectroscopic binary (Aab). An incorrect value of the orbital period of the inner system Aab about 27 d was accepted in literature more than 40 yr. A new solution of orbit with the 128-d period was determined. Relative position measurements of the outer visual binary system (AB) from Washington Double Star Catalog were compared with known orbital models. Furthermore, it was shown that astrometric motion in system AB is well described by the model of Andrade with a 308-yr orbital period. Parameters of A and B components were utilized to estimate individual brightness for all components and their masses from evolutionary tracks. Although we found several facts which support the gravitational bond between them, unbound solution cannot be fully excluded yet.

Validation of minicams for measuring concentrations of chemical agent in environmental air

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

Menton, R.G.; Hayes, T.L.; Chou, Y.L.

1993-05-13

Environmental monitoring for chemical agents is necessary to ensure that notification and appropriate action will be taken in the, event that there is a release exceeding control limits of such agents into the workplace outside of engineering controls. Prior to implementing new analytical procedures for environmental monitoring, precision and accuracy (PA) tests are conducted to ensure that an agent monitoring system performs according to specified accuracy, precision, and sensitivity requirements. This testing not only establishes the accuracy and precision of the method, but also determines what factors can affect the method's performance. Performance measures that are particularly important in agentmore » monitoring include the Detection Limit (DL), Decision Limit (DC), Found Action Level (FAL), and the Target Action Level (TAL). PA experiments were performed at Battelle's Medical Research and Evaluation Facility (MREF) to validate the use of the miniature chemical agent monitoring system (MINICAMs) for measuring environmental air concentrations of sulfur mustard (HD). This presentation discusses the experimental and statistical approaches for characterizing the performance of MINICAMS for measuring HD in air.« less

Hydrogen fluoride (HF) substance flow analysis for safe and sustainable chemical industry.

PubMed

Kim, Junbeum; Hwang, Yongwoo; Yoo, Mijin; Chen, Sha; Lee, Ik-Mo

2017-11-01

In this study, the chemical substance flow of hydrogen fluoride (hydrofluoric acid, HF) in domestic chemical industries in 2014 was analyzed in order to provide a basic material and information for the establishment of organized management system to ensure safety during HF applications. A total of 44,751 tons of HF was made by four domestic companies (in 2014); import amount was 95,984 tons in 2014 while 21,579 tons of HF was imported in 2005. The export amount of HF was 2180 tons, of which 2074 ton (China, 1422 tons, U.S. 524 tons, and Malaysia, 128 tons) was exported for the manufacturing of semiconductors. Based on the export and import amounts, it can be inferred that HF was used for manufacturing semiconductors. The industries applications of 161,123 tons of HF were as follows: manufacturing of basic inorganic chemical substance (27,937 tons), manufacturing of other chemical products such as detergents (28,208 tons), manufacturing of flat display (24,896 tons), and manufacturing of glass container package (22,002 tons). In this study, an analysis of the chemical substance flow showed that HF was mainly used in the semiconductor industry as well as glass container manufacturing. Combined with other risk management tools and approaches in the chemical industry, the chemical substance flow analysis (CSFA) can be a useful tool and method for assessment and management. The current CSFA results provide useful information for policy making in the chemical industry and national systems. Graphical abstract Hydrogen fluoride chemical substance flows in 2014 in South Korea.

A novel method to measure conspicuous facial pores using computer analysis of digital-camera-captured images: the effect of glycolic acid chemical peeling.

PubMed

Kakudo, Natsuko; Kushida, Satoshi; Tanaka, Nobuko; Minakata, Tatsuya; Suzuki, Kenji; Kusumoto, Kenji

2011-11-01

Chemical peeling is becoming increasingly popular for skin rejuvenation in dermatological esthetic surgery. Conspicuous facial pores are one of the most frequently encountered skin problems in women of all ages. This study was performed to analyze the effectiveness of reducing conspicuous facial pores using glycolic acid chemical peeling (GACP) based on a novel computer analysis of digital-camera-captured images. GACP was performed a total of five times at 2-week intervals in 22 healthy women. Computerized image analysis of conspicuous, open, and darkened facial pores was performed using the Robo Skin Analyzer CS 50. The number of conspicuous facial pores decreased significantly in 19 (86%) of the 22 subjects, with a mean improvement rate of 34.6%. The number of open pores decreased significantly in 16 (72%) of the subjects, with a mean improvement rate of 11.0%. The number of darkened pores decreased significantly in 18 (81%) of the subjects, with a mean improvement rate of 34.3%. GACP significantly reduces the number of conspicuous facial pores. The Robo Skin Analyzer CS 50 is useful for the quantification and analysis of 'pore enlargement', a subtle finding in dermatological esthetic surgery. © 2011 John Wiley & Sons A/S.

Analysis of the Precursors, Simulants and Degradation Products of Chemical Warfare Agents.

PubMed

Witkiewicz, Zygfryd; Neffe, Slawomir; Sliwka, Ewa; Quagliano, Javier

2018-09-03

Recent advances in analysis of precursors, simulants and degradation products of chemical warfare agents (CWA) are reviewed. Fast and reliable analysis of precursors, simulants and CWA degradation products is extremely important at a time, when more and more terrorist groups and radical non-state organizations use or plan to use chemical weapons to achieve their own psychological, political and military goals. The review covers the open source literature analysis after the time, when the chemical weapons convention had come into force (1997). The authors stated that during last 15 years increased number of laboratories are focused not only on trace analysis of CWA (mostly nerve and blister agents) in environmental and biological samples, but the growing number of research are devoted to instrumental analysis of precursors and degradation products of these substances. The identification of low-level concentration of CWA degradation products is often more important and difficult than the original CWA, because of lower level of concentration and a very large number of compounds present in environmental and biological samples. Many of them are hydrolysis products and are present in samples in the ionic form. For this reason, two or three instrumental methods are used to perform a reliable analysis of these substances.

Chemical analysis of Panax quinquefolius (North American ginseng): A review.

PubMed

Wang, Yaping; Choi, Hyung-Kyoon; Brinckmann, Josef A; Jiang, Xue; Huang, Linfang

2015-12-24

Panax quinquefolius (PQ) is one of the best-selling natural health products due to its proposed beneficial anti-aging, anti-cancer, anti-stress, anti-fatigue, and anxiolytic effects. In recent years, the quality of PQ has received considerable attention. Sensitive and accurate methods for qualitative and quantitative analyses of chemical constituents are necessary for the comprehensive quality control to ensure the safety and efficacy of PQ. This article reviews recent progress in the chemical analysis of PQ and its preparations. Numerous analytical techniques, including spectroscopy, thin-layer chromatography (TLC), gas chromatography (GC), high-performance liquid chromatography (HPLC), liquid chromatography/mass spectrometry (LC/MS), high-speed centrifugal partition chromatography (HSCPC), high-performance counter-current chromatography (HPCCC), nuclear magnetic resonance spectroscopy (NMR), and immunoassay, are described. Among these techniques, HPLC coupled with mass spectrometry (MS) is the most promising method for quality control. The challenges encountered in the chemical analysis of PQ are also briefly discussed, and the remaining questions regarding the quality control of PQ that require further investigation are highlighted. Copyright © 2015 Elsevier B.V. All rights reserved.

Instrument for the measurement and determination of chemical pulse column parameters

DOEpatents

Marchant, Norman J.; Morgan, John P.

1990-01-01

An instrument for monitoring and measuring pneumatic driving force pulse parameters applied to chemical separation pulse columns obtains real time pulse frequency and root mean square amplitude values, calculates column inch values and compares these values against preset limits to alert column operators to the variations of pulse column operational parameters beyond desired limits.

Evolution of Quantitative Measures in NMR: Quantum Mechanical qHNMR Advances Chemical Standardization of a Red Clover (Trifolium pratense) Extract

PubMed Central

2017-01-01

Chemical standardization, along with morphological and DNA analysis ensures the authenticity and advances the integrity evaluation of botanical preparations. Achievement of a more comprehensive, metabolomic standardization requires simultaneous quantitation of multiple marker compounds. Employing quantitative 1H NMR (qHNMR), this study determined the total isoflavone content (TIfCo; 34.5–36.5% w/w) via multimarker standardization and assessed the stability of a 10-year-old isoflavone-enriched red clover extract (RCE). Eleven markers (nine isoflavones, two flavonols) were targeted simultaneously, and outcomes were compared with LC-based standardization. Two advanced quantitative measures in qHNMR were applied to derive quantities from complex and/or overlapping resonances: a quantum mechanical (QM) method (QM-qHNMR) that employs 1H iterative full spin analysis, and a non-QM method that uses linear peak fitting algorithms (PF-qHNMR). A 10 min UHPLC-UV method provided auxiliary orthogonal quantitation. This is the first systematic evaluation of QM and non-QM deconvolution as qHNMR quantitation measures. It demonstrates that QM-qHNMR can account successfully for the complexity of 1H NMR spectra of individual analytes and how QM-qHNMR can be built for mixtures such as botanical extracts. The contents of the main bioactive markers were in good agreement with earlier HPLC-UV results, demonstrating the chemical stability of the RCE. QM-qHNMR advances chemical standardization by its inherent QM accuracy and the use of universal calibrants, avoiding the impractical need for identical reference materials. PMID:28067513

Equatorial F region neutral winds and shears near sunset measured with chemical release techniques

NASA Astrophysics Data System (ADS)

Kiene, A.; Larsen, M. F.; Kudeki, E.

2015-10-01

The period near sunset is a dynamic and critical time for the daily development of the equatorial nighttime ionosphere and the instabilities that occur there. It is during these hours that the preconditions necessary for the later development of Equatorial Spread F (ESF) plasma instabilities occur. The neutral dynamics of the sunset ionosphere are also of critical importance to the generation of currents and electric fields; however, the behavior of the neutrals is experimentally understood primarily through very limited single-altitude measurements or measurements that provide weighted altitude means of the winds as a function of time. To date, there have been very few vertically resolved neutral wind measurements in the F region at sunset. We present two sets of sounding rocket chemical release measurements, one from a launch in the Marshall Islands on Kwajalein atoll and one from Alcantara, Brazil. Analysis of the release motions has yielded vertically resolved neutral wind profiles that show both the mean horizontal winds and the vertical shears in the winds. In both experiments, we observe significant vertical gradients in the zonal wind that are unexpected by classical assumptions about the behavior of the neutral wind at these altitudes at sunset near the geomagnetic equator.

Search for Chemical Biomarkers on Mars Using the Sample Analysis at Mars Instrument Suite on the Mars Science Laboratory

NASA Technical Reports Server (NTRS)

Glavin, D. P.; Conrad, P.; Dworkin, J. P.; Eigenbrode, J.; Mahaffy, P. R.

2011-01-01

One key goal for the future exploration of Mars is the search for chemical biomarkers including complex organic compounds important in life on Earth. The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) will provide the most sensitive measurements of the organic composition of rocks and regolith samples ever carried out in situ on Mars. SAM consists of a gas chromatograph (GC), quadrupole mass spectrometer (QMS), and tunable laser spectrometer to measure volatiles in the atmosphere and released from rock powders heated up to 1000 C. The measurement of organics in solid samples will be accomplished by three experiments: (1) pyrolysis QMS to identify alkane fragments and simple aromatic compounds; pyrolysis GCMS to separate and identify complex mixtures of larger hydrocarbons; and (3) chemical derivatization and GCMS extract less volatile compounds including amino and carboxylic acids that are not detectable by the other two experiments.

Noncatalytic thermocouple coatings produced with chemical vapor deposition for flame temperature measurements.

PubMed

Bahlawane, N; Struckmeier, U; Kasper, T S; Osswald, P

2007-01-01

Chemical vapor deposition (CVD) and metal-organic chemical vapor deposition (MOCVD) have been employed to develop alumina thin films in order to protect thermocouples from catalytic overheating in flames and to minimize the intrusion presented to the combustion process. Alumina films obtained with a CVD process using AlCl(3) as the precursor are dense, not contaminated, and crystallize in the corundum structure, while MOCVD using Al(acetyl acetone)(3) allows the growth of corundum alumina with improved growth rates. These films, however, present a porous columnar structure and show some carbon contamination. Therefore, coated thermocouples using AlCl(3)-CVD were judged more suitable for flame temperature measurements and were tested in different fuels over a typical range of stoichiometries. Coated thermocouples exhibit satisfactory measurement reproducibility, no temporal drifts, and do not suffer from catalytic effects. Furthermore, their increased radiative heat loss (observed by infrared spectroscopy) allows temperature measurements over a wider range when compared to uncoated thermocouples. A flame with a well-known temperature profile established with laser-based techniques was used to determine the radiative heat loss correction to account for the difference between the apparent temperature measured by the coated thermocouple and the true flame temperature. The validity of the correction term was confirmed with temperature profile measurements for several flames previously studied in different laboratories with laser-based techniques.

A Novel Thermal Sensor for the Sensitive Measurement of Chemical Oxygen Demand

PubMed Central

Yao, Na; Liu, Zhuan; Chen, Ying; Zhou, Yikai; Xie, Bin

2015-01-01

A novel rapid methodology for determining the chemical oxygen demand (COD) based on a thermal sensor with a flow injection analysis system was proposed and experimentally validated. The ability of this sensor to detect and monitor COD was based on the degree of enthalpy increase when sodium hypochlorite reacted with the organic content in water samples. The measurement results were correlated with COD and were compared against the conventional method using potassium dichromate. The assay required only 5–7 min rather than the 2 h required for evaluation by potassium dichromate. The linear range was 5–1000 mg/L COD, and the limit of detection was very low, 0.74 mg/L COD. Moreover, this method exhibited high tolerance to chloride ions; 0.015 mol/L chloride ions had no influence on the response. Finally, the sensor was used to detect the COD of different water samples; the results were verified by the standard dichromate method. PMID:26295397

Risk management measures for chemicals: the "COSHH essentials" approach.

PubMed

Garrod, A N I; Evans, P G; Davy, C W

2007-12-01

"COSHH essentials" was developed in Great Britain to help duty holders comply with the Control of Substances Hazardous to Health (COSHH) Regulations. It uses a similar approach to that described in the new European "REACH" Regulation (Registration, Evaluation, Authorisation and Restriction of Chemicals; EC No. 1907/2006 of the European Parliament), insofar as it identifies measures for managing the risk for specified exposure scenarios. It can therefore assist REACH duty holders with the identification and communication of appropriate risk-management measures. The technical basis for COSHH essentials is explained in the original papers published in the Annals of Occupational Hygiene. Its details will, therefore, not be described here; rather, its ability to provide a suitable means for communicating risk-management measures will be explored. COSHH essentials is a simple tool based on an empirical approach to risk assessment and risk management. The output is a "Control Guidance Sheet" that lists the "dos" and "don'ts" for control in a specific task scenario. The guidance in COSHH essentials recognises that exposure in the workplace will depend not just on mechanical controls, but also on a number of other factors, including administrative and behavioural controls, such as systems of work, supervision and training. In 2002, COSHH essentials was made freely available via the internet (http://www.coshh-essentials.org.uk/). This electronic delivery enabled links to be made between product series that share tasks, such as drum filling, and with ancillary guidance, such as setting up health surveillance for work with a respiratory sensitiser. COSHH essentials has proved to be a popular tool for communicating good control practice. It has attracted over 1 million visits to its site since its launch. It offers a common benchmark of good practice for chemical users, manufacturers, suppliers and importers, as well as regulators and health professionals.

Droplet activation, separation, and compositional analysis: laboratory studies and atmospheric measurements

NASA Astrophysics Data System (ADS)

Hiranuma, N.; Kohn, M.; Pekour, M. S.; Nelson, D. A.; Shilling, J. E.; Cziczo, D. J.

2011-10-01

Droplets produced in a cloud condensation nuclei chamber (CCNC) as a function of supersaturation have been separated from unactivated aerosol particles using counterflow virtual impaction. Residual material after droplets were evaporated was chemically analyzed with an Aerodyne Aerosol Mass Spectrometer (AMS) and the Particle Analysis by Laser Mass Spectrometry (PALMS) instrument. Experiments were initially conducted to verify activation conditions for monodisperse ammonium sulfate particles and to determine the resulting droplet size distribution as a function of supersaturation. Based on the observed droplet size, the counterflow virtual impactor cut-size was set to differentiate droplets from unactivated interstitial particles. Validation experiments were then performed to verify that only droplets with sufficient size passed through the counterflow virtual impactor for subsequent analysis. A two-component external mixture of monodisperse particles was also exposed to a supersaturation which would activate one of the types (hygroscopic salts) but not the other (polystyrene latex spheres or adipic acid). The mass spectrum observed after separation indicated only the former, validating separation of droplets from unactivated particles. Results from ambient measurements using this technique and AMS analysis were inconclusive, showing little chemical differentiation between ambient aerosol and activated droplet residuals, largely due to low signal levels. When employing as single particle mass spectrometer for compositional analysis, however, we observed enhancement of sulfate in droplet residuals.

Neutron activation analysis: A primary method of measurement

NASA Astrophysics Data System (ADS)

Greenberg, Robert R.; Bode, Peter; De Nadai Fernandes, Elisabete A.

2011-03-01

Neutron activation analysis (NAA), based on the comparator method, has the potential to fulfill the requirements of a primary ratio method as defined in 1998 by the Comité Consultatif pour la Quantité de Matière — Métrologie en Chimie (CCQM, Consultative Committee on Amount of Substance — Metrology in Chemistry). This thesis is evidenced in this paper in three chapters by: demonstration that the method is fully physically and chemically understood; that a measurement equation can be written down in which the values of all parameters have dimensions in SI units and thus having the potential for metrological traceability to these units; that all contributions to uncertainty of measurement can be quantitatively evaluated, underpinning the metrological traceability; and that the performance of NAA in CCQM key-comparisons of trace elements in complex matrices between 2000 and 2007 is similar to the performance of Isotope Dilution Mass Spectrometry (IDMS), which had been formerly designated by the CCQM as a primary ratio method.

International Research Project on the Effects of Chemical Ageing of Polymers on Performance Properties: Chemical and Thermal Analysis

NASA Technical Reports Server (NTRS)

Bulluck, J. W.; Rushing, R. A.

1996-01-01

Work during the past six months has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted small changes in the molecular weight distribution. Again these changes may result in variations in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, Ultra- Violet Scanning Analysis, GC/Mass Spectrometry, Differential Scanning Calorimetry and Thermomechanical Analysis. In the ultra-violet analysis we noted the presence of an absorption band indicative of triene formation. We investigated a number of aged samples of both Tefzel and Coflon that were forwarded from MERL. We also cast films at SWT and subjected these films to a refluxing methanol 1% ethylene diamine solution. An updated literature search was conducted using Dialog and DROLLS to identify any new papers that may have been published in the open literature since the start of this project. The updated literature search and abstracts are contained in the Appendix section of this report.

Intercomparison of an Aerosol Chemical Speciation Monitor (ACSM) with ambient fine aerosol measurements in downtown Atlanta, Georgia

NASA Astrophysics Data System (ADS)

Budisulistiorini, S. H.; Canagaratna, M. R.; Croteau, P. L.; Baumann, K.; Edgerton, E. S.; Kollman, M. S.; Ng, N. L.; Verma, V.; Shaw, S. L.; Knipping, E. M.; Worsnop, D. R.; Jayne, J. T.; Weber, R. J.; Surratt, J. D.

2014-07-01

Currently, there are a limited number of field studies that evaluate the long-term performance of the Aerodyne Aerosol Chemical Speciation Monitor (ACSM) against established monitoring networks. In this study, we present seasonal intercomparisons of the ACSM with collocated fine aerosol (PM2.5) measurements at the Southeastern Aerosol Research and Characterization (SEARCH) Jefferson Street (JST) site near downtown Atlanta, GA, during 2011-2012. Intercomparison of two collocated ACSMs resulted in strong correlations (r2 > 0.8) for all chemical species, except chloride (r2 = 0.21) indicating that ACSM instruments are capable of stable and reproducible operation. In general, speciated ACSM mass concentrations correlate well (r2 > 0.7) with the filter-adjusted continuous measurements from JST, although the correlation for nitrate is weaker (r2 = 0.55) in summer. Correlations of the ACSM NR-PM1 (non-refractory particulate matter with aerodynamic diameter less than or equal to 1 μm) plus elemental carbon (EC) with tapered element oscillating microbalance (TEOM) PM2.5 and Federal Reference Method (FRM) PM1 mass are strong with r2 > 0.7 and r2 > 0.8, respectively. Discrepancies might be attributed to evaporative losses of semi-volatile species from the filter measurements used to adjust the collocated continuous measurements. This suggests that adjusting the ambient aerosol continuous measurements with results from filter analysis introduced additional bias to the measurements. We also recommend to calibrate the ambient aerosol monitoring instruments using aerosol standards rather than gas-phase standards. The fitting approach for ACSM relative ionization for sulfate was shown to improve the comparisons between ACSM and collocated measurements in the absence of calibrated values, suggesting the importance of adding sulfate calibration into the ACSM calibration routine.

Chemical and Thermal Analysis

NASA Technical Reports Server (NTRS)

Bulluck, J. W.; Rushing, R. A.

1995-01-01

During the past six months we have conducted significant research in several domains in order to clarify and understanding the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. We organized numerous analytical studies with methods including Fourier Transform Infrared Spectroscopy, Dynamic Mechanical Analysis, Differential Scanning Calorimetry, and Stress Relaxation experiments. In addition we have reanalyzed previous thermogravimetric data concerning the rate of deplasticization of Coflon pipe. We investigated a number of aged samples of both Tefzel and Coflon that were forwarded from MERL. We conducted stress relaxation experiments of Coflon pipe at several temperatures and determined an activation energy. We also examined the dynamic mechanical response PVDF during deplasticization and during methanol plasticization. We performed numerous DSC analyses to research the changing crystalline morphology. We have noted significant changes in crystallinity upon aging for both PVDF and Tefzel. Little variation in elemental composition was noted for many of the aged Coflon and Tefzel samples tested.

The ambient organic aerosol soluble in water: Measurements, chemical characterization, and an investigation of sources

NASA Astrophysics Data System (ADS)

Sullivan, Amy P.

This thesis characterizes the ambient fine organic carbon (OC) aerosol and investigates its sources through the development and deployment of new analytical measurement techniques. Recognizing that OC is highly chemically complex, the approach was to develop methods capable of quantitatively measuring a large chemical fraction of the aerosol instead of specific chemical speciation. The focus is on organic compounds that are soluble in water (WSOC) since little is known about its chemical nature. The results from this thesis show that WSOC has mainly two sources: biomass burning and secondary organic aerosol (SOA). In urban areas, WSOC increases with plume age, and tracks other photochemically produced compounds. Chemical analysis of WSOC suggests that in urban Atlanta, the SOA is mainly small-chain aliphatic compounds indirectly linked to vehicle emissions. A method was first developed for quantitative on-line measurements of WSOC by extending the application of the Particle-into-Liquid Sampler (PILS) from inorganic to organic aerosol measurements. In this approach a PILS captures ambient particles into a flow of purified water, which is then forced through a liquid filter and the carbonaceous content quantified on-line by a Total Organic Carbon (TOC) analyzer. An instrument was first developed for ground-based measurements and then modified for airborne deployment. Ground-based measurements at the St. Louis - Midwest Supersite during the summer of 2003 showed that the fraction of OC that is water-soluble can have a highly diurnal pattern with WSOC to OC ratios reaching 0.80 during the day and lows of 0.40 during the night. During extended periods under stagnation pollution events, this pattern was well correlated with ozone concentrations. The results are consistent with formation of SOA. Airborne PILS-TOC measurements from the NOAA WP-3D during the New England Air Quality Study/Intercontinental Transport and Chemical Transformation (NEAQS/ITCT) 2004 program

Phthalic acid chemical probes synthesized for protein-protein interaction analysis.

PubMed

Liang, Shih-Shin; Liao, Wei-Ting; Kuo, Chao-Jen; Chou, Chi-Hsien; Wu, Chin-Jen; Wang, Hui-Min

2013-06-24

Plasticizers are additives that are used to increase the flexibility of plastic during manufacturing. However, in injection molding processes, plasticizers cannot be generated with monomers because they can peel off from the plastics into the surrounding environment, water, or food, or become attached to skin. Among the various plasticizers that are used, 1,2-benzenedicarboxylic acid (phthalic acid) is a typical precursor to generate phthalates. In addition, phthalic acid is a metabolite of diethylhexyl phthalate (DEHP). According to Gene_Ontology gene/protein database, phthalates can cause genital diseases, cardiotoxicity, hepatotoxicity, nephrotoxicity, etc. In this study, a silanized linker (3-aminopropyl triethoxyslane, APTES) was deposited on silicon dioxides (SiO2) particles and phthalate chemical probes were manufactured from phthalic acid and APTES-SiO2. These probes could be used for detecting proteins that targeted phthalic acid and for protein-protein interactions. The phthalic acid chemical probes we produced were incubated with epithelioid cell lysates of normal rat kidney (NRK-52E cells) to detect the interactions between phthalic acid and NRK-52E extracted proteins. These chemical probes interacted with a number of chaperones such as protein disulfide-isomerase A6, heat shock proteins, and Serpin H1. Ingenuity Pathways Analysis (IPA) software showed that these chemical probes were a practical technique for protein-protein interaction analysis.

Optofluidic Microsystems for Chemical and Biological Analysis

PubMed Central

Fan, Xudong; White, Ian M.

2011-01-01

Optofluidics – the synergistic integration of photonics and microfluidics – has recently emerged as a new analytical field that provides a number of unique characteristics for enhanced sensing performance and simplification of microsystems. In this review, we describe various optofluidic architectures developed in the past five years, emphasize the mechanisms by which optofluidics enhances bio/chemical analysis capabilities, including sensing and the precise control of biological micro/nanoparticles, and envision new research directions to which optofluidics leads. PMID:22059090

Diagnostic Chemical Analysis of Exhaled Human Breath Using a Novel Sub-Millimeter Spectroscopic Approach

NASA Astrophysics Data System (ADS)

Fosnight, Alyssa M.; Moran, Benjamin L.; Branco, Daniela R.; Thomas, Jessica R.; Medvedev, Ivan R.

2013-06-01

As many as 3000 chemicals are reported to be found in exhaled human breath. Many of these chemicals are linked to certain health conditions and environmental exposures. Present state of the art techniques used for analysis of exhaled human breath include mass spectrometry based methods, infrared spectroscopic sensors, electro chemical sensors and semiconductor oxide based testers. Some of these techniques are commercially available but are somewhat limited in their specificity and exhibit fairly high probability of false alarm. Here, we present the results of our most recent study which demonstrated a novel application of a terahertz high resolutions spectroscopic technique to the analysis of exhaled human breath, focused on detection of ethanol in the exhaled breath of a person which consumed an alcoholic drink. This technique possesses nearly ``absolute'' specificity and we demonstrated its ability to uniquely identify ethanol, methanol, and acetone in human breath. This project is now complete and we are looking to extend this method of chemical analysis of exhaled human breath to a broader range of chemicals in an attempt to demonstrate its potential for biomedical diagnostic purposes.

Possibility of successive SRXFA use along with chemical-spectral methods for palladium analysis in geological samples

NASA Astrophysics Data System (ADS)

Kislov, E. V.; Kulikov, A. A.; Kulikova, A. B.

1989-10-01

Samples of basit-ultrabasit rocks and NiCu ores of the Ioko-Dovyren and Chaya massifs were analysed by SRXFA and a chemical-spectral method. SRXFA perfectly satisfies the quantitative noble-metals analysis of ore-free rocks. Combination of SRXFA and chemical-spectral analysis has good prospects. After analysis of a great number of samples by SRXFA it is necessary to select samples which would show minimal and maximal results for the chemical-spectral method.

Flow Velocity Computation, from Temperature and Number Density Measurements using Spontaneous Raman Scattering, for Supersonic Chemically Reacting Flows.

NASA Astrophysics Data System (ADS)

Satish Jeyashekar, Nigil; Seiner, John

2006-11-01

The closure problem in chemically reacting turbulent flows would be solved when velocity, temperature and number density (transport variables) are known. The transport variables provide input to momentum, heat and mass transport equations leading to analysis of turbulence-chemistry interaction, providing a pathway to improve combustion efficiency. There are no measurement techniques to determine all three transport variables simultaneously. This paper shows the formulation to compute flow velocity from temperature and number density measurements, made from spontaneous Raman scattering, using kinetic theory of dilute gases coupled with Maxwell-Boltzmann velocity distribution. Temperature and number density measurements are made in a mach 1.5 supersonic air flow with subsonic hydrogen co-flow. Maxwell-Boltzmann distribution can be used to compute the average molecular velocity of each species, which in turn is used to compute the mass-averaged velocity or flow velocity. This formulation was validated by Raman measurements in a laminar adiabatic burner where the computed flow velocities were in good agreement with hot-wire velocity measurements.

Naval Research Laboratory Industrial Chemical Analysis and Respiratory Filter Standards Development

DTIC Science & Technology

2017-09-29

Filter Standards Development September 29, 2017 Approved for public release; distribution is unlimited. Thomas E. suTTo Materials and Systems Branch...LIMITATION OF ABSTRACT Naval Research Laboratory Industrial Chemical Analysis and Respiratory Filter Standards Development Thomas E. Sutto Naval Research...approach, developed by NRL, is tested by examining the filter behavior against a number of chemicals to determine if the NRL approach resulted in the

Pretreatment and integrated analysis of spectral data reveal seaweed similarities based on chemical diversity.

PubMed

Wei, Feifei; Ito, Kengo; Sakata, Kenji; Date, Yasuhiro; Kikuchi, Jun

2015-03-03

Extracting useful information from high dimensionality and large data sets is a major challenge for data-driven approaches. The present study was aimed at developing novel integrated analytical strategies for comprehensively characterizing seaweed similarities based on chemical diversity. The chemical compositions of 107 seaweed and 2 seagrass samples were analyzed using multiple techniques, including Fourier transform infrared (FT-IR) and solid- and solution-state nuclear magnetic resonance (NMR) spectroscopy, thermogravimetry-differential thermal analysis (TG-DTA), inductively coupled plasma-optical emission spectrometry (ICP-OES), CHNS/O total elemental analysis, and isotope ratio mass spectrometry (IR-MS). The spectral data were preprocessed using non-negative matrix factorization (NMF) and NMF combined with multivariate curve resolution-alternating least-squares (MCR-ALS) methods in order to separate individual component information from the overlapping and/or broad spectral peaks. Integrated analysis of the preprocessed chemical data demonstrated distinct discrimination of differential seaweed species. Further network analysis revealed a close correlation between the heavy metal elements and characteristic components of brown algae, such as cellulose, alginic acid, and sulfated mucopolysaccharides, providing a componential basis for its metal-sorbing potential. These results suggest that this integrated analytical strategy is useful for extracting and identifying the chemical characteristics of diverse seaweeds based on large chemical data sets, particularly complicated overlapping spectral data.

Petroleomics: the next grand challenge for chemical analysis.

PubMed

Marshall, Alan G; Rodgers, Ryan P

2004-01-01

Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry has recently revealed that petroleum crude oil contains heteroatom-containing (N,O,S) organic components having more than 20,000 distinct elemental compositions (C(c)H(h)N(n)O(o)S(s)). It is therefore now possible to contemplate the ultimate characterization of all of the chemical constituents of petroleum, along with their interactions and reactivity, a concept we denote as "petroleomics". Such knowledge has already proved capable of distinguishing petroleum and its distillates according to their geochemical origin and maturity, distillation cut, extraction method, catalytic processing, etc. The key features that have opened up this new field have been (a) ultrahigh-resolution FT-ICR mass analysis, specifically, the capability to resolve species differing in elemental composition by C(3) vs SH(4) (i.e., 0.0034 Da); (b) higher magnetic field to cover the whole mass range at once; (c) dynamic range extension by external mass filtering; and (d) plots of Kendrick mass defect vs nominal Kendrick mass as a means for sorting different compound "classes" (i.e., numbers of N, O, and S atoms), "types" (rings plus double bonds), and alkylation ((-CH(2))(n)) distributions, thereby extending to >900 Da the upper limit for unique assignment of elemental composition based on accurate mass measurement. The same methods are also being applied successfully to analysis of humic and fulvic acids, coals, and other complex natural mixtures, often without prior or on-line chromatographic separation.

Risk Analysis in Support of the Chemical Stockpile Disposal Program. Volume 1. Analysis

DTIC Science & Technology

1987-12-17

Analysis of Event Probability A-14 A.4.2 Analysis of Event Consequence A-14 A.4.2.1 Agent Release to Atmosphere A-14 A.4.2.2 Toxic P-lume Size A-16 A...Disposal Program (CSDP), which comprises several alternatives for carrying out the disposal effort (U.S. Army Toxic and Hazardous Materials Agency, 1986...or unavoidable accident or event could occur that would expose a nearby civilian population to these toxic chemicals. Such events could occur even

Chemical Ionization Mass Spectrometry-Based Measurements of HO2 and RO2 During TRACE-P

NASA Technical Reports Server (NTRS)

Cantrell, Christopher A.; Eisele, Fred L.

2004-01-01

The Transport and Chemical Evolution over the Pacific (TRACE-P) mission extends NASA's Global Tropospheric Experiment (GTE) series of campaigns. TRACE-P was an aircraft-based campaign that was part of a larger ground-based and aircraft-based program (APARE) under the auspices of the International Global Atmospheric Chemistry (IGAC) program. TRACE-P was designed to (1) determine the chemical composition of Asian outflow over the western Pacific, and to (2) determine the chemical evolution of the Asian outflow. These objectives were addressed through a variety of observations and numerical modeling exercises. In particular, the goals included sampling strategies that would improve understanding of the budgets of odd hydrogen species (OH and HO2), budgets of NOx (NO, NO2, and their reservoirs), and impacts of oxidants produced in the outflow on air quality in the United States. The NASA DC-8 and P-3B aircraft were deployed in the March and April, 2001 out of primary bases of operation in Hong Kong and Yokota Air Base in Japan. These two aircraft have complementary capabilities which allow high altitude and long range impacts, as well as low altitude, local impacts to be assessed. In order to quantify the composition and evolution of Asian outflow, it is important to quantify as many species as possible including photochemically active species (e.g. NO2, CH2O, O3, acetone, etc.), sources species (VOCs, CO, NOx, SO2, aerosols), reactive intermediates including free radicals (OH, HO2, RO2, and their reservoirs), and end products (nitric acid, sulfuric acid, secondary aerosols, etc.). The more complete the measurement suite, the more tightly constrained the numerical modeling can be (within the uncertainties of the measurements). The numerical models range in sophistication from simple steady state box models (as employed in this study) to multi-dimensional chemical transport models. Data were collected on approximately 20 flights of the DC-8 and 21 flights of the P-3B

Chemical Abundance Analysis of Moving Group W11450 (Latham 1)

NASA Astrophysics Data System (ADS)

O'Connell, Julia E.; Martens, Kylee; Frinchaboy, Peter M.

2016-12-01

We present elemental abundances for all seven stars in Moving Group W11450 (Latham 1) to determine if they may be chemically related. These stars appear to be both spatially and kinematically related, but no spectroscopic abundance analysis exists in literature. Abundances for eight elements were derived via equivalent width analyses of high-resolution (R ˜ 60,000), high-signal-to-noise ratio (< {{S}}/{{N}}> ˜ 100) spectra obtained with the Otto Struve 2.1 m telescope and the Sandiford Echelle Spectrograph at McDonald Observatory. The large star-to-star scatter in metallicity, -0.55 ≤ [Fe/H] ≤slant 0.06 dex (σ = 0.25), implies these stars were not produced from the same chemically homogeneous molecular cloud, and are therefore not part of a remnant or open cluster as previously proposed. Prior to this analysis, it was suggested that two stars in the group, W11449 and W11450, are possible wide binaries. The candidate wide binary pair show similar chemical abundance patterns with not only iron but with other elements analyzed in this study, suggesting the proposed connection between these two stars may be real.

Microorganisms in inorganic chemical analysis.

PubMed

Godlewska-Zyłkiewicz, Beata

2006-01-01

There are innumerable strains of microbes (bacteria, yeast and fungi) that degrade or transform chemicals and compounds into simpler, safer or less toxic substances. These bioprocesses have been used for centuries in the treatment of municipal wastes, in wine, cheese and bread making, and in bioleaching and metal recovery processes. Recent literature shows that microorganisms can be also used as effective sorbents for solid phase extraction procedures. This review reveals that fundamental nonanalytical studies on the parameters and conditions of biosorption processes and on metal-biomass interactions often result in efficient analytical procedures and biotechnological applications. Some selected examples illustrate the latest developments in the biosorption of metals by microbial biomass, which have opened the door to the application of microorganisms to analyte preconcentration, matrix separation and speciation analysis.

Chemical Analysis of Exhaled Human Breath Using High Resolution Mm-Wave Rotational Spectra

NASA Astrophysics Data System (ADS)

Guo, Tianle; Branco, Daniela; Thomas, Jessica; Medvedev, Ivan; Dolson, David; Nam, Hyun-Joo; O, Kenneth

2014-06-01

High resolution rotational spectroscopy enables chemical sensors that are both sensitive and highly specific, which is well suited for analysis of expired human breath. We have previously reported on detection of breath ethanol, methanol, acetone, and acetaldehyde using THz sensors. This paper will outline our present efforts in this area, with specific focus on our ongoing quest to correlate levels of blood glucose with concentrations of a few breath chemicals known to be affected by elevated blood sugar levels. Prospects, challenges and future plans will be outlined and discussed. Fosnight, A.M., B.L. Moran, and I.R. Medvedev, Chemical analysis of exhaled human breath using a terahertz spectroscopic approach. Applied Physics Letters, 2013. 103(13): p. 133703-5.

Comprehensive Mass Analysis for Chemical Processes, a Case Study on L-Dopa Manufacture

EPA Science Inventory

To evaluate the “greenness” of chemical processes in route selection and process development, we propose a comprehensive mass analysis to inform the stakeholders from different fields. This is carried out by characterizing the mass intensity for each contributing chemical or wast...

Variability of chemical analysis of reinforcing bar produced in Saudi Arabia

NASA Astrophysics Data System (ADS)

Salman, A.; Djavanroodi, F.

2018-04-01

In view of the importance and demanding roles of steel rebar’s in the reinforced concrete structures, accurate information on the properties of the steels is important at the design stage. In the steelmaking process, production variations in chemical composition are unavoidable. The aim of this work is to study the variability of the chemical composition of reinforcing steel produced throughout the Saudi Arabia and asses the quality of steel rebar’s acoording to ASTM A615. 68 samples of ASTM A615 Grade 60 from different manufacturers were collected and tested using the Spectrometer test to obtain Chemical Compositions. EasyFit (5.6) software is utilized to conducted statistical analysis. Chemical compositions distributions and, control charts are generated for the compositions. Results showed that some compositions are above the upper line of the control chart. Finally, the analyses show that less than 3% of the steel failed to meet minimum ASTM standards for chemical composition.

Measurement of kinaesthetic properties of in-brine table olives by microstructure of fracture surface, sensory evaluation and texture profile analysis (TPA).

PubMed

Lanza, Barbara; Amoruso, Filomena

2018-02-02

A series of transformations occur in olive fruit both during ripening and processing. In particular, significant changes in the microstructural composition affect the flavour, texture, nutrients and overall quality of the end product. Texture is one of the sensory quality attributes of greatest importance to consumer acceptance. In the present work, kinaesthetic properties of in-brine table olives of three cultivars of Olea europaea L. (Bella di Cerignola, Peranzana and Taggiasca cvs) were provided by several measurements of olive tissue texture by sensory, rheological and microstructural approaches. Olives at the same stage of ripening and processed with the same technology, but belonging to different cultivars, showed significant differences at microstructural, sensorial and rheological levels. To describe the relationship between the three variables, multiple regression analysis and principal component analysis were chosen. Differences in microstructure were closely related both in terms of hardness measured by texture profile analysis and hardness measured by sensory analysis. The information provided could be an aid for screening and training of a sensory panel. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

Are electrostatic potentials between regions of different chemical composition measurable? The Gibbs-Guggenheim Principle reconsidered, extended and its consequences revisited.

PubMed

Pethica, Brian A

2007-12-21

As indicated by Gibbs and made explicit by Guggenheim, the electrical potential difference between two regions of different chemical composition cannot be measured. The Gibbs-Guggenheim Principle restricts the use of classical electrostatics in electrochemical theories as thermodynamically unsound with some few approximate exceptions, notably for dilute electrolyte solutions and concomitant low potentials where the linear limit for the exponential of the relevant Boltzmann distribution applies. The Principle invalidates the widespread use of forms of the Poisson-Boltzmann equation which do not include the non-electrostatic components of the chemical potentials of the ions. From a thermodynamic analysis of the parallel plate electrical condenser, employing only measurable electrical quantities and taking into account the chemical potentials of the components of the dielectric and their adsorption at the surfaces of the condenser plates, an experimental procedure to provide exceptions to the Principle has been proposed. This procedure is now reconsidered and rejected. No other related experimental procedures circumvent the Principle. Widely-used theoretical descriptions of electrolyte solutions, charged surfaces and colloid dispersions which neglect the Principle are briefly discussed. MD methods avoid the limitations of the Poisson-Bolzmann equation. Theoretical models which include the non-electrostatic components of the inter-ion and ion-surface interactions in solutions and colloid systems assume the additivity of dispersion and electrostatic forces. An experimental procedure to test this assumption is identified from the thermodynamics of condensers at microscopic plate separations. The available experimental data from Kelvin probe studies are preliminary, but tend against additivity. A corollary to the Gibbs-Guggenheim Principle is enunciated, and the Principle is restated that for any charged species, neither the difference in electrostatic potential nor the

A kinetic and equilibrium analysis of silicon carbide chemical vapor deposition on monofilaments

NASA Technical Reports Server (NTRS)

Gokoglu, S. A.; Kuczmarski, M. A.

1993-01-01

Chemical kinetics of atmospheric pressure silicon carbide (SiC) chemical vapor deposition (CVD) from dilute silane and propane source gases in hydrogen is numerically analyzed in a cylindrical upflow reactor designed for CVD on monofilaments. The chemical composition of the SiC deposit is assessed both from the calculated total fluxes of carbon and silicon and from chemical equilibrium considerations for the prevailing temperatures and species concentrations at and along the filament surface. The effects of gas and surface chemistry on the evolution of major gas phase species are considered in the analysis.

Chemical Analysis for Chitin as a Measure of Fungal Infiltration of Cellulosic Materials.

DTIC Science & Technology

1976-12-01

the addition of 50 n’.illiliters of I 2N hydrochloric acid). Store at .~lO0 C. (11) Bushnell-Haas medium (12) Glucosamine hydrochloride (I milliliter...Infiltration Cellu!.jsic Materials Fungus-Induced Deterioration Glucosamine A TRACT (Cl~ i~s ,.v.ra. ia. ~V ~~~~~a . y d Sd.niIl ~ By block ni b.,) A chemical...EXPERIMENTAL PROCEDURE 3. Approach to the Problem. Carry out laboratory experiments to investigate variables as: shelf life of stock glucosamine , digestion

Chemical preconcentrator

DOEpatents

Manginell, Ronald P.; Frye-Mason, Gregory C.

2001-01-01

A chemical preconcentrator is disclosed with applications to chemical sensing and analysis. The preconcentrator can be formed by depositing a resistive heating element (e.g. platinum) over a membrane (e.g. silicon nitride) suspended above a substrate. A coating of a sorptive material (e.g. a microporous hydrophobic sol-gel coating or a polymer coating) is formed on the suspended membrane proximate to the heating element to selective sorb one or more chemical species of interest over a time period, thereby concentrating the chemical species in the sorptive material. Upon heating the sorptive material with the resistive heating element, the sorbed chemical species are released for detection and analysis in a relatively high concentration and over a relatively short time period. The sorptive material can be made to selectively sorb particular chemical species of interest while not substantially sorbing other chemical species not of interest. The present invention has applications for use in forming high-sensitivity, rapid-response miniaturized chemical analysis systems (e.g. a "chem lab on a chip").

Measurement Protocols for In situ Analysis of Organic Compounds at Mars and Comets

NASA Technical Reports Server (NTRS)

Mahaffy, P. R.; Brinckerhuff, W. B.; Buch, A.; Cabane, M.; Coll, P.; Demick, J.; Glavin, D. P.; Navarro-Gonzalez, R.

2005-01-01

The determination of the abundance and chemical and isotopic composition of organic molecules in comets and those that might be found in protected environments at Mars is a first step toward understanding prebiotic chemistries on these solar system bodies. While future sample return missions from Mars and comets will enable detailed chemical and isotopic analysis with a wide range of analytical techniques, precursor insitu investigations can complement these missions and facilitate the identification of optimal sites for sample return. Robust automated experiments that make efficient use of limited spacecraft power, mass, and data volume resources are required for use by insitu missions. Within these constraints we continue to explore a range of instrument techniques and measurement protocols that can maximize the return from such insitu investigations.

Measurement Protocols for In Situ Analysis of Organic Compounds at Mars and Comets

NASA Technical Reports Server (NTRS)

Mahaffy, P. R.; Brinckerhoff, W. B.; Buch, A.; Cabane, M.; Coll, P.; Demick, J.; Glavin, D. P.; Navarro-Gonzalez, R.

2005-01-01

The determination of the abundance and chemical and isotopic composition of organic molecules in comets and those that might be found in protected environments at Mars is a first step toward understanding prebiotic chemistries on these solar system bodies. While future sample return missions from Mars and comets will enable detailed chemical and isotopic analysis with a wide range of analytical techniques, precursor insitu investigations can complement these missions and facilitate the identification of optimal sites for sample return. Robust automated experiments that make efficient use of limited spacecraft power, mass, and data volume resources are required for use by insitu missions. Within these constraints we continue to explore a range of instrument techniques and measurement protocols that can maximize the return from such insitu investigations.

Analysis of selected chemical parameters in Piemontese wines.

PubMed

Stępień, Agnieszka E; Stawarczyk, Kinga; Bilek, Maciej; Kędziora, Katarzyna M

2015-01-01

Piemontese wines are well known and valued all over the world. The most popular of them are Barolo and Barbaresco wines. However, in Poland, they are still little known and only now are being gradually introduced to a wider range of consumers. The aim of this study was to evaluate the content of inorganic anions, minerals, sugars and glycerol of Piemontese wines from micro-region Langhe, classified as DOCG ("Denominazione di Origine Controllata e Garantita", ie. controlled designation of origin guaranteed) and DOC ("Denominazione di Origine Controllata", ie. controlled designation of origin) products. Seven types of red wines and one type of white wine were tested. High Performance Ion Chromatography with conductometric detection (HPLC-CD) was used to measure the content of inorganic anions, ie. fluorides, chlorides, sulfates and phosphates. Flame atomic absorption spectrometry (F-AAS) was used to measure the content of minerals, ie. magnesium, calcium, sodium, copper, potassium, zinc and iron, while High Performance Liquid Chromatography with charged aerosol detection (HPLC-CAD) was used to measure the content of glycerol and sugars, ie. fructose, glucose and sucrose. Our studies show that although Piemontese wines are characterized by a relatively low content of minerals in comparison with the wines from other regions, they contain a lot of ingredients that have beneficial effects for human health. Moreover, we observed that the studied wines contain particularly high concentration of inorganic ions--phosphates and fluorides. Furthermore, all tested red wines show far reaching similarities in their chemical properties, which is possibly a direct consequence of using in their production locally cultivated grape varieties. Analysis of the wines from the Piemont region, classified as DOCG, DOC, confirmed that these are dry wines of a high quality.

Application of Surface Analysis Methods to Nanomaterials: Summaryof ISO/TC 201 Technical Report: ISO 14187:2011 -Surface Chemical Analysis- Characterization of Nanomaterials

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

Baer, Donald R.

ISO Technical Report (TR) 14187 provides an introduction to (and examples of) the information that can be obtained about nanostructured materials using surface-analysis tools. In addition, both general issues and challenges associated with characterising nanostructured materials and the specific opportunities and challenges associated with individual analytical methods are identified. As the size of objects or components of materials approaches a few nanometres, the distinctions among 'bulk', 'surface' and 'particle' analysis blur. This Technical Report focuses on issues specifically relevant to surface chemical analysis of nanostructured materials. The report considers a variety of analysis methods but focuses on techniques that aremore » in the domain of ISO/TC 201 including Auger electron spectroscopy, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and scanning probe microscopy. Measurements of nanoparticle surface properties such as surface potential that are often made in a solution are not discussed.« less

Surface characterization and chemical analysis of bamboo substrates pretreated by alkali hydrogen peroxide.

PubMed

Song, Xueping; Jiang, Yan; Rong, Xianjian; Wei, Wei; Wang, Shuangfei; Nie, Shuangxi

2016-09-01

The surface characterization and chemical analysis of bamboo substrates by alkali hydrogen peroxide pretreatment (AHPP) were investigated in this study. The results tended to manifest that AHPP prior to enzymatic and chemical treatment was potential for improving accessibility and reactivity of bamboo substrates. The inorganic components, organic solvent extractives and acid-soluble lignin were effectively removed by AHPP. X-ray photoelectron spectroscopy (XPS) analysis indicated that the surface of bamboo chips had less lignin but more carbohydrate after pre-treatment. Fiber surfaces became etched and collapsed, and more pores and debris on the substrate surface were observed with Scanning Electron Microscopy (SEM). Brenauer-Emmett-Teller (BET) results showed that both of pore volume and surface area were increased after AHPP. Although XRD analysis showed that AHPP led to relatively higher crystallinity, pre-extraction could overall enhance the accessibility of enzymes and chemicals into the bamboo structure. Copyright © 2016. Published by Elsevier Ltd.

Hydrogeology, chemical and microbial activity measurement through deep permafrost

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

Stotler, R.L.; Frape, S.K.; Freifeld, B.M.

2010-04-01

Little is known about hydrogeochemical conditions beneath thick permafrost, particularly in fractured crystalline rock, due to difficulty in accessing this environment. The purpose of this investigation was to develop methods to obtain physical, chemical, and microbial information about the subpermafrost environment from a surface-drilled borehole. Using a U-tube, gas and water samples were collected, along with temperature, pressure, and hydraulic conductivity measurements, 420 m below ground surface, within a 535 m long, angled borehole at High Lake, Nunavut, Canada, in an area with 460-m-thick permafrost. Piezometric head was well above the base of the permafrost, near land surface. Initial watermore » samples were contaminated with drill fluid, with later samples <40% drill fluid. The salinity of the non-drill fluid component was <20,000 mg/L, had a Ca/Na ratio above 1, with {delta}{sup 18}O values {approx}5{per_thousand} lower than the local surface water. The fluid isotopic composition was affected by the permafrost-formation process. Nonbacteriogenic CH{sub 4} was present and the sample location was within methane hydrate stability field. Sampling lines froze before uncontaminated samples from the subpermafrost environment could be obtained, yet the available time to obtain water samples was extended compared to previous studies. Temperature measurements collected from a distributed temperature sensor indicated that this issue can be overcome easily in the future. The lack of methanogenic CH{sub 4} is consistent with the high sulfate concentrations observed in cores. The combined surface-drilled borehole/U-tube approach can provide a large amount of physical, chemical, and microbial data from the subpermafrost environment with few, controllable, sources of contamination.« less

Hydrogeology, Chemical and Microbial Activity Measurement Through Deep Permafrost

USGS Publications Warehouse

Stotler, R.L.; Frape, S.K.; Freifeld, B.M.; Holden, B.; Onstott, T.C.; Ruskeeniemi, T.; Chan, E.

2011-01-01

Little is known about hydrogeochemical conditions beneath thick permafrost, particularly in fractured crystalline rock, due to difficulty in accessing this environment. The purpose of this investigation was to develop methods to obtain physical, chemical, and microbial information about the subpermafrost environment from a surface-drilled borehole. Using a U-tube, gas and water samples were collected, along with temperature, pressure, and hydraulic conductivity measurements, 420 m below ground surface, within a 535 m long, angled borehole at High Lake, Nunavut, Canada, in an area with 460-m-thick permafrost. Piezometric head was well above the base of the permafrost, near land surface. Initial water samples were contaminated with drill fluid, with later samples <40% drill fluid. The salinity of the non-drill fluid component was <20,000 mg/L, had a Ca/Na ratio above 1, with ??18O values ???5??? lower than the local surface water. The fluid isotopic composition was affected by the permafrost-formation process. Nonbacteriogenic CH4 was present and the sample location was within methane hydrate stability field. Sampling lines froze before uncontaminated samples from the subpermafrost environment could be obtained, yet the available time to obtain water samples was extended compared to previous studies. Temperature measurements collected from a distributed temperature sensor indicated that this issue can be overcome easily in the future. The lack of methanogenic CH4 is consistent with the high sulfate concentrations observed in cores. The combined surface-drilled borehole/U-tube approach can provide a large amount of physical, chemical, and microbial data from the subpermafrost environment with few, controllable, sources of contamination. ?? 2010 The Author(s). Journal compilation ?? 2010 National Ground Water Association.

Empirical Correction for Differences in Chemical Exchange Rates in Hydrogen Exchange-Mass Spectrometry Measurements.

PubMed

Toth, Ronald T; Mills, Brittney J; Joshi, Sangeeta B; Esfandiary, Reza; Bishop, Steven M; Middaugh, C Russell; Volkin, David B; Weis, David D

2017-09-05

A barrier to the use of hydrogen exchange-mass spectrometry (HX-MS) in many contexts, especially analytical characterization of various protein therapeutic candidates, is that differences in temperature, pH, ionic strength, buffering agent, or other additives can alter chemical exchange rates, making HX data gathered under differing solution conditions difficult to compare. Here, we present data demonstrating that HX chemical exchange rates can be substantially altered not only by the well-established variables of temperature and pH but also by additives including arginine, guanidine, methionine, and thiocyanate. To compensate for these additive effects, we have developed an empirical method to correct the hydrogen-exchange data for these differences. First, differences in chemical exchange rates are measured by use of an unstructured reporter peptide, YPI. An empirical chemical exchange correction factor, determined by use of the HX data from the reporter peptide, is then applied to the HX measurements obtained from a protein of interest under different solution conditions. We demonstrate that the correction is experimentally sound through simulation and in a proof-of-concept experiment using unstructured peptides under slow-exchange conditions (pD 4.5 at ambient temperature). To illustrate its utility, we applied the correction to HX-MS excipient screening data collected for a pharmaceutically relevant IgG4 mAb being characterized to determine the effects of different formulations on backbone dynamics.

Correlation analyses of phytochemical composition, chemical, and cellular measures of antioxidant activity of broccoli (Brassica oleracea L. Var. italica).

PubMed

Eberhardt, Marian V; Kobira, Kanta; Keck, Anna-Sigrid; Juvik, John A; Jeffery, Elizabeth H

2005-09-21

Chemical measures of antioxidant activity within the plant, such as the oxygen radical absorbance capacity (ORAC) assay, have been reported for many plant-based foods. However, the extent to which chemical measures relate to cellular measures of oxidative stress is unclear. The natural variation in the phytochemical content of 22 broccoli genotypes was used to determine correlations among chemical composition (carotenoids, tocopherols and polyphenolics), chemical antioxidant activity (ORAC), and measures of cellular antioxidation [prevention of DNA oxidative damage and of oxidation of the biomarker dichlorofluorescein (DCFH) in HepG2 cells] using hydrophilic and lipophilic extracts of broccoli. For lipophilic extracts, ORAC (ORAC-L) correlated with inhibition of cellular oxidation of DCFH (DCFH-L, r = 0.596, p = 0.006). Also, DNA damage in the presence of the lipophilic extract was negatively correlated with both chemical and cellular measures of antioxidant activity as measured by ORAC-L (r = -0.705, p = 0.015) and DCFH-L (r = -0.671, p = 0.048), respectively. However, no correlations were observed for hydrophilic (-H) extracts, except between polyphenol content and ORAC (ORAC-H; r = 0.778, p < 0.001). Inhibition of cellular oxidation by hydrophilic extracts (DCFH-H) and ORAC-H were approximately 8- and 4-fold greater than DCFH-L and ORAC-L, respectively. Whether ORAC-H has more biological relevance than ORAC-L because of its magnitude or whether ORAC-L bears more biological relevance because it relates to cellular estimates of antioxidant activity remains to be determined. Chemical estimates of antioxidant capacity within the plant may not accurately reflect the complex nature of the full antioxidant activity of broccoli extracts within cells.

ISS Expeditions 16 & 17: Chemical Analysis Results for Potable Water

NASA Technical Reports Server (NTRS)

Straub, John E., II; Plumlee, Debrah K.; Schultz, John R.

2009-01-01

During the twelve month span of Expeditions 16 and 17 beginning October of 2007, the chemical quality of the potable water onboard the International Space Station (ISS) was verified safe for crew consumption through the return and chemical analysis of water samples by the Water and Food Analytical Laboratory (WAFAL) at Johnson Space Center (JSC). Reclaimed cabin humidity condensate and Russian ground-supplied water were the principle sources of potable water and for the first time, European groundsupplied water was also available. Although water was transferred from Shuttle to ISS during Expeditions 16 and 17, no Shuttle potable water was consumed during this timeframe. A total of 12 potable water samples were collected using U.S. hardware during Expeditions 16 and 17 and returned on Shuttle flights 1E (STS122), 1JA (STS123), and 1J (STS124). The average sample volume was sufficient for complete chemical characterization to be performed. The results of JSC chemical analyses of these potable water samples are presented in this paper. The WAFAL also received potable water samples for analysis from the Russian side collected inflight with Russian hardware, as well as preflight samples of Rodnik potable water delivered to ISS on Russian Progress vehicles 28 to 30. Analytical results for these additional potable water samples are also reported and discussed herein. Although the potable water supplies available during Expeditions 16 and 17 were judged safe for crew consumption, a recent trending of elevated silver levels in the SVOZV water is a concern for longterm consumption and efforts are being made to lower these levels.

ISS Expeditions 16 Thru 20: Chemical Analysis Results for Potable Water

NASA Technical Reports Server (NTRS)

Straub, John E., II; Plumlee, Debrah K.; Schultz, John R.

2010-01-01

This slide presentation reviews the results of the chemical analysis of the potable water supply from the International Space Station (ISS) expeditions 16 thru 20. Both Russian ground water and shuttle-transferred water are available for the use of the ISS crew's requirements. This is supplemented with condensate water and water form the Water Recovery System (WRS). An overview of the condensate H2O recovery system is given and the WRS is described and diagrammed. The water quality requirements, the handling, and analytical methods for the inorganic and organic tests are reviewed. The chemical analysis results for expeditions 16-20 archival water samples collected from the various water sources indicate that all of the ISS potable water supplies were acceptable for crew consumption.

Discrimination Enhancement with Transient Feature Analysis of a Graphene Chemical Sensor.

PubMed

Nallon, Eric C; Schnee, Vincent P; Bright, Collin J; Polcha, Michael P; Li, Qiliang

2016-01-19

A graphene chemical sensor is subjected to a set of structurally and chemically similar hydrocarbon compounds consisting of toluene, o-xylene, p-xylene, and mesitylene. The fractional change in resistance of the sensor upon exposure to these compounds exhibits a similar response magnitude among compounds, whereas large variation is observed within repetitions for each compound, causing a response overlap. Therefore, traditional features depending on maximum response change will cause confusion during further discrimination and classification analysis. More robust features that are less sensitive to concentration, sampling, and drift variability would provide higher quality information. In this work, we have explored the advantage of using transient-based exponential fitting coefficients to enhance the discrimination of similar compounds. The advantages of such feature analysis to discriminate each compound is evaluated using principle component analysis (PCA). In addition, machine learning-based classification algorithms were used to compare the prediction accuracies when using fitting coefficients as features. The additional features greatly enhanced the discrimination between compounds while performing PCA and also improved the prediction accuracy by 34% when using linear discrimination analysis.

Chemical information obtained from Auger depth profiles by means of advanced factor analysis (MLCFA)

NASA Astrophysics Data System (ADS)

De Volder, P.; Hoogewijs, R.; De Gryse, R.; Fiermans, L.; Vennik, J.

1993-01-01

The advanced multivariate statistical technique "maximum likelihood common factor analysis (MLCFA)" is shown to be superior to "principal component analysis (PCA)" for decomposing overlapping peaks into their individual component spectra of which neither the number of components nor the peak shape of the component spectra is known. An examination of the maximum resolving power of both techniques, MLCFA and PCA, by means of artificially created series of multicomponent spectra confirms this finding unambiguously. Substantial progress in the use of AES as a chemical-analysis technique is accomplished through the implementation of MLCFA. Chemical information from Auger depth profiles is extracted by investigating the variation of the line shape of the Auger signal as a function of the changing chemical state of the element. In particular, MLCFA combined with Auger depth profiling has been applied to problems related to steelcord-rubber tyre adhesion. MLCFA allows one to elucidate the precise nature of the interfacial layer of reaction products between natural rubber vulcanized on a thin brass layer. This study reveals many interesting chemical aspects of the oxi-sulfidation of brass undetectable with classical AES.

Single-Molecule Electronics: Chemical and Analytical Perspectives.

PubMed

Nichols, Richard J; Higgins, Simon J

2015-01-01

It is now possible to measure the electrical properties of single molecules using a variety of techniques including scanning probe microcopies and mechanically controlled break junctions. Such measurements can be made across a wide range of environments including ambient conditions, organic liquids, ionic liquids, aqueous solutions, electrolytes, and ultra high vacuum. This has given new insights into charge transport across molecule electrical junctions, and these experimental methods have been complemented with increasingly sophisticated theory. This article reviews progress in single-molecule electronics from a chemical perspective and discusses topics such as the molecule-surface coupling in electrical junctions, chemical control, and supramolecular interactions in junctions and gating charge transport. The article concludes with an outlook regarding chemical analysis based on single-molecule conductance.

Ultrasonic nebulization extraction/low pressure photoionization mass spectrometry for direct analysis of chemicals in matrices.

PubMed

Liu, Chengyuan; Zhu, Yanan; Zhou, Zhongyue; Yang, Jiuzhong; Qi, Fei; Pan, Yang

2015-09-03

A novel ultrasonic nebulization extraction/low-pressure photoionization (UNE-LPPI) system has been designed and employed for the rapid mass spectrometric analysis of chemicals in matrices. An ultrasonic nebulizer was used to extract the chemicals in solid sample and nebulize the solvent in the nebulization cell. Aerosols formed by ultrasonic were evaporated by passing through a transferring tube, and desolvated chemicals were ionized by the emitted light (10.6 eV) from a Krypton discharge lamp at low pressure (∼68 Pa). First, a series of semi/non-volatile compounds with different polarities, such as polycyclic aromatic hydrocarbons (PAHs), amino acids, dipeptides, drugs, nucleic acids, alkaloids, and steroids were used to test the system. Then, the quantification capability of UNE-LPPI was checked with: 1) pure chemicals, such as 9,10-phenanthrenequinone and 1,4-naphthoquinone dissolved in solvent; 2) soil powder spiked with different amounts of phenanthrene and pyrene. For pure chemicals, the correlation coefficient (R(2)) for the standard curve of 9,10-phenanthrenequinone in the range of 3 ng-20 μg mL(-1) was 0.9922, and the measured limits of detection (LOD) was 1 ng ml(-1). In the case of soil powder, linear relationships for phenanthrene and pyrene from 10 to 400 ng mg(-1) were obtained with correlation coefficients of 0.9889 and 0.9893, respectively. At last, the feasibility of UNE-LPPI for the detection of chemicals in real matrices such as tablets and biological tissues (tea, Citrus aurantium peel and sage (Salvia officinalis) leaf) were successfully demonstrated. Copyright © 2015 Elsevier B.V. All rights reserved.

Improved Devices for Collecting Sweat for Chemical Analysis

NASA Technical Reports Server (NTRS)

Feeback, Daniel L.; Clarke, Mark S. F.

2011-01-01

Improved devices have been proposed for collecting sweat for biochemical analysis especially for determination of the concentration of Ca2+ ions in sweat as a measure of loss of Ca from bones. Unlike commercially available sweat-collection patches used previously in monitoring osteoporosis and in qualitative screening for some drugs, the proposed devices would not allow evaporation of the volatile chemical components (mostly water) of sweat. Moreover, the proposed devices would be designed to enable determination of the volumes of collected sweat. From these volumes and the quantities of Ca2+ and/or other analytes as determined by other means summarized below, one could determine the concentrations of the analytes in sweat. A device according to the proposal would be flexible and would be worn like a commercial sweat-collection patch. It would be made of molded polydimethylsiloxane (silicone rubber) or other suitable material having properties that, for the purpose of analyzing sweat, are similar to those of glass. The die for molding the silicone rubber would be fabricated by a combination of lithography and electroplating. The die would reproducibly form, in the silicone rubber, a precisely defined number of capillary channels per unit area, each channel having a precisely defined volume. Optionally, electrodes for measuring the Ca2+ content of the sweat could be incorporated into the device. The volume of sweat collected in the capillary channels of the device would be determined from (1) the amount of light or radio waves of a given wavelength absorbed by the device and (2) the known geometry of the array of capillary channels. Then, in one of two options, centrifugation would be performed to move the sweat from the capillary tubes to the region containing the electrodes, which would be used to measure the Ca2+ content by a standard technique. In the other option, centrifugation would be performed to remove the sweat from the device to make the sweat available

Improved Devices for Collecting Sweat for Chemical Analysis

NASA Technical Reports Server (NTRS)

Feedback, Daniel L.; Clarke, Mark S. F.

2011-01-01

Improved devices have been proposed for collecting sweat for biochemical analysis - especially for determination of the concentration of Ca2+ ions in sweat as a measure of loss of Ca from bones. Unlike commercially available sweat-collection patches used previously in monitoring osteoporosis and in qualitative screening for some drugs, the proposed devices would not allow evaporation of the volatile chemical components (mostly water) of sweat. Moreover, the proposed devices would be designed to enable determination of the volumes of collected sweat. From these volumes and the quantities of Ca(2+) and/or other analytes as determined by other means summarized below, one could determine the concentrations of the analytes in sweat. A device according to the proposal would be flexible and would be worn like a commercial sweat-collection patch. It would be made of molded polydimethylsiloxane (silicone rubber) or other suitable material having properties that, for the purpose of analyzing sweat, are similar to those of glass. The die for molding the silicone rubber would be fabricated by a combination of lithography and electroplating. The die would reproducibly form, in the silicone rubber, a precisely defined number of capillary channels per unit area, each channel having a precisely defined volume. Optionally, electrodes for measuring the Ca(2+) content of the sweat could be incorporated into the device. The volume of sweat collected in the capillary channels of the device would be determined from (1) the amount of light or radio waves of a given wavelength absorbed by the device and (2) the known geometry of the array of capillary channels. Then, in one of two options, centrifugation would be performed to move the sweat from the capillary tubes to the region containing the electrodes, which would be used to measure the Ca(2+) content by a standard technique. In the other option, centrifugation would be performed to remove the sweat from the device to make the sweat

Thermodynamic analysis of alternate energy carriers, hydrogen and chemical heat pipes

NASA Technical Reports Server (NTRS)

Cox, K. E.; Carty, R. H.; Conger, W. L.; Soliman, M. A.; Funk, J. E.

1976-01-01

The paper discusses the production concept and efficiency of two new energy transmission and storage media intended to overcome the disadvantages of electricity as an overall energy carrier. These media are hydrogen produced by water-splitting and the chemical heat pipe. Hydrogen can be transported or stored, and burned as energy is needed, forming only water and thus obviating pollution problems. The chemical heat pipe envisions a system in which heat is stored as the heat of reaction in chemical species. The thermodynamic analysis of these two methods is discussed in terms of first-law and second-law efficiency. It is concluded that chemical heat pipes offer large advantages over thermochemical hydrogen generation schemes on a first-law efficiency basis except for the degradation of thermal energy in temperature thus providing a source of low-temperature (800 K) heat for process heat applications. On a second-law efficiency basis, hydrogen schemes are superior in that the amount of available work is greater as compared to chemical heat pipes.

Evidence of Chemical Cloud Processing from In Situ Measurements in the Polluted Marine Environment

NASA Astrophysics Data System (ADS)

Hudson, J. G.; Noble, S. R., Jr.

2017-12-01

Chemical cloud processing alters activated cloud condensation nuclei (CCN). Aqueous oxidation of trace gases dissolved within cloud droplets adds soluble material. As most cloud droplets evaporate, the residual material produces CCN that are larger and with a different hygroscopicity (κ). This improves the CCN, lowering the critical supersaturation (Sc), making it more easily activated. This process separates the processed (accumulation) and unprocessed (Aitken) modes creating bimodal CCN distributions (Hudson et al., 2015). Various measurements made during the MArine Stratus/stratocumulus Experiment (MASE), including CCN, exhibited aqueous processing signals. Particle size distributions; measured by a differential mobility analyzer; were compared with CCN distributions; measured by the Desert Research Institute CCN spectrometer; by converting size to Sc using κ to overlay concurrent distributions. By tuning each mode to the best agreement, κ for each mode is determined; processed κ (κp), unprocessed κ (κu). In MASE, 59% of bimodal distributions had different κ for the two modes indicating dominance of chemical processing via aqueous oxidation. This is consistent with Hudson et al. (2015). Figure 1A also indicates chemical processing with larger κp between 0.35-0.75. Processed CCN had an influx of soluble material from aqueous oxidation which increased κp versus κu. Above 0.75 κp is lower than κu (Fig. 1A). When κu is high and sulfate material is added, κp tends towards κ of the added material. Thus, κp is reduced by additional material that is less soluble than the original material. Chemistry measurements in MASE also indicate in-cloud aqueous oxidation (Fig. 1B and 1C). Higher fraction of CCN concentrations in the processed mode are also associated with larger amounts of sulfates (Fig. 1B, red) and nitrates (Fig. 1C, orange) while SO2 (Fig. 1B, black) and O3 (Fig. 1C, blue) have lower amounts. This larger amount of sulfate is at the expense of

Chemical Composition Analysis of Extracts from Ficus Hirta Using Supercritical Fluid

NASA Astrophysics Data System (ADS)

Deng, S. B.; Chen, J. P.; Chen, Y. Z.; Yu, C. Q.; Yang, Y.; Wu, S. H.; Chen, C. Z.

2018-05-01

Ficus hirta was extracted by supercritical carbon dioxide. The volatile chemical components of extracts were analyzed using gas chromatography-mass spectrometry (GC-MS). The percentage of products extracted by Supercritical Fluid Extraction(SFE) was 2.5%. Nineteen volatile compounds were identified. The main volatile components were Elemicin, Psoralen, Palmitic acid, Bergapten, α-Linolenic acid, Medicarpin, Retinoic Acid, Maackiain, and Squalene. The method is simple and quick, and can be used for the preliminary analysis of chemical constituents of supercritical extracts of Ficus hirta.

Chemical Analysis of the Moon at the Surveyor VII Landing Site: Preliminary Results.

PubMed

Turkevich, A L; Franzgrote, E J; Patterson, J H

1968-10-04

The alpha-scattering experiment aboard Surveyor VII has provided a chemical analysis of the moon in the area of the crater Tycho. The preliminary results indicate a chemical composition similar to that already found at two mare sites, but with a lower concentration of elements of the iron group (titanium through copper).

Computer vision-based analysis of foods: a non-destructive colour measurement tool to monitor quality and safety.

PubMed

Mogol, Burçe Ataç; Gökmen, Vural

2014-05-01

Computer vision-based image analysis has been widely used in food industry to monitor food quality. It allows low-cost and non-contact measurements of colour to be performed. In this paper, two computer vision-based image analysis approaches are discussed to extract mean colour or featured colour information from the digital images of foods. These types of information may be of particular importance as colour indicates certain chemical changes or physical properties in foods. As exemplified here, the mean CIE a* value or browning ratio determined by means of computer vision-based image analysis algorithms can be correlated with acrylamide content of potato chips or cookies. Or, porosity index as an important physical property of breadcrumb can be calculated easily. In this respect, computer vision-based image analysis provides a useful tool for automatic inspection of food products in a manufacturing line, and it can be actively involved in the decision-making process where rapid quality/safety evaluation is needed. © 2013 Society of Chemical Industry.

Measuring Dimensions of Spirituality in Chemical Dependence Treatment and Recovery: Research and Practice

ERIC Educational Resources Information Center

Shorkey, Clayton; Uebel, Michael; Windsor, Liliane C.

2008-01-01

Spirituality and religiousness have long been associated with physical and mental health. The scientific treatment of religiosity as a multi-dimensional phenomenon is well established, especially in relation to chemical dependence treatment. Indeed, over 100 instruments are available for measuring various dimensions of religiosity. The more recent…

Laser-induced fluorescence spectroscopy for improved chemical analysis

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

Gelbwachs, J.A.

1983-09-01

This report summarizes the progress achieved over the past five years in the laser-induced fluorescence spectroscopy (LIFS) for improved chemical analysis program. Our initial efforts yielded significantly lower detection limits for trace elemental analysis by the use of both cw and pulsed laser excitations. New methods of LIFS were developed that were shown to overcome many of the traditional limitations to LIFS techniques. LIFS methods have been applied to yield fundamental scientific data that further the understanding of forces between atoms and other atoms and molecules. In recent work, two-photon ionization was combined with LIFS and applied, for the firstmore » time, to the study of energy transfer in ions.« less

Using the gini coefficient to measure the chemical diversity of small-molecule libraries.

PubMed

Weidlich, Iwona E; Filippov, Igor V

2016-08-15

Modern databases of small organic molecules contain tens of millions of structures. The size of theoretically available chemistry is even larger. However, despite the large amount of chemical information, the "big data" moment for chemistry has not yet provided the corresponding payoff of cheaper computer-predicted medicine or robust machine-learning models for the determination of efficacy and toxicity. Here, we present a study of the diversity of chemical datasets using a measure that is commonly used in socioeconomic studies. We demonstrate the use of this diversity measure on several datasets that were constructed to contain various congeneric subsets of molecules as well as randomly selected molecules. We also apply our method to a number of well-known databases that are frequently used for structure-activity relationship modeling. Our results show the poor diversity of the common sources of potential lead compounds compared to actual known drugs. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Sorption of organic chemicals at biogeochemical interfaces - calorimetric measurements

NASA Astrophysics Data System (ADS)

Krüger, J.; Lang, F.; Siemens, J.; Kaupenjohann, M.

2009-04-01

Biogeochemical interfaces in soil act as sorbents for organic chemicals, thereby controlling the degradation and mobility of these substances in terrestrial environments. Physicochemical properties of the organic chemicals and the sorbent determine sorptive interactions. We hypothesize that the sorption of hydrophobic organic chemicals ("R-determined" chemicals) is an entropy-driven partitioning process between the bulk aqueous phase and biogeochemical interface and that the attachment of more polar organic chemicals ("F-determined" chemicals) to mineral surfaces is due to electrostatic interactions and ligand exchange involving functional groups. In order to determine thermodynamic parameters of sorbate/sorbent interactions calorimetric titration experiments have been conducted at 20˚ C using a Nanocalorimeter (TAM III, Thermometric). Solutions of different organic substances ("R-determined" chemicals: phenanthrene, bisphenol A, "F-determined" chemicals: MCPA, bentazone) with concentrations of 100 mol l-1 were added to suspensions of pure minerals (goethite, muscovite, and kaolinite and to polygalacturonic acid (PGA) as model substance for biofilms in soil. Specific surface, porosity, N and C content, particle size and point of zero charge of the mineral were analyzed to characterize the sorbents. The obtained heat quantities for the initial injection of the organic chemicals to the goethite were 55 and 71 J for bisphenol A and phenanthrene ("R-determined representatives") and 92 and 105 J for MCPA and bentazone ("F-determined" representatives). Further experiments with muscovite, kaolinite and PGA are in progress to determine G and H of the adsorption process.

Traits and causes of environmental loss-related chemical accidents in China based on co-word analysis.

PubMed

Wu, Desheng; Song, Yu; Xie, Kefan; Zhang, Baofeng

2018-04-25

Chemical accidents are major causes of environmental losses and have been debated due to the potential threat to human beings and environment. Compared with the single statistical analysis, co-word analysis of chemical accidents illustrates significant traits at various levels and presents data into a visual network. This study utilizes a co-word analysis of the keywords extracted from the Web crawling texts of environmental loss-related chemical accidents and uses the Pearson's correlation coefficient to examine the internal attributes. To visualize the keywords of the accidents, this study carries out a multidimensional scaling analysis applying PROXSCAL and centrality identification. The research results show that an enormous environmental cost is exacted, especially given the expected environmental loss-related chemical accidents with geographical features. Meanwhile, each event often brings more than one environmental impact. Large number of chemical substances are released in the form of solid, liquid, and gas, leading to serious results. Eight clusters that represent the traits of these accidents are formed, including "leakage," "poisoning," "explosion," "pipeline crack," "river pollution," "dust pollution," "emission," and "industrial effluent." "Explosion" and "gas" possess a strong correlation with "poisoning," located at the center of visualization map.

Chemical state analysis of Cl Kα and Kβ1,3 X-ray emission lines using polychromatic WDXRF spectrometer

NASA Astrophysics Data System (ADS)

Kainth, Harpreet Singh; Upmanyu, Arun; Sharma, Hitesh; Singh, Tejbir; Kumar, Sanjeev

2018-02-01

With the support of research projects focusing on sampling and data analysing of different varieties of chemical compounds, wavelength dispersive X-ray fluorescence (WDXRF) technique is commonly used in many research laboratories throughout the world wide to determine the elemental composition of various unknown samples. In the present study, first time we have employed polychromatic S8 TIGER WDXRF spectrometer to study the chemical state analysis in Cl Kα and Kβ1,3 X-ray emission lines. A Voigt function is used to determine the central peak position of the K shell emission lines in all samples. From the present measurements, it is seen that both positive and negative shifts have been observed in Cl Kα (2.622 keV) and Kβ1,3 (2.817 keV) emission peaks. It has been also seen that the effective charge, relative line-width and relative intensity ratio I(Kβ1,3/Kα) are found proportional with the chemical shift. Furthermore, a parabolic relation is also established between them.

Embedded fragments from U.S. military personnel--chemical analysis and potential health implications.

PubMed

Centeno, José A; Rogers, Duane A; van der Voet, Gijsbert B; Fornero, Elisa; Zhang, Lingsu; Mullick, Florabel G; Chapman, Gail D; Olabisi, Ayodele O; Wagner, Dean J; Stojadinovic, Alexander; Potter, Benjamin K

2014-01-23

The majority of modern war wounds are characterized by high-energy blast injuries containing a wide range of retained foreign materials of a metallic or composite nature. Health effects of retained fragments range from local or systemic toxicities to foreign body reactions or malignancies, and dependent on the chemical composition and corrosiveness of the fragments in vivo. Information obtained by chemical analysis of excised fragments can be used to guide clinical decisions regarding the need for fragment removal, to develop therapeutic interventions, and to better anticipate future medical problems from retained fragment related injuries. In response to this need, a new U.S Department of Defense (DoD) directive has been issued requiring characterization of all removed fragments to provide a database of fragment types occurring in combat injuries. The objective of this study is to determine the chemical composition of retained embedded fragments removed from injured military personnel, and to relate results to histological findings in tissue adjacent to fragment material. We describe an approach for the chemical analysis and characterization of retained fragments and adjacent tissues, and include case examples describing fragments containing depleted uranium (DU), tungsten (W), lead (Pb), and non-metal foreign bodies composed of natural and composite materials. Fragments obtained from four patients with penetrating blast wounds to the limbs were studied employing a wide range of chemical and microscopy techniques. Available adjacent tissues from three of the cases were histologically, microscopically, and chemically examined. The physical and compositional properties of the removed foreign material surfaces were examined with energy dispersive x-ray fluorescence spectrometry (EDXRF), scanning electron microscopy (SEM), laser ablation inductively-coupled plasma mass-spectrometry (LA-ICP-MS), and confocal laser Raman microspectroscopy (CLRM). Quantitative chemical

Embedded Fragments from U.S. Military Personnel—Chemical Analysis and Potential Health Implications

PubMed Central

Centeno, José A.; Rogers, Duane A.; van der Voet, Gijsbert B.; Fornero, Elisa; Zhang, Lingsu; Mullick, Florabel G.; Chapman, Gail D.; Olabisi, Ayodele O.; Wagner, Dean J.; Stojadinovic, Alexander; Potter, Benjamin K.

2014-01-01

Background: The majority of modern war wounds are characterized by high-energy blast injuries containing a wide range of retained foreign materials of a metallic or composite nature. Health effects of retained fragments range from local or systemic toxicities to foreign body reactions or malignancies, and dependent on the chemical composition and corrosiveness of the fragments in vivo. Information obtained by chemical analysis of excised fragments can be used to guide clinical decisions regarding the need for fragment removal, to develop therapeutic interventions, and to better anticipate future medical problems from retained fragment related injuries. In response to this need, a new U.S Department of Defense (DoD) directive has been issued requiring characterization of all removed fragments to provide a database of fragment types occurring in combat injuries. Objectives: The objective of this study is to determine the chemical composition of retained embedded fragments removed from injured military personnel, and to relate results to histological findings in tissue adjacent to fragment material. Methods: We describe an approach for the chemical analysis and characterization of retained fragments and adjacent tissues, and include case examples describing fragments containing depleted uranium (DU), tungsten (W), lead (Pb), and non-metal foreign bodies composed of natural and composite materials. Fragments obtained from four patients with penetrating blast wounds to the limbs were studied employing a wide range of chemical and microscopy techniques. Available adjacent tissues from three of the cases were histologically, microscopically, and chemically examined. The physical and compositional properties of the removed foreign material surfaces were examined with energy dispersive x-ray fluorescence spectrometry (EDXRF), scanning electron microscopy (SEM), laser ablation inductively-coupled plasma mass-spectrometry (LA-ICP-MS), and confocal laser Raman

Chemical and isotopic measurements of micrometeoroids by secondary ion mass spectrometry (A0187-2)

NASA Technical Reports Server (NTRS)

Foote, J. H.; Swan, P. D.; Walker, R. M.; Zinner, E. K.; Bahr, D.; Fechtig, H.; Jessberger, E.; Igenbergs, E.; Kreitmayr, U.; Kuczera, H.

1984-01-01

The objective of this experiment is to measure the chemical and isotopic composition of interplanetary dust particles of mass greater than 10 to the minus 10 power G for most of thermator elements expected to be present.

Identification of Chemical-Genetic Interactions via Parallel Analysis of Barcoded Yeast Strains.

PubMed

Suresh, Sundari; Schlecht, Ulrich; Xu, Weihong; Miranda, Molly; Davis, Ronald W; Nislow, Corey; Giaever, Guri; St Onge, Robert P

2016-09-01

The Yeast Knockout Collection is a complete set of gene deletion strains for the budding yeast, Saccharomyces cerevisiae In each strain, one of approximately 6000 open-reading frames is replaced with a dominant selectable marker flanked by two DNA barcodes. These barcodes, which are unique to each gene, allow the growth of thousands of strains to be individually measured from a single pooled culture. The collection, and other resources that followed, has ushered in a new era in chemical biology, enabling unbiased and systematic identification of chemical-genetic interactions (CGIs) with remarkable ease. CGIs link bioactive compounds to biological processes, and hence can reveal the mechanism of action of growth-inhibitory compounds in vivo, including those of antifungal, antibiotic, and anticancer drugs. The chemogenomic profiling method described here measures the sensitivity induced in yeast heterozygous and homozygous deletion strains in the presence of a chemical inhibitor of growth (termed haploinsufficiency profiling and homozygous profiling, respectively, or HIPHOP). The protocol is both scalable and amenable to automation. After competitive growth of yeast knockout collection cultures, with and without chemical inhibitors, CGIs can be identified and quantified using either array- or sequencing-based approaches as described here. © 2016 Cold Spring Harbor Laboratory Press.

The Use of Chemical-Chemical Interaction and Chemical Structure to Identify New Candidate Chemicals Related to Lung Cancer

PubMed Central

Zheng, Mingyue; Kong, Xiangyin; Huang, Tao; Cai, Yu-Dong

2015-01-01

Lung cancer causes over one million deaths every year worldwide. However, prevention and treatment methods for this serious disease are limited. The identification of new chemicals related to lung cancer may aid in disease prevention and the design of more effective treatments. This study employed a weighted network, constructed using chemical-chemical interaction information, to identify new chemicals related to two types of lung cancer: non-small lung cancer and small-cell lung cancer. Then, a randomization test as well as chemical-chemical interaction and chemical structure information were utilized to make further selections. A final analysis of these new chemicals in the context of the current literature indicates that several chemicals are strongly linked to lung cancer. PMID:26047514

Fertilizer/Chemical Sales and Service Worker. Ohio's Competency Analysis Profile.

ERIC Educational Resources Information Center

Ohio State Univ., Columbus. Vocational Instructional Materials Lab.

This Ohio Competency Analysis Profile (OCAP), derived from a modified Developing a Curriculum (DACUM) process, is a current comprehensive and verified employer competency program list for fertilizer/chemical sales and service workers. Each unit (with or without subunits) contains competencies and competency builders that identify the occupational,…

Measurement of HO2 chemical kinetics with a new detection method

NASA Technical Reports Server (NTRS)

Lee, Long C.; Suto, Masako

1986-01-01

Reaction rate constants of HO2+O3 were measured at various temperatures using a newly developed HO2 detection method. HO2 was detected by the OH(A-X) emission produced from photodissociative excitation of HO2 at 147 nm. In order to examine the possible interference of other emitting species with the HO2 detection, the photoexcitation processes of all the chemical species existing in the discharge flow tube were also investigated. The results are summarized.

Implementation of the NMR CHEmical Shift Covariance Analysis (CHESCA): A Chemical Biologist's Approach to Allostery.

PubMed

Boulton, Stephen; Selvaratnam, Rajeevan; Ahmed, Rashik; Melacini, Giuseppe

2018-01-01

Mapping allosteric sites is emerging as one of the central challenges in physiology, pathology, and pharmacology. Nuclear Magnetic Resonance (NMR) spectroscopy is ideally suited to map allosteric sites, given its ability to sense at atomic resolution the dynamics underlying allostery. Here, we focus specifically on the NMR CHEmical Shift Covariance Analysis (CHESCA), in which allosteric systems are interrogated through a targeted library of perturbations (e.g., mutations and/or analogs of the allosteric effector ligand). The atomic resolution readout for the response to such perturbation library is provided by NMR chemical shifts. These are then subject to statistical correlation and covariance analyses resulting in clusters of allosterically coupled residues that exhibit concerted responses to the common set of perturbations. This chapter provides a description of how each step in the CHESCA is implemented, starting from the selection of the perturbation library and ending with an overview of different clustering options.

Consumer Product Chemicals in Indoor Dust: A Quantitative Meta-analysis of U.S. Studies

PubMed Central

2016-01-01

Indoor dust is a reservoir for commercial consumer product chemicals, including many compounds with known or suspected health effects. However, most dust exposure studies measure few chemicals in small samples. We systematically searched the U.S. indoor dust literature on phthalates, replacement flame retardants (RFRs), perfluoroalkyl substances (PFASs), synthetic fragrances, and environmental phenols and estimated pooled geometric means (GMs) and 95% confidence intervals for 45 chemicals measured in ≥3 data sets. In order to rank and contextualize these results, we used the pooled GMs to calculate residential intake from dust ingestion, inhalation, and dermal uptake from air, and then identified hazard traits from the Safer Consumer Products Candidate Chemical List. Our results indicate that U.S. indoor dust consistently contains chemicals from multiple classes. Phthalates occurred in the highest concentrations, followed by phenols, RFRs, fragrance, and PFASs. Several phthalates and RFRs had the highest residential intakes. We also found that many chemicals in dust share hazard traits such as reproductive and endocrine toxicity. We offer recommendations to maximize comparability of studies and advance indoor exposure science. This information is critical in shaping future exposure and health studies, especially related to cumulative exposures, and in providing evidence for intervention development and public policy. PMID:27623734

Exploring sources of biogenic secondary organic aerosol compounds using chemical analysis and the FLEXPART model

NASA Astrophysics Data System (ADS)

Martinsson, Johan; Monteil, Guillaume; Sporre, Moa K.; Kaldal Hansen, Anne Maria; Kristensson, Adam; Eriksson Stenström, Kristina; Swietlicki, Erik; Glasius, Marianne

2017-09-01

Molecular tracers in secondary organic aerosols (SOAs) can provide information on origin of SOA, as well as regional scale processes involved in their formation. In this study 9 carboxylic acids, 11 organosulfates (OSs) and 2 nitrooxy organosulfates (NOSs) were determined in daily aerosol particle filter samples from Vavihill measurement station in southern Sweden during June and July 2012. Several of the observed compounds are photo-oxidation products from biogenic volatile organic compounds (BVOCs). Highest average mass concentrations were observed for carboxylic acids derived from fatty acids and monoterpenes (12. 3 ± 15. 6 and 13. 8 ± 11. 6 ng m-3, respectively). The FLEXPART model was used to link nine specific surface types to single measured compounds. It was found that the surface category sea and ocean was dominating the air mass exposure (56 %) but contributed to low mass concentration of observed chemical compounds. A principal component (PC) analysis identified four components, where the one with highest explanatory power (49 %) displayed clear impact of coniferous forest on measured mass concentration of a majority of the compounds. The three remaining PCs were more difficult to interpret, although azelaic, suberic, and pimelic acid were closely related to each other but not to any clear surface category. Hence, future studies should aim to deduce the biogenic sources and surface category of these compounds. This study bridges micro-level chemical speciation to air mass surface exposure at the macro level.

Analysis of the atmospheric distribution, sources, and sinks of oxygenated volatile organic chemicals based on measurements over the Pacific during TRACE-P

NASA Astrophysics Data System (ADS)

Singh, H. B.; Salas, L. J.; Chatfield, R. B.; Czech, E.; Fried, A.; Walega, J.; Evans, M. J.; Field, B. D.; Jacob, D. J.; Blake, D.; Heikes, B.; Talbot, R.; Sachse, G.; Crawford, J. H.; Avery, M. A.; Sandholm, S.; Fuelberg, H.

2004-08-01

Airborne measurements of a large number of oxygenated volatile organic chemicals (OVOC) were carried out in the Pacific troposphere (0.1-12 km) in winter/spring of 2001 (24 February to 10 April). Specifically, these measurements included acetone (CH3COCH3), methylethyl ketone (CH3COC2H5, MEK), methanol (CH3OH), ethanol (C2H5OH), acetaldehyde (CH3CHO), propionaldehyde (C2H5CHO), peroxyacylnitrates (PANs) (CnH2n+1COO2NO2), and organic nitrates (CnH2n+1ONO2). Complementary measurements of formaldehyde (HCHO), methyl hydroperoxide (CH3OOH), and selected tracers were also available. OVOC were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Background mixing ratios were typically highest in the lower troposphere and declined toward the upper troposphere and the lowermost stratosphere. Their total abundance (ΣOVOC) was nearly twice that of nonmethane hydrocarbons (ΣC2-C8 NMHC). Throughout the troposphere, the OH reactivity of OVOC is comparable to that of methane and far exceeds that of NMHC. A comparison of these data with western Pacific observations collected some 7 years earlier (February-March 1994) did not reveal significant differences. Mixing ratios of OVOC were strongly correlated with each other as well as with tracers of fossil and biomass/biofuel combustion. Analysis of the relative enhancement of selected OVOC with respect to CH3Cl and CO in 12 plumes originating from fires and sampled in the free troposphere (3-11 km) is used to assess their primary and secondary emissions from biomass combustion. The composition of these plumes also indicates a large shift of reactive nitrogen into the PAN reservoir thereby limiting ozone formation. A three-dimensional global model that uses state of the art chemistry and source information is used to compare measured and simulated mixing ratios of selected OVOC. While there is reasonable agreement in many cases, measured aldehyde concentrations are significantly larger than

Application of headspace analysis to the study of sorption of hydrophobic organic chemicals to α-Al2O3

USGS Publications Warehouse

Pelinger, Judith A.; Eisenreich, Steven J.; Capel, Paul D.

1993-01-01

The sorption of hydrophobic organic chemicals (HOCs) to ??-Al2O3 was investigated with a headspace analysis method. The semiautomated headspace analyzer gave rapid, precise, and accurate results for a homologous series alkylbenzenes even at low percentages of solute mass sorbed (3-50%). Sorption experiments carried out with benzene alone indicated weak interactions with well-characterized aluminum oxide, and a solids concentration effect was observed. When the sorption coefficients for benzene alone obtained by headspace analysis were extrapolated up to the solids concentrations typically used in batch sorption experiments, the measured sorption coefficients agreed with reported sorption coefficients for HOCs and sediments of low fractional organic carbon content. Sorbed concentrations increased exponentially with aqueous concentration in isotherms with mixtures of alkylbenzenes, indicating solute-solute interactions at the mineral surface. Sorption was, however, greater than predicted for partitioning of a solute between its pure liquid phase and water, indicating additional influences of the surface and/or the structured liquid near the mineral surface. ?? 1993 American Chemical Society.

In vitro Cytotoxicity and Genotoxicity Analysis of Ten Tannery Chemicals Using SOS/umu Tests and High-content In vitro Micronucleus Tests.

PubMed

Huang, Zehao; Li, Na; Rao, Kaifeng; Liu, Cuiting; Wang, Zijian; Ma, Mei

2018-01-01

More than 2,000 chemicals have been used in the tannery industry. Although some tannery chemicals have been reported to have harmful effects on both human health and the environment, only a few have been subjected to genotoxicity and cytotoxicity evaluations. This study focused on cytotoxicity and genotoxicity of ten tannery chemicals widely used in China. DNA-damaging effects were measured using the SOS/umu test with Salmonella typhimurium TA1535/pSK1002. Chromosome-damaging and cytotoxic effects were determined with the high-content in vitro Micronucleus test (MN test) using the human-derived cell lines MGC-803 and A549. The cytotoxicity of the ten tannery chemicals differed somewhat between the two cell assays, with A549 cells being more sensitive than MGC-803 cells. None of the chemicals induced DNA damage before metabolism, but one was found to have DNA-damaging effects on metabolism. Four of the chemicals, DY64, SB1, DB71 and RR120, were found to have chromosome-damaging effects. A Quantitative Structure-Activity Relationship (QSAR) analysis indicated that one structural feature favouring chemical genotoxicity, Hacceptor-path3-Hacceptor, may contribute to the chromosome-damaging effects of the four MN-test-positive chemicals. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Analysis of the stochastic excitability in the flow chemical reactor

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

Bashkirtseva, Irina

2015-11-30

A dynamic model of the thermochemical process in the flow reactor is considered. We study an influence of the random disturbances on the stationary regime of this model. A phenomenon of noise-induced excitability is demonstrated. For the analysis of this phenomenon, a constructive technique based on the stochastic sensitivity functions and confidence domains is applied. It is shown how elaborated technique can be used for the probabilistic analysis of the generation of mixed-mode stochastic oscillations in the flow chemical reactor.

Analysis of the stochastic excitability in the flow chemical reactor

NASA Astrophysics Data System (ADS)

Bashkirtseva, Irina

2015-11-01

A dynamic model of the thermochemical process in the flow reactor is considered. We study an influence of the random disturbances on the stationary regime of this model. A phenomenon of noise-induced excitability is demonstrated. For the analysis of this phenomenon, a constructive technique based on the stochastic sensitivity functions and confidence domains is applied. It is shown how elaborated technique can be used for the probabilistic analysis of the generation of mixed-mode stochastic oscillations in the flow chemical reactor.

LDEX-PLUS: Lunar Dust Experiment with Chemical Analysis Capability to search for Water

NASA Astrophysics Data System (ADS)

Horanyi, M.; Sternovsky, Z.; Gruen, E.; Kempf, S.; Srama, R.; Postberg, F.

2010-12-01

The Lunar Dust Experiment (LDEX) onboard the Lunar Atmosphee and Dust Explorer Mission (LADEE) is scheduled for launch in early 2013. It will map the variability of the density and size distributions of dust in the lunar vicinity. LDEX is an impact ionization instrument, at an impact speed of > 1.6 km/s, it is capable of measuring the mass of grains with m > 10^(-11) g, and it can also identify a population of smaller grains with m > 10^(-14) kg with a density of n > 10^(-4) cm^(-3). This talk is to introduce the LDEX-PLUS instrument that extends the LDEX capabilities to also measure the chemical composition of the impacting particles with a mass resolution of M/ΔM > 30. We will summarize the science goals, measurement requirements, and the resource needs of this instrument. Traditional methods to analyze surfaces of airless planetary objects from an orbiter are IR and gamma ray spectroscopy, and neutron backscatter measurements. Here we present a complementary method to analyze dust particles as samples of planetary objects from which they were released. The Moon, Mercury, and all other airless planetary object are exposed to the ambient meteoroid bombardment that erodes their surface and generates secondary ejecta particles. Therefore, such objects are enshrouded in clouds of dust particles that have been lifted from their surfaces. In situ mass spectroscopic analysis of these dust particles impacting onto a detector of an orbiting spacecraft reveals their composition, and the origin of each analyzed grain can be determined with an accuracy at the surface that is approximately the altitude of the orbit. Since the detection rates can be on the order of thousands per day, a spatially resolved mapping of the surface composition can be achieved. Possible enhancements include the addition of a dust trajectory sensor to improve the spatial resolution on the surface to ~ 10 km from an altitude of 100 km, and a reflectron type instrument geometry to increase the

Chemically bonded stationary phases that use synthetic hosts containing aromatic binding clefts: HPLC analysis of nitro-substituted polycyclic aromatic hydrocarbons.

PubMed Central

Zimmerman, S C; Saionz, K W; Zeng, Z

1993-01-01

The synthesis of hosts with improved binding affinities for nitroaromatic guests is described. Association constants for several host-guest complexes were measured in chloroform solution and ranged over three orders of magnitude. Two hosts were covalently linked to silica gel to produce chemically bonded stationary phases for HPLC. The use of these phases for HPLC analysis of nitro-substituted polycyclic aromatic hydrocarbons is discussed. PMID:8433981

Chemical evaluation of electronic cigarettes

PubMed Central

Cheng, Tianrong

2014-01-01

Objective To review the available evidence evaluating the chemicals in refill solutions, cartridges, aerosols and environmental emissions of electronic cigarettes (e-cigarettes). Methods Systematic literature searches were conducted to identify research related to e-cigarettes and chemistry using 5 reference databases and 11 search terms. The search date range was January 2007 to September 2013. The search yielded 36 articles, of which 29 were deemed relevant for analysis. Results The levels of nicotine, tobacco-specific nitrosamines (TSNAs), aldehydes, metals, volatile organic compounds (VOCs), flavours, solvent carriers and tobacco alkaloids in e-cigarette refill solutions, cartridges, aerosols and environmental emissions vary considerably. The delivery of nicotine and the release of TSNAs, aldehydes and metals are not consistent across products. Furthermore, the nicotine level listed on the labels of e-cigarette cartridges and refill solutions is often significantly different from measured values. Phenolic compounds, polycyclic aromatic hydrocarbons and drugs have also been reported in e-cigarette refill solutions, cartridges and aerosols. Varying results in particle size distributions of particular matter emissions from e-cigarettes across studies have been observed. Methods applied for the generation and chemical analyses of aerosols differ across studies. Performance characteristics of e-cigarette devices also vary across and within brands. Conclusions Additional studies based on knowledge of e-cigarette user behaviours and scientifically validated aerosol generation and chemical analysis methods would be helpful in generating reliable measures of chemical quantities. This would allow comparisons of e-cigarette aerosol and traditional smoke constituent levels and would inform an evaluation of the toxicity potential of e-cigarettes. PMID:24732157

Chemical evaluation of electronic cigarettes.

PubMed

Cheng, Tianrong

2014-05-01

To review the available evidence evaluating the chemicals in refill solutions, cartridges, aerosols and environmental emissions of electronic cigarettes (e-cigarettes). Systematic literature searches were conducted to identify research related to e-cigarettes and chemistry using 5 reference databases and 11 search terms. The search date range was January 2007 to September 2013. The search yielded 36 articles, of which 29 were deemed relevant for analysis. The levels of nicotine, tobacco-specific nitrosamines (TSNAs), aldehydes, metals, volatile organic compounds (VOCs), flavours, solvent carriers and tobacco alkaloids in e-cigarette refill solutions, cartridges, aerosols and environmental emissions vary considerably. The delivery of nicotine and the release of TSNAs, aldehydes and metals are not consistent across products. Furthermore, the nicotine level listed on the labels of e-cigarette cartridges and refill solutions is often significantly different from measured values. Phenolic compounds, polycyclic aromatic hydrocarbons and drugs have also been reported in e-cigarette refill solutions, cartridges and aerosols. Varying results in particle size distributions of particular matter emissions from e-cigarettes across studies have been observed. Methods applied for the generation and chemical analyses of aerosols differ across studies. Performance characteristics of e-cigarette devices also vary across and within brands. Additional studies based on knowledge of e-cigarette user behaviours and scientifically validated aerosol generation and chemical analysis methods would be helpful in generating reliable measures of chemical quantities. This would allow comparisons of e-cigarette aerosol and traditional smoke constituent levels and would inform an evaluation of the toxicity potential of e-cigarettes.

Simultaneous assimilation of satellite NO2, O3, CO, and HNO3 data for the analysis of the tropospheric chemical composition

NASA Astrophysics Data System (ADS)

Miyazaki, K.; Eskes, H.; Sudo, K.

2012-04-01

Carbon monoxide (CO) and nitrogen oxides (NOx) play an important role in tropospheric chemistry through their influences on the ozone and hydroxyl radical (OH). The simultaneous optimization of various chemical components is expected to improve the emission inversion through the better description of the chemical feedbacks in the NOx- and CO-chemistry. This study aims to reproduce chemical composition distributions in the troposphere by combining information obtained from multiple satellite data sets. The emissions of CO and NOx, together with the 3D concentration fields of all forecasted chemical species in the global CTM CHASER have been simultaneously optimized using the ensemble Kalman filter (EnKF) data assimilation technique, and NO2, O3, CO, and HNO3 data obtained from OMI, TES, MOPITT, and MLS satellite measurements. The performance is evaluated against independent data from ozone sondes, aircraft measurements, GOME-2, and SCIAMACHY satellite data. Observing System Experiments (OSEs) have been carried out. These OSEs quantify the relative importance of each data set on constraining the emissions and concentrations. We confirmed that the simultaneous data assimilation improved the agreement with these independent data sets. The combined analysis of multiple data sets by means of advanced data assimilation system can provide a useful framework for the air quality research.

Voltage and partial pressure dependent defect chemistry in (La,Sr)FeO3-δ thin films investigated by chemical capacitance measurements.

PubMed

Schmid, Alexander; Rupp, Ghislain M; Fleig, Jürgen

2018-05-03

La0.6Sr0.4FeO3-δ (LSF) thin films of different thickness were prepared by pulsed laser deposition on yttria stabilized zirconia (YSZ) and characterized by using three electrode impedance spectroscopy. Electrochemical film capacitance was analyzed in relation to oxygen partial pressure (0.25 mbar to 1 bar), DC polarization (0 m to -600 m) and temperature (500 to 650 °C). For most measurement parameters, the chemical bulk capacitance dominates the overall capacitive properties and the corresponding defect chemical state depends solely on the oxygen chemical potential inside the film, independent of atmospheric oxygen pressure and DC polarization. Thus, defect chemical properties (defect concentrations and defect formation enthalpies) could be deduced from such measurements. Comparison with LSF defect chemical bulk data from the literature showed good agreement for vacancy formation energies but suggested larger electronic defect concentrations in the films. From thickness-dependent measurements at lower oxygen chemical potentials, an additional capacitive contribution could be identified and attributed to the LSF|YSZ interface. Deviations from simple chemical capacitance models at high pressures are most probably due to defect interactions.

Natural chemical shielding analysis of nuclear magnetic resonance shielding tensors from gauge-including atomic orbital calculations

NASA Astrophysics Data System (ADS)

Bohmann, Jonathan A.; Weinhold, Frank; Farrar, Thomas C.

1997-07-01

Nuclear magnetic shielding tensors computed by the gauge including atomic orbital (GIAO) method in the Hartree-Fock self-consistent-field (HF-SCF) framework are partitioned into magnetic contributions from chemical bonds and lone pairs by means of natural chemical shielding (NCS) analysis, an extension of natural bond orbital (NBO) analysis. NCS analysis complements the description provided by alternative localized orbital methods by directly calculating chemical shieldings due to delocalized features in the electronic structure, such as bond conjugation and hyperconjugation. Examples of NCS tensor decomposition are reported for CH4, CO, and H2CO, for which a graphical mnemonic due to Cornwell is used to illustrate the effect of hyperconjugative delocalization on the carbon shielding.

TESTING DUPLICATE DIET SAMPLE COLLECTION METHODS FOR MEASURING PERSONAL DIETARY EXPOSURES TO CHEMICAL CONTAMINANTS

EPA Science Inventory

Dietary ingestion may be a significant pathway of human exposure to many potentially toxic chemicals. The U.S.Environmental Protection Agency-National Human Exposure Laboratory has made the development of methods for measuring persoanl dietary exposures a high priority for its di...

[Measurement of chemical agents in metallurgy field: electric steel plant].

PubMed

Cottica, D; Grignani, E; Ghitti, R; Festa, D; Apostoli, P

2012-01-01

The steel industry maintains its important position in the context of the Italian production involving thousands of workers. The iron and steel processes are divided into primary steel industry, production of intermediate minerals, and secondary steel, scrap from the production of semi-finished industrial and consumer sector (metal inserted into components and metal used for dissipative uses, primarily coatings) and industrial waste. The paper presents the results of environmental monitoring carried out in some electric steel plant for the measurement of airborne chemicals that characterize the occupational exposure of workers employed in particular area like electric oven, to treatment outside the furnace, continuous casting area. For the sampling of the pollutants were used both personal and in fixed positions samplers. The pollutants measured are those typical of steel processes inhalable dust, metals, respirable dust, crystalline silica, but also Polycyclic Aromatic Hydrocarbons (PAH), polychlorinated dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs).

Quantitative Chemical Imaging and Unsupervised Analysis Using Hyperspectral Coherent Anti-Stokes Raman Scattering Microscopy

PubMed Central

2013-01-01

In this work, we report a method to acquire and analyze hyperspectral coherent anti-Stokes Raman scattering (CARS) microscopy images of organic materials and biological samples resulting in an unbiased quantitative chemical analysis. The method employs singular value decomposition on the square root of the CARS intensity, providing an automatic determination of the components above noise, which are retained. Complex CARS susceptibility spectra, which are linear in the chemical composition, are retrieved from the CARS intensity spectra using the causality of the susceptibility by two methods, and their performance is evaluated by comparison with Raman spectra. We use non-negative matrix factorization applied to the imaginary part and the nonresonant real part of the susceptibility with an additional concentration constraint to obtain absolute susceptibility spectra of independently varying chemical components and their absolute concentration. We demonstrate the ability of the method to provide quantitative chemical analysis on known lipid mixtures. We then show the relevance of the method by imaging lipid-rich stem-cell-derived mouse adipocytes as well as differentiated embryonic stem cells with a low density of lipids. We retrieve and visualize the most significant chemical components with spectra given by water, lipid, and proteins segmenting the image into the cell surrounding, lipid droplets, cytosol, and the nucleus, and we reveal the chemical structure of the cells, with details visualized by the projection of the chemical contrast into a few relevant channels. PMID:24099603

Chemical composition of aerosol measurements in the air pollution plume during KORUS-AQ

NASA Astrophysics Data System (ADS)

Park, T.; Lee, J. B.; Lim, Y. J.; Ahn, J.; Park, J. S.; Soo, C. J.; Kim, J.; Park, S.; Lee, Y.; Desyaterik, Y.; Collett, J. L., Jr.; Lee, T.

2017-12-01

The Korean peninsula is a great place to study different sources of the aerosols: urban, rural and marine. In addition, Seoul is one of the large metropolitan areas in the world and has a variety of sources because half of the Korean population lives in Seoul, which comprises only 12% of the country's area. To understand the chemical composition of aerosol form long-range transport and local sources better, an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed on an airborne platform (NASA DC-8 aircraft). The HR-ToF-AMS is capable of measuring non-refractory size resolved chemical composition of submicron particle(NR-PM1) in the air pollution plume, including mass concentration of organic carbon, nitrate, sulfate, and ammonium with 10 seconds time resolution. The measurements were performed twenty times research flight for understanding characteristic of the air pollution from May to June, 2016 on the South Korean peninsula during KORUS-AQ 2016 campaign. The scientific goal of this study is to characterize aerosol chemical properties and mass concentration in order to understand the role of the long-range transport from northeast Asia to South Korea, and influence of the local sources. To brief, organics dominated during all of flights. Also, organics and nitrate were dominant around energy industrial complex near by Taean, South Korea. The presentation will provide an overview of the composition of NR-PM1 measured in air pollution plumes, and deliver detail information about width, depth and spatial distribution of the pollutant in the air pollution plumes. The results of this study will provide high temporal and spatial resolved details on the air pollution plumes, which are valuable input parameters of aerosol properties for the current air quality models.

Histopathological image analysis of chemical-induced hepatocellular hypertrophy in mice.

PubMed

Asaoka, Yoshiji; Togashi, Yuko; Mutsuga, Mayu; Imura, Naoko; Miyoshi, Tomoya; Miyamoto, Yohei

2016-04-01

Chemical-induced hepatocellular hypertrophy is frequently observed in rodents, and is mostly caused by the induction of phase I and phase II drug metabolic enzymes and peroxisomal lipid metabolic enzymes. Liver weight is a sensitive and commonly used marker for detecting hepatocellular hypertrophy, but is also increased by a number of other factors. Histopathological observations subjectively detect changes such as hepatocellular hypertrophy based on the size of a hepatocyte. Therefore, quantitative microscopic observations are required to evaluate histopathological alterations objectively. In the present study, we developed a novel quantitative method for an image analysis of hepatocellular hypertrophy using liver sections stained with hematoxylin and eosin, and demonstrated its usefulness for evaluating hepatocellular hypertrophy induced by phenobarbital (a phase I and phase II enzyme inducer) and clofibrate (a peroxisomal enzyme inducer) in mice. The algorithm of this imaging analysis was designed to recognize an individual hepatocyte through a combination of pixel-based and object-based analyses. Hepatocellular nuclei and the surrounding non-hepatocellular cells were recognized by the pixel-based analysis, while the areas of the recognized hepatocellular nuclei were then expanded until they ran against their expanding neighboring hepatocytes and surrounding non-hepatocellular cells by the object-based analysis. The expanded area of each hepatocellular nucleus was regarded as the size of an individual hepatocyte. The results of this imaging analysis showed that changes in the sizes of hepatocytes corresponded with histopathological observations in phenobarbital and clofibrate-treated mice, and revealed a correlation between hepatocyte size and liver weight. In conclusion, our novel image analysis method is very useful for quantitative evaluations of chemical-induced hepatocellular hypertrophy. Copyright © 2015 Elsevier GmbH. All rights reserved.

A silicone column for GC analysis of polar and nonpolar chemicals

NASA Technical Reports Server (NTRS)

Shen, T. C.

1991-01-01

The investigation of the Saturnian System is being proposed jointly by NASA and the European Space Agency (ESA). The mission is scheduled for a launch in 1996. The mission provides an opportunity for close observation and exploration of Saturn's atmosphere, the complex Saturnian System of satellites and rings, Titan (Saturn's planet-sized moon), and Saturn's magnetosphere. The mission gives special attention to Titan which is blanketed by a thick, opaque atmosphere. An atmospheric probe will be deposited into the Titan Atmosphere for in situ measurement during a slow, three hour descent to the surface. The results from this analysis may provide the information which is important to the research of chemical evolution, and the origin of life. An analytical system was developed as a part of the Titan Aerosol Gas Experiment (TAGEX), a proposed experiment for the Cassini Mission. This system will use two highly sensitive detectors, the Metastable Ionization Detector (MID) and the Ion Mobility Spectrometer (IMS). Unfortunately, when commercial columns are utilized with these highly sensitive detectors, volatile components continuously bleed from the column and interfere with the detector. In addition, light columns must be able to separate polar and nonpolar organic chemicals within 10-15 minutes under isothermal conditions for the Titan Mission. Therefore, a highly crosslinked silicone polymeric packed column was developed which is able to efficiently separate amines, alcohols, and hydrocarbons with retention times less that 15 minutes at 100 C isothermal condition.

Cross-Scale Molecular Analysis of Chemical Heterogeneity in Shale Rocks

DOE PAGES

Hao, Zhao; Bechtel, Hans A.; Kneafsey, Timothy; ...

2018-02-07

The organic and mineralogical heterogeneity in shale at micrometer and nanometer spatial scales contributes to the quality of gas reserves, gas flow mechanisms and gas production. Here, we demonstrate two molecular imaging approaches based on infrared spectroscopy to obtain mineral and kerogen information at these mesoscale spatial resolutions in large-sized shale rock samples. The first method is a modified microscopic attenuated total reflectance measurement that utilizes a large germanium hemisphere combined with a focal plane array detector to rapidly capture chemical images of shale rock surfaces spanning hundreds of micrometers with micrometer spatial resolution. The second method, synchrotron infrared nano-spectroscopy,more » utilizes a metallic atomic force microscope tip to obtain chemical images of micrometer dimensions but with nanometer spatial resolution. This chemically "deconvoluted" imaging at the nano-pore scale is then used to build a machine learning model to generate a molecular distribution map across scales with a spatial span of 1000 times, which enables high-throughput geochemical characterization in greater details across the nano-pore and micro-grain scales and allows us to identify co-localization of mineral phases with chemically distinct organics and even with gas phase sorbents. Finally, this characterization is fundamental to understand mineral and organic compositions affecting the behavior of shales.« less

Cross-Scale Molecular Analysis of Chemical Heterogeneity in Shale Rocks

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

Hao, Zhao; Bechtel, Hans A.; Kneafsey, Timothy

The organic and mineralogical heterogeneity in shale at micrometer and nanometer spatial scales contributes to the quality of gas reserves, gas flow mechanisms and gas production. Here, we demonstrate two molecular imaging approaches based on infrared spectroscopy to obtain mineral and kerogen information at these mesoscale spatial resolutions in large-sized shale rock samples. The first method is a modified microscopic attenuated total reflectance measurement that utilizes a large germanium hemisphere combined with a focal plane array detector to rapidly capture chemical images of shale rock surfaces spanning hundreds of micrometers with micrometer spatial resolution. The second method, synchrotron infrared nano-spectroscopy,more » utilizes a metallic atomic force microscope tip to obtain chemical images of micrometer dimensions but with nanometer spatial resolution. This chemically "deconvoluted" imaging at the nano-pore scale is then used to build a machine learning model to generate a molecular distribution map across scales with a spatial span of 1000 times, which enables high-throughput geochemical characterization in greater details across the nano-pore and micro-grain scales and allows us to identify co-localization of mineral phases with chemically distinct organics and even with gas phase sorbents. Finally, this characterization is fundamental to understand mineral and organic compositions affecting the behavior of shales.« less

ISS Expeditions 16 through 20: Chemical Analysis Results for Potable Water

NASA Technical Reports Server (NTRS)

Straub, John E., II; Plumlee, Debrah K.; Schultz, John R.

2010-01-01

During the 2-year span from Expedition 16 through Expedition 20, the chemical quality of the potable water onboard the International Space Station (ISS) was verified safe for crew consumption through the return and chemical analysis of archival water samples by the Water and Food Analytical Laboratory (WAFAL) at Johnson Space Center (JSC). Reclaimed cabin humidity condensate and Russian ground-supplied water were the principal sources of potable water for Expeditions 16 through 18. During Expedition 18 the U.S. water processor assembly was delivered, installed, and tested during a 90-day checkout period. Beginning with Expedition 19, U.S. potable water recovered from a combined waste stream of humidity condensate and pretreated urine was also available for ISS crew use. A total of 74 potable water samples were collected using U.S. sampling hardware during Expeditions 16 through 20 and returned on both Shuttle and Soyuz vehicles. The results of JSC chemical analyses of these ISS potable water samples are presented in this paper. Eight potable water samples collected in flight with Russian hardware were also received for analysis, as well as 5 preflight samples of Rodnik potable water delivered to ISS on Russian Progress vehicles 28 to 34. Analytical results for these additional potable water samples are also reported and discussed.

Global Analysis Reveals Families of Chemical Motifs Enriched for hERG Inhibitors

PubMed Central

Du, Fang; Babcock, Joseph J.; Yu, Haibo; Zou, Beiyan; Li, Min

2015-01-01

Promiscuous inhibition of the human ether-à-go-go-related gene (hERG) potassium channel by drugs poses a major risk for life threatening arrhythmia and costly drug withdrawals. Current knowledge of this phenomenon is derived from a limited number of known drugs and tool compounds. However, in a diverse, naïve chemical library, it remains unclear which and to what degree chemical motifs or scaffolds might be enriched for hERG inhibition. Here we report electrophysiology measurements of hERG inhibition and computational analyses of >300,000 diverse small molecules. We identify chemical ‘communities’ with high hERG liability, containing both canonical scaffolds and structurally distinctive molecules. These data enable the development of more effective classifiers to computationally assess hERG risk. The resultant predictive models now accurately classify naïve compound libraries for tendency of hERG inhibition. Together these results provide a more complete reference map of characteristic chemical motifs for hERG liability and advance a systematic approach to rank chemical collections for cardiotoxicity risk. PMID:25700001

Demonstration of Laser Induced Acoustic Desoprtion - Chemical Ionization Mass Spectrometry (LIAD-CIMS) for Fragment-Free Measurements of Organic Aerosol Molecular Composition

NASA Astrophysics Data System (ADS)

Browne, E. C.; Abdelhamid, A.; Berry, J.; Alton, M.

2017-12-01

Organic compounds account for a significant portion of fine atmospheric aerosol. Current analytical techniques have provided insights on organic aerosol (OA) sources, composition, and chemical modification pathways. Despite this knowledge, large uncertainties remain and hinder our understanding of aerosol impacts on climate, air quality, and health. Measuring OA composition is challenging due to the complex chemical composition and the wide variation in the properties (e.g., vapor pressure, solubility, reactivity) of organic compounds. In many current measurement techniques, the ability to chemically resolve and quantify OA components is complicated by molecular decomposition, matrix effects, and/or preferential ionization mechanisms. Here, we utilize a novel desorption technique, laser induced acoustic desorption (LIAD), that generates fragment-free, neutral gas-phase molecules. We couple LIAD with a high-resolution chemical ionization mass spectrometer (CIMS) to provide molecular composition OA measurements. Through a series of laboratory experiments, we demonstrate the ability of this technique to measure large, thermally labile species without fragmentation/thermal decomposition. We discuss quantification and detection limits of this technique. We compare LIAD-CIMS measurements with thermal desorption-CIMS measurements using off-line measurements of ambient aerosol collected in Boulder, CO. Lastly, we discuss future development for on-line measurements of OA using LIAD-CIMS.

VHH antibodies: Emerging reagents for the analysis of environmental chemicals

PubMed Central

Bever, Candace S.; Dong, Jie-Xian; Vasylieva, Natalia; Barnych, Bogdan; Cui, Yongliang; Xu, Zhen-Lin; Hammock, Bruce D.; Gee, Shirley J.

2016-01-01

A VHH antibody (or nanobody) is the antigen binding fragment of heavy chain only antibodies. Discovered nearly 25 years ago, they have been investigated for their use in clinical therapeutics and immunodiagnostics, and more recently for environmental monitoring applications. A new and valuable immunoreagent for the analysis of small molecular weight environmental chemicals, VHH will overcome many pitfalls encountered with conventional reagents. In the work so far, VHH antibodies often perform comparably to conventional antibodies for small molecule analysis, are amenable to numerous genetic engineering techniques, and show ease of adaption to other immunodiagnostic platforms for use in environmental monitoring. Recent reviews cover the structure and production of VHH antibodies as well as their use in clinical settings. However, no report focuses on the use of these VHH antibodies to small environmental chemicals (MW <1,500 Da). This review article summarizes the efforts made to produce VHHs to various environmental targets, compares the VHH-based assays with conventional antibody assays, and discusses the advantages and limitations in developing these new antibody reagents particularly to small molecule targets. PMID:27209591

Final Report for SERDP Project RC-1649: Advanced Chemical Measurements of Smoke from DoD-prescribed Burns

Treesearch

T.J. Johnson; R.J. Yokelson; S.K. Akagi; I.R. Burling; D.R. Weise; S.P. Urbanski; C.E. Stockwell; J. Reardon; E.N. Lincoln; L.T.M. Profeta; A. Mendoza; M.D.W. Schneider; R.L. Sams; S.D. Williams; C.E. Wold; D.W.T. Griffith; M. Cameron; J.B. Gilman; C. Warneke; J.M. Roberts; P. Veres; W.C. Kuster; J de Gouw

2014-01-01

Project RC-1649, "Advanced Chemical Measurement of Smoke from DoD-prescribed Burns" was undertaken to use advanced instrumental techniques to study in detail the particulate and vapor-phase chemical composition of the smoke that results from prescribed fires used as a land management tool on DoD bases, particularly bases in the southeastern U.S. The statement...

The Relationship between Perceived Sleep Quality, Polysomnographic Measures and Depressive Symptoms in Chemically-Injured Veterans: A Pilot Study.

PubMed

Moshkani Farahani, Davood; Tavallaie, Abbas; Vahedi, Ensieh; Rezaiemaram, Peyman; Naderi, Zohreh; Talaie, Akram

2014-07-01

Sleep complaints are common among Iranian chemically-injured veterans. The growing body of research has investigated (in) equalities between such subjective complaints and objective sleep records. Moreover, sleep complaints are associated with depressive symptoms. Depressive symptoms, also, have been frequently reported in chemically-injured veterans. Therefore, the purpose of this pilot study was to investigate the relationship between perceived sleep quality, polysomnographic measures and depressive symptoms in Iranian veterans with chemical injuries. In this pilot study, 35 Iranian veterans with chemical injuries complaining of a sleep problem were selected. Initially, participants were evaluated via all-night polysomnography, then, they completed the research questionnaires. Collected data were analyzed using Pearson correlation coefficients. Data analyses showed that there was no significant correlation between many of self-reposted variables and polysomnogaphic recordings, however, remarkable relationships were found between the Pittsburgh Sleep Quality Index and the Beck Depression Inventory scores. The findings indicated that sleep complaints of chemically-injured veterans are not equivalent to objective sleep disturbances, however, these complaints are largely associated with level of depression. This study emphasizes the important role of mood in sleep evaluation. Further, the findings suggest using a combination of both subjective and objective measures for accurate assessment of sleep quality in Iranian veterans with chemical injuries (i.e., multimethod approach).

In situ mineralogical-chemical analysis of Martian materials at landing/roving sites by active and passive remote sensing methods

NASA Technical Reports Server (NTRS)

Neukum, G.; Lehmann, F.; Regner, P.; Jaumann, R.

1988-01-01

Remote sensing of the Martian surface from the ground and from orbiting spacecraft has provided some first-order insight into the mineralogical-chemical composition and the weathering state of Martian surface materials. Much more detailed information can be gathered from performing such measurements in situ at the landing sites or from a rover in combination with analogous measurements from orbit. Measurements in the wavelength range of approximately 0.3 to 12.0 micrometers appear to be suitable to characterize much of the physical, mineralogical, petrological, and chemical properties of Martian surface materials and the weathering and other alteration processes that have acted on them. It is of particular importance to carry out measurements at the same time over a broad wavelength range since the reflectance signatures are caused by different effects and hence give different and complementing information. It appears particularly useful to employ a combination of active and passive methods because the use of active laser spectroscopy allows the obtaining of specific information on thermal infrared reflectance of surface materials. It seems to be evident that a spectrometric survey of Martian materials has to be focused on the analysis of altered and fresh mafic materials and rocks, water-bearing silicates, and possibly carbonates.

In situ laser-induced breakdown spectroscopy measurements of chemical compositions in stainless steels during tungsten inert gas welding

NASA Astrophysics Data System (ADS)

Taparli, Ugur Alp; Jacobsen, Lars; Griesche, Axel; Michalik, Katarzyna; Mory, David; Kannengiesser, Thomas

2018-01-01

A laser-induced breakdown spectroscopy (LIBS) system was combined with a bead-on-plate Tungsten Inert Gas (TIG) welding process for the in situ measurement of chemical compositions in austenitic stainless steels during welding. Monitoring the weld pool's chemical composition allows governing the weld pool solidification behavior, and thus enables the reduction of susceptibility to weld defects. Conventional inspection methods for weld seams (e.g. ultrasonic inspection) cannot be performed during the welding process. The analysis system also allows in situ study of the correlation between the occurrence of weld defects and changes in the chemical composition in the weld pool or in the two-phase region where solid and liquid phase coexist. First experiments showed that both the shielding Ar gas and the welding arc plasma have a significant effect on the selected Cr II, Ni II and Mn II characteristic emissions, namely an artificial increase of intensity values via unspecific emission in the spectra. In situ investigations showed that this artificial intensity increase reached a maximum in presence of weld plume. Moreover, an explicit decay has been observed with the termination of the welding plume due to infrared radiation during sample cooling. Furthermore, LIBS can be used after welding to map element distribution. For austenitic stainless steels, Mn accumulations on both sides of the weld could be detected between the heat affected zone (HAZ) and the base material.

Analysis of Environmental Chemical Mixtures and Non-Hodgkin Lymphoma Risk in the NCI-SEER NHL Study

PubMed Central

Czarnota, Jenna; Gennings, Chris; Colt, Joanne S.; De Roos, Anneclaire J.; Cerhan, James R.; Severson, Richard K.; Hartge, Patricia; Ward, Mary H.

2015-01-01

Background There are several suspected environmental risk factors for non-Hodgkin lymphoma (NHL). The associations between NHL and environmental chemical exposures have typically been evaluated for individual chemicals (i.e., one-by-one). Objectives We determined the association between a mixture of 27 correlated chemicals measured in house dust and NHL risk. Methods We conducted a population-based case–control study of NHL in four National Cancer Institute–Surveillance, Epidemiology, and End Results centers—Detroit, Michigan; Iowa; Los Angeles County, California; and Seattle, Washington—from 1998 to 2000. We used weighted quantile sum (WQS) regression to model the association of a mixture of chemicals and risk of NHL. The WQS index was a sum of weighted quartiles for 5 polychlorinated biphenyls (PCBs), 7 polycyclic aromatic hydrocarbons (PAHs), and 15 pesticides. We estimated chemical mixture weights and effects for study sites combined and for each site individually, and also for histologic subtypes of NHL. Results The WQS index was statistically significantly associated with NHL overall [odds ratio (OR) = 1.30; 95% CI: 1.08, 1.56; p = 0.006; for one quartile increase] and in the study sites of Detroit (OR = 1.71; 95% CI: 1.02, 2.92; p = 0.045), Los Angeles (OR = 1.44; 95% CI: 1.00, 2.08; p = 0.049), and Iowa (OR = 1.76; 95% CI: 1.23, 2.53; p = 0.002). The index was marginally statistically significant in Seattle (OR = 1.39; 95% CI: 0.97, 1.99; p = 0.071). The most highly weighted chemicals for predicting risk overall were PCB congener 180 and propoxur. Highly weighted chemicals varied by study site; PCBs were more highly weighted in Detroit, and pesticides were more highly weighted in Iowa. Conclusions An index of chemical mixtures was significantly associated with NHL. Our results show the importance of evaluating chemical mixtures when studying cancer risk. Citation Czarnota J, Gennings C, Colt JS, De Roos AJ, Cerhan JR, Severson RK, Hartge P, Ward MH

Chemical analysis of extracting transition metal oxides from polymetallic ore by sulphate process

NASA Astrophysics Data System (ADS)

Enkh-Uyanga, Otgon-Uul; Munkhtsetseg, Baatar; Urangoo, Urtnasan; Tserendulam, Enkhtur; Agiimaa, Davaadorj

2017-06-01

In this research work we attempt to improve the purity of polymetallic ores in Mongolia whilst developing practical applications of its refinement processes and this paper presents the results of chemical research of extracting transition metal titanium oxides, ferrous oxide and rare earth oxides from polymetallic ore. Thereby, chemical and mineral analysis of polymetallic ore is carried out basis of responses to the support process at various degrees of water whereas transition metal sulphates solubility differ. As a result of sulphate and resulphurization process we have extracted anatase with 62.5 percent titanium dioxide and brookite mineral with 89.6 percent of titanium dioxide as well as mineral with 83.8 percent of ferrous oxide hematite and rare earth oxides with 57.6 percent of cerium oxide. These oxides are identified under various conditions in the thermal processing. The morphology structure and chemical content compound of the mineral has been verified as a result of the XRF, XRD, SEM-EDX analysis.

Laser-based mass spectrometry for in situ chemical composition analysis of planetary surfaces

NASA Astrophysics Data System (ADS)

Frey, Samira; Neuland, Maike B.; Grimaudo, Valentine; Moreno-García, Pavel; Riedo, Andreas; Tulej, Marek; Broekmann, Peter; Wurz, Peter

2016-04-01

Mass spectrometry is an important analytical technique in space research. The chemical composition of planetary surface material is a key scientific question on every space mission to a planet, moon or asteroid. Chemical composition measurements of rocky material on the surface are of great importance to understand the origin and evolution of the planetary body.[1] A miniature laser ablation/ionisation reflectron- type time-of-flight mass spectrometer (instrument name LMS) was designed and built at the University of Bern for planetary research.[2] Despite its small size and light weight, the LMS instrument still maintains the same capabilities as large laboratory systems, which makes it suitable for its application on planetary space missions.[3-5] The high dynamic range of about eight orders of magnitude, high lateral (μm-level) and vertical (sub-nm level) resolution and high detection sensitivity for almost all elements (10 ppb, atomic fraction) make LMS a versatile instrument for various applications. LMS is a suitable instrument for in situ measurements of elemental and isotope composition with high precision and accuracy. Measurements of Pb- isotope abundances can be used for dating of planetary material. Measurements of bio-relevant elements allow searching for past or present life on a planetary surface. The high spatial resolution, both in lateral and vertical direction, is of considerable interest, e.g. for analysis of inhomogeneous, extraterrestrial samples as well as weathering processes of planetary material. References [1] P. Wurz, D. Abplanalp, M. Tulej, M. Iakovleva, V.A. Fernandes, A. Chumikov, and G. Managadze, "Mass Spectrometric Analysis in Planetary Science: Investigation of the Surface and the Atmosphere", Sol. Sys. Res., 2012, 46, 408. [2] U. Rohner, J.A. Whitby, P. Wurz, "A miniature laser ablation time of flight mass spectrometer for in situ planetary exploration" Meas. Sci. Tch., 2003, 14, 2159. [3] M. Tulej, A. Riedo, M.B. Neuland, S

Chemical analysis of plants that poison livestock: Successes, challenges, and opportunities

USDA-ARS?s Scientific Manuscript database

Poisonous plants have a devastating impact on the livestock industry, as well as human health. In order to fully understand the effects of poisonous plants, multiple scientific disciplines are required. Chemical analysis of plant secondary compounds is key to identifying the responsible toxins, char...

The dilemma in prioritizing chemicals for environmental analysis: known versus unknown hazards.

PubMed

Anna, Sobek; Sofia, Bejgarn; Christina, Rudén; Magnus, Breitholtz

2016-08-10

A major challenge for society is to manage the risks posed by the many chemicals continuously emitted to the environment. All chemicals in production and use cannot be monitored and science-based strategies for prioritization are essential. In this study we review available data to investigate which substances are included in environmental monitoring programs and published research studies reporting analyses of chemicals in Baltic Sea fish between 2000 and 2012. Our aim is to contribute to the discussion of priority settings in environmental chemical monitoring and research, which is closely linked to chemical management. In total, 105 different substances or substance groups were analyzed in Baltic Sea fish. Polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were the most studied substances or substance groups. The majority, 87%, of all analyses comprised 20% of the substances or substance groups, whereas 46 substance groups (44%) were analyzed only once. Almost three quarters of all analyses regarded a POP-substance (persistent organic pollutant). These results demonstrate that the majority of analyses on environmental contaminants in Baltic Sea fish concern a small number of already regulated chemicals. Legacy pollutants such as POPs pose a high risk to the Baltic Sea due to their hazardous properties. Yet, there may be a risk that prioritizations for chemical analyses are biased based on the knowns of the past. Such biases may lead to society failing in identifying risks posed by yet unknown hazardous chemicals. Alternative and complementary ways to identify priority chemicals are needed. More transparent communication between risk assessments performed as part of the risk assessment process within REACH and monitoring programs, and information on chemicals contained in consumer articles, would offer ways to identify chemicals for environmental analysis.

Association of environmental chemicals & estrogen metabolites in children.

PubMed

Ihde, Erin Speiser; Loh, Ji Meng; Rosen, Lawrence

2015-12-17

The prevalence of pediatric hormonal disorders and hormonally-sensitive cancers are rising. Chemicals including bisphenol A (BPA), phthalates, parabens, 4-nonylphenol (4NP) and triclosan have been linked to disruption of endocrine pathways and altered hormonal status in both animal and human studies. Additionally, changes in estrogen metabolism have been associated with pediatric endocrine disorders and linked to estrogen-dependent cancers. The main objective of the study was to measure the presence of these environmental chemicals in prepubescent children and assess the relationship between chemical metabolites and estrogen metabolism. 50 subjects (25 male, 25 female) were recruited from the principal investigator's existing patient population at his pediatric primary care office. The first 5 boys and 5 girls in each age group (4 through 8 years old inclusive) who presented for annual examinations were included, as long as they were Tanner Stage I (prepubertal) on physical exam, without diagnosis of hormonally-related condition and/or cancer and able to give a urine sample. Urine samples were collected in glass containers for analysis of chemical and estrogen metabolites. Study kits and lab analysis were provided by Genova Diagnostics (Duluth, GA). Summary statistics for the concentrations of each chemical metabolite as well as estrogen metabolites were computed (minimum, maximum, median and inter-quartile range) for males only, for females only and for all subjects. Comparisons between groups (e.g. males v. females) were assessed using the nonparametric Wilcoxon test, since the data was skewed. The correlation between concentrations of chemical metabolites and estrogen metabolites in prepubescent children were examined by the Spearman's correlation coefficient (ρ). 100 % of subjects had detectable levels of at least five chemicals [corrected] in their urine, and 74 % had detectable levels of eight or more chemicals. 28 % of subjects had measurable levels of 4NP

A Finite Rate Chemical Analysis of Nitric Oxide Flow Contamination Effects on Scramjet Performance

NASA Technical Reports Server (NTRS)

Cabell, Karen F.; Rock, Kenneth E.

2003-01-01

The level of nitric oxide contamination in the test gas of the Langley Research Center Arc-Heated Scramjet Test Facility and the effect of the contamination on scramjet test engine performance were investigated analytically. A finite rate chemical analysis was performed to determine the levels of nitric oxide produced in the facility at conditions corresponding to Mach 6 to 8 flight simulations. Results indicate that nitric oxide levels range from one to three mole percent, corroborating previously obtained measurements. A three-stream combustor code with finite rate chemistry was used to investigate the effects of nitric oxide on scramjet performance. Results indicate that nitric oxide in the test gas causes a small increase in heat release and thrust performance for the test conditions investigated. However, a rate constant uncertainty analysis suggests that the effect of nitric oxide ranges from no net effect, to an increase of about 10 percent in thrust performance.

Meta-Analysis of Mass Balances Examining Chemical Fate during Wastewater Treatment

PubMed Central

2008-01-01

Mass balances are an instructive means for investigating the fate of chemicals during wastewater treatment. In addition to the aqueous-phase removal efficiency (Φ), they can inform on chemical partitioning, transformation, and persistence, as well as on the chemical loading to streams and soils receiving, respectively, treated effluent and digested sewage sludge (biosolids). Release rates computed on a per-capita basis can serve to extrapolate findings to a larger scale. This review examines over a dozen mass balances conducted for various organic wastewater contaminants, including prescription drugs, estrogens, fragrances, antimicrobials, and surfactants of differing sorption potential (hydrophobicity), here expressed as the 1-octanol−water partition coefficient (KOW) and the organic carbon normalized sorption coefficient (KOC). Major challenges to mass balances are the collection of representative samples and accurate quantification of chemicals in sludge. A meta-analysis of peer-reviewed data identified sorption potential as the principal determinant governing chemical persistence in biosolids. Occurrence data for organic wastewater compounds detected in digested sludge followed a simple nonlinear model that required only KOW or KOC as the input and yielded a correlation coefficient of 0.9 in both instances. The model predicted persistence in biosolids for the majority (>50%) of the input load of organic wastewater compounds featuring a log10KOW value of greater than 5.2 (log10KOC > 4.4). In contrast, hydrophobicity had no or only limited value for estimating, respectively, Φ and the overall persistence of a chemical during conventional wastewater treatment. PMID:18800497

Measurement of spin-lattice relaxation times and concentrations in systems with chemical exchange using the one-pulse sequence: breakdown of the Ernst model for partial saturation in nuclear magnetic resonance spectroscopy.

PubMed

Spencer, R G; Fishbein, K W

2000-01-01

A fundamental problem in Fourier transform NMR spectroscopy is the calculation of observed resonance amplitudes for a repetitively pulsed sample, as first analyzed by Ernst and Anderson in 1966. Applications include determination of spin-lattice relaxation times (T(1)'s) by progressive saturation and correction for partial saturation in order to determine the concentrations of the chemical constituents of a spectrum. Accordingly, the Ernst and Anderson formalism has been used in innumerable studies of chemical and, more recently, physiological systems. However, that formalism implicitly assumes that no chemical exchange occurs. Here, we present an analysis of N sites in an arbitrary chemical exchange network, explicitly focusing on the intermediate exchange rate regime in which the spin-lattice relaxation rates and the chemical exchange rates are comparable in magnitude. As a special case of particular importance, detailed results are provided for a system with three sites undergoing mutual exchange. Specific properties of the N-site network are then detailed. We find that (i) the Ernst and Anderson analysis describing the response of a system to repetitive pulsing is inapplicable to systems with chemical exchange and can result in large errors in T(1) and concentration measurements; (ii) T(1)'s for systems with arbitrary exchange networks may still be correctly determined from a one-pulse experiment using the Ernst formula, provided that a short interpulse delay time and a large flip angle are used; (iii) chemical concentrations for exchanging systems may be correctly determined from a one-pulse experiment either by using a short interpulse delay time with a large flip angle, as for measuring T(1)'s, and correcting for partial saturation by use of the Ernst formula, or directly by using a long interpulse delay time to avoid saturation; (iv) there is a significant signal-to-noise penalty for performing one-pulse experiments under conditions which permit accurate

Capacitive chemical sensor

DOEpatents

Manginell, Ronald P; Moorman, Matthew W; Wheeler, David R

2014-05-27

A microfabricated capacitive chemical sensor can be used as an autonomous chemical sensor or as an analyte-sensitive chemical preconcentrator in a larger microanalytical system. The capacitive chemical sensor detects changes in sensing film dielectric properties, such as the dielectric constant, conductivity, or dimensionality. These changes result from the interaction of a target analyte with the sensing film. This capability provides a low-power, self-heating chemical sensor suitable for remote and unattended sensing applications. The capacitive chemical sensor also enables a smart, analyte-sensitive chemical preconcentrator. After sorption of the sample by the sensing film, the film can be rapidly heated to release the sample for further analysis. Therefore, the capacitive chemical sensor can optimize the sample collection time prior to release to enable the rapid and accurate analysis of analytes by a microanalytical system.

Combining color chart, colorimetric measurement and chemical compounds for postharvest quality of white wine grapes.

PubMed

Sollazzo, Marco; Baccelloni, Simone; D'Onofrio, Claudio; Bellincontro, Andrea

2018-01-03

This paper provides data for the potential use of a color chart to establish the best quality of white wine grapes destined for postharvest processing. Grechetto, Vermentino and Muscat of Alexandria white wine grape varieties were tested by sampling berries at different dates during their quality attribute evolution. A color chart and reflectance spectrocolorimeter were used in combination with analyses of total carotenoids and chlorophylls in all three varieties and of volatile organic compounds (VOCs) in Grechetto alone. Total carotenoids decreased from 0.85 to 0.76 µg g -1 in Grechetto berries and from 0.70 to 0.46 µg g -1 in Vermentino berries while increased from 0.70 to 0.80 µg g -1 in Muscat berries during ripening. Total chlorophylls decreased in all varieties, and a strict correlation was found between hue angle (measured by color chart or spectrocolorimeter) and chlorophyll disappearance, with R 2 ranging from 0.81 to 0.95 depending on the variety. VOCs were only measured in Grechetto grapes, and a significant increase in glycosylation was found with ripening. The concentration of different classes of VOCs exhibited a clear decrease during ripening, except for terpenoids and esters which showed a peak at the beginning. The benzenoid class reached the highest concentration, which was almost 50% of the total. Cluster analysis using Ward's method enabled the best grape quality to be identified. This experimental work highlights that a color chart is cheap and easy to use to define the right quality stage for white wine grapes. The color chart enabled the enochemical features to be matched with the VOC results for the aromatic maturity of Grechetto. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

Application of Graph Theory to Cost-Effective Fire Protection of Chemical Plants During Domino Effects.

PubMed

Khakzad, Nima; Landucci, Gabriele; Reniers, Genserik

2017-09-01

In the present study, we have introduced a methodology based on graph theory and multicriteria decision analysis for cost-effective fire protection of chemical plants subject to fire-induced domino effects. By modeling domino effects in chemical plants as a directed graph, the graph centrality measures such as out-closeness and betweenness scores can be used to identify the installations playing a key role in initiating and propagating potential domino effects. It is demonstrated that active fire protection of installations with the highest out-closeness score and passive fire protection of installations with the highest betweenness score are the most effective strategies for reducing the vulnerability of chemical plants to fire-induced domino effects. We have employed a dynamic graph analysis to investigate the impact of both the availability and the degradation of fire protection measures over time on the vulnerability of chemical plants. The results obtained from the graph analysis can further be prioritized using multicriteria decision analysis techniques such as the method of reference point to find the most cost-effective fire protection strategy. © 2016 Society for Risk Analysis.

RESULTS OF A DATING ATTEMPT -CHEMICAL AND PHYSICAL MEASUREMENTS RELEVANT TO THE CASE OF THE CRETACEOUS TERTIARY EXTINCTIONS

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

Asaro, Frank; Michel, Helen V.; Alvarez, Luis W.

1980-09-01

In Gubbio, Italy, a l em layer of clay between extensive limestone formations marks the boundary between the Cretaceous and Tertiary Periods. This clay layer was known to have been deposited about 65 million years ago when many life forms became extinct, but the length of time associated with the deposition was not known. In an attempt to measure this time with normally deposited meteoritic material as a clock, extensive measurements of iridium abundances (and those of many other elements) were made on the Gubbio rocks. Neutron activation analysis was the principal tool used in these studies. About 50 elementsmore » are searched for in materials like the earth's crust, about 40 are detected and about 30 are measured with useful precision. We were not able to determine exactly how long the clay deposition took. Instead the laboratory studies on the chemical and physical nature of the Cretaceous-Tertiary boundary led to the theory that an asteroid collision with the earth was responsible for the extinction of many forms of life including the dinosaurs.« less

Volatility-resolved Measurements of the Chemical Composition of Arctic Aerosol Particles

NASA Astrophysics Data System (ADS)

Ehn, M.; Kroll, J.; Coffman, D.; Quinn, P.; Bates, T.; Williams, E.; Kulmala, M.; Worsnop, D.

2008-12-01

Here we describe measurements of the chemical composition of submicron particles in the Arctic marine boundary layer, taken on board the R/V Knorr during the IPY-ICEALOT mission (March-April 2008). Measurements were made with an Aerodyne high-resolution aerosol mass spectrometer (HR-AMS) for the measurement of the non-refractory fraction of the aerosol, in particular allowing for the determination of the oxygen/carbon (O/C) ratio of the particulate organics and the unambiguous identification of trace inorganic species. Sampling alternated between ambient air and air sent through a thermodenuder (TD), continually scanned between 50 and 250C in order to remove aerosol components by volatility. The mass spectra of particulate matter in the Arctic (including Arctic haze) were dominated by sulfur-containing peaks and the CO2+ ion (at m/z 44), indicating the main non-refractory components of the aerosol are acidic sulfate and highly oxygenated organics. Thermodenuder measurements allow for the clear speciation of sulfate compounds by volatility, as well as the comparison of the degree of atmospheric aging of the organics to measurements taken elsewhere (including at terrestrial sites). AMS measurements will be compared to results from a hygroscopicity tandem differential mobility analyzer (HTDMA), also downstream of the thermodenuder, as well as from semicontinuous (PILS) and offline (filter) measurements of particle composition.

Chemical data visualization and analysis with incremental generative topographic mapping: big data challenge.

PubMed

Gaspar, Héléna A; Baskin, Igor I; Marcou, Gilles; Horvath, Dragos; Varnek, Alexandre

2015-01-26

This paper is devoted to the analysis and visualization in 2-dimensional space of large data sets of millions of compounds using the incremental version of generative topographic mapping (iGTM). The iGTM algorithm implemented in the in-house ISIDA-GTM program was applied to a database of more than 2 million compounds combining data sets of 36 chemicals suppliers and the NCI collection, encoded either by MOE descriptors or by MACCS keys. Taking advantage of the probabilistic nature of GTM, several approaches to data analysis were proposed. The chemical space coverage was evaluated using the normalized Shannon entropy. Different views of the data (property landscapes) were obtained by mapping various physical and chemical properties (molecular weight, aqueous solubility, LogP, etc.) onto the iGTM map. The superposition of these views helped to identify the regions in the chemical space populated by compounds with desirable physicochemical profiles and the suppliers providing them. The data sets similarity in the latent space was assessed by applying several metrics (Euclidean distance, Tanimoto and Bhattacharyya coefficients) to data probability distributions based on cumulated responsibility vectors. As a complementary approach, data sets were compared by considering them as individual objects on a meta-GTM map, built on cumulated responsibility vectors or property landscapes produced with iGTM. We believe that the iGTM methodology described in this article represents a fast and reliable way to analyze and visualize large chemical databases.

Analysis of the Atmospheric Distribution, Sources, and Sinks of Oxygenated Volatile Organic Chemicals Based on Measurements over the Pacific during TRACE-P

NASA Technical Reports Server (NTRS)

Singh, H. B.; Salas, L. J.; Chatfield, r. B.; Czech, E.; Fried, A.; Walega, J.; Evans, M. J.; Field, B. D.; Jacob, D. J.; Blake, D.;

Voltage and partial pressure dependent defect chemistry in (La,Sr)FeO3–δ thin films investigated by chemical capacitance measurements

PubMed Central

Rupp, Ghislain M.; Fleig, Jürgen

2018-01-01

La0.6Sr0.4FeO3–δ (LSF) thin films of different thickness were prepared by pulsed laser deposition on yttria stabilized zirconia (YSZ) and characterized by using three electrode impedance spectroscopy. Electrochemical film capacitance was analyzed in relation to oxygen partial pressure (0.25 mbar to 1 bar), DC polarization (0 m to –600 m) and temperature (500 to 650 °C). For most measurement parameters, the chemical bulk capacitance dominates the overall capacitive properties and the corresponding defect chemical state depends solely on the oxygen chemical potential inside the film, independent of atmospheric oxygen pressure and DC polarization. Thus, defect chemical properties (defect concentrations and defect formation enthalpies) could be deduced from such measurements. Comparison with LSF defect chemical bulk data from the literature showed good agreement for vacancy formation energies but suggested larger electronic defect concentrations in the films. From thickness-dependent measurements at lower oxygen chemical potentials, an additional capacitive contribution could be identified and attributed to the LSF|YSZ interface. Deviations from simple chemical capacitance models at high pressures are most probably due to defect interactions. PMID:29671421

Measurement of 13C chemical shift tensor principal values with a magic-angle turning experiment.

PubMed

Hu, J Z; Orendt, A M; Alderman, D W; Pugmire, R J; Ye, C; Grant, D M

1994-08-01

The magic-angle turning (MAT) experiment introduced by Gan is developed into a powerful and routine method for measuring the principal values of 13C chemical shift tensors in powdered solids. A large-volume MAT probe with stable rotation frequencies down to 22 Hz is described. A triple-echo MAT pulse sequence is introduced to improve the quality of the two-dimensional baseplane. It is shown that measurements of the principal values of chemical shift tensors in complex compounds can be enhanced by using either short contact times or dipolar dephasing pulse sequences to isolate the powder patterns from protonated or non-protonated carbons, respectively. A model compound, 1,2,3-trimethoxybenzene, is used to demonstrate these techniques, and the 13C principal values in 2,3-dimethylnaphthalene and Pocahontas coal are reported as typical examples.

Scanning angle Raman spectroscopy: Investigation of Raman scatter enhancement techniques for chemical analysis

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

Meyer, Matthew W.

2013-01-01

This thesis outlines advancements in Raman scatter enhancement techniques by applying evanescent fields, standing-waves (waveguides) and surface enhancements to increase the generated mean square electric field, which is directly related to the intensity of Raman scattering. These techniques are accomplished by employing scanning angle Raman spectroscopy and surface enhanced Raman spectroscopy. A 1064 nm multichannel Raman spectrometer is discussed for chemical analysis of lignin. Extending dispersive multichannel Raman spectroscopy to 1064 nm reduces the fluorescence interference that can mask the weaker Raman scattering. Overall, these techniques help address the major obstacles in Raman spectroscopy for chemical analysis, which include themore » inherently weak Raman cross section and susceptibility to fluorescence interference.« less

A combined qualitative and quantitative procedure for the chemical analysis of urinary calculi

PubMed Central

Hodgkinson, A.

1971-01-01

A better understanding of the physico-chemical principles underlying the formation of calculus has led to a need for more precise information on the chemical composition of stones. A combined qualitative and quantitative procedure for the chemical analysis of urinary calculi which is suitable for routine use is presented. The procedure involves five simple qualitative tests followed by the quantitative determination of calcium, magnesium, inorganic phosphate, and oxalate. These data are used to calculate the composition of the stone in terms of calcium oxalate, apatite, and magnesium ammonium phosphate. Analytical results and derived values for five representative types of calculi are presented. PMID:5551382

Chemical and Physical Properties of Hi-Cal-2

NASA Technical Reports Server (NTRS)

Spakowski, A. E.; Allen, Harrison, Jr.; Caves, Robert M.

1955-01-01

As part of the Navy Project Zip to consider various boron-containing materials as possible high-energy fuels, the chemical and physical properties of Hi-Cal-2 prepared by the Callery Chemical Company were evaluated at the NACA Lewis laboratory. Elemental chemical analysis, heat of combustion, vapor pressure and decomposition, freezing point, density, self ignition temperature, flash point, and blow-out velocity were determined for the fuel. Although the precision of measurement of these properties was not equal to that obtained for hydrocarbons, this special release research memorandum was prepared to make the data available as soon as possible.

Letters from China: A History of the Origins of the Chemical Analysis of Ceramics.

PubMed

Pollard, A M

2015-02-01

This paper is an attempt to document the early history of the quantitative chemical analysis of ceramic materials in Europe, with a specific interest in the analysis of archaeological ceramics. This inevitably leads to a study of the attempts made in Europe to imitate the miraculous material--porcelain--imported from China from the fourteenth century onwards. It is clear that before the end of the eighteenth century progress was made in this endeavor by systematic but essentially trial-and-error firing of various raw materials, culminating in the successful production of European porcelain by Böttger and von Tschirnhaus in 1709. Shortly after this, letters describing the Chinese manufacture of porcelain, and, more importantly, samples of raw and fired material, began to arrive in Europe from French Jesuit missionaries, which were subjected to intense study. Following the perfection of gravimetric methods of chemical analysis in the late eighteenth century, these Chinese samples, and samples of porcelain from various European factories, were regularly analysed, particularly by Brongniart at Sèvres. Similar work was carried out on English porcelain by Simeon Shaw and Sir Arthur Church. The origins of the chemical analysis of archaeological ceramics are still somewhat obscure, but must date to the late eighteenth or early nineteenth centuries, by the likes of Vauquelin and Chaptal.

Analysis of chemical concepts as the basic of virtual laboratory development and process science skills in solubility and solubility product subject

NASA Astrophysics Data System (ADS)

Syafrina, R.; Rohman, I.; Yuliani, G.

2018-05-01

This study aims to analyze the concept characteristics of solubility and solubility products that will serve as the basis for the development of virtual laboratory and students' science process skills. Characteristics of the analyzed concepts include concept definitions, concept attributes, and types of concepts. The concept analysis method uses concept analysis according to Herron. The results of the concept analysis show that there are twelve chemical concepts that become the prerequisite concept before studying the solubility and solubility and five core concepts that students must understand in the solubility and Solubility product. As many as 58.3% of the definitions of the concepts contained in high school textbooks support students' science process skills, the rest of the definition of the concept is memorized. Concept attributes that meet three levels of chemical representation and can be poured into a virtual laboratory have a percentage of 66.6%. Type of concept, 83.3% is a concept based on principle; and 16.6% concepts that state the process. Meanwhile, the science process skills that can be developed based on concept analysis are the ability to observe, calculate, measure, predict, interpret, hypothesize, apply, classify, and inference.

Identification or Development of Chemical Analysis Methods for Plants and Animal Tissues

DTIC Science & Technology

1981-01-01

Report No. DRXTH-TE-CR-80086 [E EMWSTEEACISITE - IDENTIFICATION OR DEVELOPMENT OF CHEMICAL ANALYSISI METHODS FOR PLANTS AND ANIMAL TISSUES D l...86i 4TITLE (ansdo"t) TYPE or" P 4. Iih~iti.)Final epwt. )9 A4,417 ~, Identlifiation or Development of Chemical I-g 9 O d 18 Analysis Methods for Plants...n TN oT sacmpihdo in. wEr DContinng er adetcsr aid Iuent bybopkmertda lo aeo 1.5th 1/s deeipta24ndectr Tritrotasolsoepae d andT Boloia Matrc,, 1473

Evaluation of High-Throughput Chemical Exposure Models via Analysis of Matched Environmental and Biological Media Measurements

EPA Science Inventory

The U.S. EPA, under its ExpoCast program, is developing high-throughput near-field modeling methods to estimate human chemical exposure and to provide real-world context to high-throughput screening (HTS) hazard data. These novel modeling methods include reverse methods to infer ...

Regional-Scale Chemical Transport Modeling in Support of the Ace-Asia Experiment

NASA Astrophysics Data System (ADS)

Guttikunda, S.; Uno, I.; Carmichael, G.; Streets, D. G.; Tang, Y.; Yienger, J. J.; Woo, J.; Thongboonchoo, N.; Clarke, A.; Blomquist, B.; McNaughton, C.

2002-12-01

Chemical Transport Models (CTMs) are playing increasingly important roles in the design, execution, and analysis of large-scale atmospheric chemistry field studies. They are being used in forecast-mode to enhance flight planning by enabling the representation of important three-dimensional atmospheric chemical structures (such as dust storm plumes, polluted air masses associated with large cities, and widespread biomass burning events) and how they evolve over time. CTM forecasts play the additional important roles of providing a 4-dimensional contextual representation of the experiment, and facilitating a quicker analysis of the field results. CTMs also facilitate the integration of the different measurements and measurement platforms (e.g., aircraft, ground stations and satellite observations). Finally, CTMs play an important role in evaluating and helping to improve emission estimates. We developed the Chemical weather FORecasting System (CFORS) to assist in the analysis of field experiments. CFORS was applied in the design and execution of the TRACE-P, ACE-Asia and the ITCT-Y2K intensive field experiments. In this paper we present a brief overview of the CFORS system, and focus on the use of the CTM on the analysis of the Ace-Asia data. ACE-Asia produced a high density of data from multiple independent measurements, and a wide variety of different types of data. These include: a) in-situ measurements from ground stations, on board ships, and on various aircraft platforms; b) remote sensed data from satellites; and c) vertical distributions from ground based lidars. This data spans vast temporal and spatial scales, and illustrates the needs and challenges of integrating these data into a consistent data analysis set. In this paper we plan to illustrate efforts to integrate measured and modeled data into a comprehensive data set for analysis by measurers and modelers. We will also outline future directions and challenges.

Effects of digestion, chemical separation, and deposition on Po-210 quantitative analysis

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

Seiner, Brienne N.; Morley, Shannon M.; Beacham, Tere A.

Polonium-210 is a radioactive isotope often used to study sedimentation processes, food chains, aerosol behavior, and atmospheric circulations related to environmental sciences. Materials for the analysis of Po-210 range from tobacco leaves or cotton fibers, to soils and sediments. The purpose of this work was to determine polonium losses from a variety of sample types (soil, cotton fiber, and air filter) due to digestion technique, chemical separation, and deposition method for alpha energy analysis. Results demonstrated that yields from a perchloric acid wet-ash were similar to that from a microwave digestion. Both were greater than the dry-ash procedure. The poloniummore » yield from the perchloric acid wet ash was 87 ± 5%, the microwave digestion had a yield of 100 ± 7%, and the dry ash had a yield of 38 ± 5%. The chemical separation of polonium by an anion exchange resin was used only on the soil samples due to the complex nature of this sample. The yield of Po-209 tracer after chemical separation and deposition for alpha analysis was 83 ± 7% for the soil samples. Spontaneous deposition yields for the cotton and air filters were 87 ± 4% and 92 ± 6%, respectively. Based on the overall process yields for each sample type the amount of Po-210 was quantified using alpha energy analysis. The soil contained 0.18 ± 0.08 Bq/g, the cotton swipe contained 0.7 mBq/g, and the air filter contained 0.04 ± 0.02 mBq/g. High and robust yields of polonium are possible using a suitable digestion, separation, and deposition method.« less

The chemical abundance analysis of normal early A- and late B-type stars

NASA Astrophysics Data System (ADS)

Fossati, L.; Ryabchikova, T.; Bagnulo, S.; Alecian, E.; Grunhut, J.; Kochukhov, O.; Wade, G.

2009-09-01

Context: Modern spectroscopy of early-type stars often aims at studying complex physical phenomena such as stellar pulsation, the peculiarity of the composition of the photosphere, chemical stratification, the presence of a magnetic field, and its interplay with the stellar atmosphere and the circumstellar environment. Comparatively less attention is paid to identifying and studying the “normal” A- and B-type stars and testing how the basic atomic parameters and standard spectral analysis allow one to fit the observations. By contrast, this kind of study is paramount for eventually allowing one to correctly quantify the impact of the various physical processes that occur inside the atmospheres of A- and B-type stars. Aims: We wish to establish whether the chemical composition of the solar photosphere can be regarded as a reference for early A- and late B-type stars. Methods: We have obtained optical high-resolution, high signal-to-noise ratio spectra of three slowly rotating early-type stars (HD 145788, 21 Peg and π Cet) that show no obvious sign of chemical peculiarity, and performed a very accurate LTE abundance analysis of up to 38 ions of 26 elements (for 21 Peg), using a vast amount of spectral lines visible in the spectral region covered by our spectra. Results: We provide an exhaustive description of the abundance characteristics of the three analysed stars with a critical review of the line parameters used to derive the abundances. We compiled a table of atomic data for more than 1100 measured lines that may be used in the future as a reference. The abundances we obtained for He, C, Al, S, V, Cr, Mn, Fe, Ni, Sr, Y, and Zr are compatible with the solar ones derived with recent 3D radiative-hydrodynamical simulations of the solar photosphere. The abundances of the remaining studied elements show some degree of discrepancy compared to the solar photosphere. Those of N, Na, Mg, Si, Ca, Ti, and Nd may well be ascribed to non-LTE effects; for P, Cl, Sc and

Dynamics of liquids, molecules, and proteins measured with ultrafast 2D IR vibrational echo chemical exchange spectroscopy.

PubMed

Fayer, M D

2009-01-01

A wide variety of molecular systems undergo fast structural changes under thermal equilibrium conditions. Such transformations are involved in a vast array of chemical problems. Experimentally measuring equilibrium dynamics is a challenging problem that is at the forefront of chemical research. This review describes ultrafast 2D IR vibrational echo chemical exchange experiments and applies them to several types of molecular systems. The formation and dissociation of organic solute-solvent complexes are directly observed. The dissociation times of 13 complexes, ranging from 4 ps to 140 ps, are shown to obey a relationship that depends on the complex's formation enthalpy. The rate of rotational gauche-trans isomerization around a carbon-carbon single bond is determined for a substituted ethane at room temperature in a low viscosity solvent. The results are used to obtain an approximate isomerization rate for ethane. Finally, the time dependence of a well-defined single structural transformation of a protein is measured.

Spatially resolved chemical analysis of cicada wings using laser-ablation electrospray ionization (LAESI) imaging mass spectrometry (IMS).

PubMed

Román, Jessica K; Walsh, Callee M; Oh, Junho; Dana, Catherine E; Hong, Sungmin; Jo, Kyoo D; Alleyne, Marianne; Miljkovic, Nenad; Cropek, Donald M

2018-03-01

Laser-ablation electrospray ionization (LAESI) imaging mass spectrometry (IMS) is an emerging bioanalytical tool for direct imaging and analysis of biological tissues. Performing ionization in an ambient environment, this technique requires little sample preparation and no additional matrix, and can be performed on natural, uneven surfaces. When combined with optical microscopy, the investigation of biological samples by LAESI allows for spatially resolved compositional analysis. We demonstrate here the applicability of LAESI-IMS for the chemical analysis of thin, desiccated biological samples, specifically Neotibicen pruinosus cicada wings. Positive-ion LAESI-IMS accurate ion-map data was acquired from several wing cells and superimposed onto optical images allowing for compositional comparisons across areas of the wing. Various putative chemical identifications were made indicating the presence of hydrocarbons, lipids/esters, amines/amides, and sulfonated/phosphorylated compounds. With the spatial resolution capability, surprising chemical distribution patterns were observed across the cicada wing, which may assist in correlating trends in surface properties with chemical distribution. Observed ions were either (1) equally dispersed across the wing, (2) more concentrated closer to the body of the insect (proximal end), or (3) more concentrated toward the tip of the wing (distal end). These findings demonstrate LAESI-IMS as a tool for the acquisition of spatially resolved chemical information from fragile, dried insect wings. This LAESI-IMS technique has important implications for the study of functional biomaterials, where understanding the correlation between chemical composition, physical structure, and biological function is critical. Graphical abstract Positive-ion laser-ablation electrospray ionization mass spectrometry coupled with optical imaging provides a powerful tool for the spatially resolved chemical analysis of cicada wings.

Chemical Analysis of Water-accommodated Fractions of Crude Oil Spills Using TIMS-FT-ICR MS.

PubMed

Benigni, Paolo; Marin, Rebecca; Sandoval, Kathia; Gardinali, Piero; Fernandez-Lima, Francisco

2017-03-03

Multiple chemical processes control how crude oil is incorporated into seawater and also the chemical reactions that occur overtime. Studying this system requires the careful preparation of the sample in order to accurately replicate the natural formation of the water-accommodated fraction that occurs in nature. Low-energy water-accommodated fractions (LEWAF) are carefully prepared by mixing crude oil and water at a set ratio. Aspirator bottles are then irradiated, and at set time points, the water is sampled and extracted using standard techniques. A second challenge is the representative characterization of the sample, which must take into consideration the chemical changes that occur over time. A targeted analysis of the aromatic fraction of the LEWAF can be performed using an atmospheric-pressure laser ionization source coupled to a custom-built trapped ion mobility spectrometry-Fourier transform-ion cyclotron resonance mass spectrometer (TIMS-FT-ICR MS). The TIMS-FT-ICR MS analysis provides high-resolution ion mobility and ultrahigh-resolution MS analysis, which further allow the identification of isomeric components by their collision cross-sections (CCS) and chemical formula. Results show that as the oil-water mixture is exposed to light, there is significant photo-solubilization of the surface oil into the water. Over time, the chemical transformation of the solubilized molecules takes place, with a decrease in the number of identifications of nitrogen- and sulfur-bearing species in favor of those with a greater oxygen content than were typically observed in the base oil.

Interlaboratory comparison of chemical analysis of uranium mononitride

NASA Technical Reports Server (NTRS)

Merkle, E. J.; Davis, W. F.; Halloran, J. T.; Graab, J. W.

1974-01-01

Analytical methods were established in which the critical variables were controlled, with the result that acceptable interlaboratory agreement was demonstrated for the chemical analysis of uranium mononitride. This was accomplished by using equipment readily available to laboratories performing metallurgical analyses. Agreement among three laboratories was shown to be very good for uranium and nitrogen. Interlaboratory precision of + or - 0.04 percent was achieved for both of these elements. Oxygen was determined to + or - 15 parts per million (ppm) at the 170-ppm level. The carbon determination gave an interlaboratory precision of + or - 46 ppm at the 320-ppm level.

Biogeographical Analysis of Chemical Co-Occurrence Data to ...

EPA Pesticide Factsheets

A challenge with multiple chemical risk assessment is the need to consider the joint behavior of chemicals in mixtures. To address this need, pharmacologists and toxicologists have developed methods over the years to evaluate and test chemical interaction. In practice, however, testing of chemical interaction more often comprises ad hoc binary combinations and rarely examines higher order combinations. One explanation for this practice is the belief that there are simply too many possible combinations of chemicals to consider. Indeed, under stochastic conditions the possible number of chemical combinations scales geometrically as the pool of chemicals increases. However, the occurrence of chemicals in the environment is determined by factors, economic in part, which favor some chemicals over others. We investigate methods from the field of biogeography, originally developed to study avian species co-occurrence patterns, and adapt these approaches to examine chemical co-occurrence. These methods were applied to a national survey of pesticide residues in 168 child care centers from across the country. Our findings show that pesticide co-occurrence in the child care center was not random but highly structured, leading to the co-occurrence of specific pesticide combinations. Thus, ecological studies of species co-occurrence parallel the issue of chemical co-occurrence at specific locations. Both are driven by processes that introduce structure in the pattern of co-o

QSAR modeling and chemical space analysis of antimalarial compounds

NASA Astrophysics Data System (ADS)

Sidorov, Pavel; Viira, Birgit; Davioud-Charvet, Elisabeth; Maran, Uko; Marcou, Gilles; Horvath, Dragos; Varnek, Alexandre

2017-05-01

Generative topographic mapping (GTM) has been used to visualize and analyze the chemical space of antimalarial compounds as well as to build predictive models linking structure of molecules with their antimalarial activity. For this, a database, including 3000 molecules tested in one or several of 17 anti- Plasmodium activity assessment protocols, has been compiled by assembling experimental data from in-house and ChEMBL databases. GTM classification models built on subsets corresponding to individual bioassays perform similarly to the earlier reported SVM models. Zones preferentially populated by active and inactive molecules, respectively, clearly emerge in the class landscapes supported by the GTM model. Their analysis resulted in identification of privileged structural motifs of potential antimalarial compounds. Projection of marketed antimalarial drugs on this map allowed us to delineate several areas in the chemical space corresponding to different mechanisms of antimalarial activity. This helped us to make a suggestion about the mode of action of the molecules populating these zones.

QSAR modeling and chemical space analysis of antimalarial compounds.

PubMed

Sidorov, Pavel; Viira, Birgit; Davioud-Charvet, Elisabeth; Maran, Uko; Marcou, Gilles; Horvath, Dragos; Varnek, Alexandre

2017-05-01

Generative topographic mapping (GTM) has been used to visualize and analyze the chemical space of antimalarial compounds as well as to build predictive models linking structure of molecules with their antimalarial activity. For this, a database, including ~3000 molecules tested in one or several of 17 anti-Plasmodium activity assessment protocols, has been compiled by assembling experimental data from in-house and ChEMBL databases. GTM classification models built on subsets corresponding to individual bioassays perform similarly to the earlier reported SVM models. Zones preferentially populated by active and inactive molecules, respectively, clearly emerge in the class landscapes supported by the GTM model. Their analysis resulted in identification of privileged structural motifs of potential antimalarial compounds. Projection of marketed antimalarial drugs on this map allowed us to delineate several areas in the chemical space corresponding to different mechanisms of antimalarial activity. This helped us to make a suggestion about the mode of action of the molecules populating these zones.

Analysis of Chemical, REP, and SEP missions to the Trojan asteroids

NASA Technical Reports Server (NTRS)

Bonfiglio, Eugene P.; Oh, David; Yen, Chen-Wan

2005-01-01

Recent studies suggest significant benefits from using 1st and 2nd generation Radioisotope Power Systems (RPS) as a power source for electric propulsion (EP) missions to the outer planets. This study focuses on trajectories to the Trojan asteroids. A high level analysis is performed with chemical trajectories to determine potential canidates for REP trajectory optimization. Extensive analysis of direct trajectories using REP is performed on these candidates. Solar Electric Propulsion (SEP) trajectories are also considered for comparison against REP trajectories.

Method for the Collection, Gravimetric and Chemical Analysis of Nonvolatile Residue (NVR) on Surfaces

NASA Technical Reports Server (NTRS)

Gordon, Keith; Rutherford, Gugu; Aranda, Denisse

2017-01-01

Nonvolatile residue (NVR), sometimes referred to as molecular contamination is the term used for the total composition of the inorganic and high boiling point organic components in particulates and molecular films deposited on critical surfaces surrounding space structures, with the particulate and NVR contamination originating primarily from pre-launch operations. The "nonvolatile" suggestion from the terminology NVR implies that the collected residue will not experience much loss under ambient conditions. NVR has been shown to have a dramatic impact on the ability to perform optical measurements from platforms based in space. Such contaminants can be detected early by the controlled application of various detection techniques and contamination analyses. Contamination analyses are the techniques used to determine if materials, components, and subsystems can be expected to meet the performance requirements of a system. Of particular concern is the quantity of NVR contaminants that might be deposited on critical payload surfaces from these sources. Subsequent chemical analysis of the contaminant samples by infrared spectroscopy and gas chromatography mass spectrometry identifies the components, gives semi-quantitative estimates of contaminant thickness, indicates possible sources of the NVR, and provides guidance for effective cleanup procedures. In this report, a method for the collection and determination of the mass of NVR was generated by the authors at NASA Langley Research Center. This report describes the method developed and implemented for collecting NVR contaminants, and procedures for gravimetric and chemical analysis of the residue obtained. The result of this NVR analysis collaboration will help pave the way for Langley's ability to certify flight hardware outgassing requirements in support of flight projects such as Stratospheric Aerosol and Gas Experiment III (SAGE III), Clouds and the Earth's Radiant Energy System (CERES), Materials International

Soil chemical sensor and precision agricultural chemical delivery system and method

DOEpatents

Colburn, Jr., John W.

1991-01-01

A real time soil chemical sensor and precision agricultural chemical delivery system includes a plurality of ground-engaging tools in association with individual soil sensors which measure soil chemical levels. The system includes the addition of a solvent which rapidly saturates the soil/tool interface to form a conductive solution of chemicals leached from the soil. A multivalent electrode, positioned within a multivalent frame of the ground-engaging tool, applies a voltage or impresses a current between the electrode and the tool frame. A real-time soil chemical sensor and controller senses the electrochemical reaction resulting from the application of the voltage or current to the leachate, measures it by resistivity methods, and compares it against pre-set resistivity levels for substances leached by the solvent. Still greater precision is obtained by calibrating for the secondary current impressed through solvent-less soil. The appropriate concentration is then found and the servo-controlled delivery system applies the appropriate amount of fertilizer or agricultural chemicals substantially in the location from which the soil measurement was taken.

Soil chemical sensor and precision agricultural chemical delivery system and method

DOEpatents

Colburn, J.W. Jr.

1991-07-23

A real time soil chemical sensor and precision agricultural chemical delivery system includes a plurality of ground-engaging tools in association with individual soil sensors which measure soil chemical levels. The system includes the addition of a solvent which rapidly saturates the soil/tool interface to form a conductive solution of chemicals leached from the soil. A multivalent electrode, positioned within a multivalent frame of the ground-engaging tool, applies a voltage or impresses a current between the electrode and the tool frame. A real-time soil chemical sensor and controller senses the electrochemical reaction resulting from the application of the voltage or current to the leachate, measures it by resistivity methods, and compares it against pre-set resistivity levels for substances leached by the solvent. Still greater precision is obtained by calibrating for the secondary current impressed through solvent-less soil. The appropriate concentration is then found and the servo-controlled delivery system applies the appropriate amount of fertilizer or agricultural chemicals substantially in the location from which the soil measurement was taken. 5 figures.

Meta-Analysis of the Chemical and Non-Chemical Stressors Affecting Childhood Obesity

EPA Science Inventory

Worldwide, approximately 42 million children under the age of 5 years are considered overweight or obese. While much research has focused on individual behaviors impacting obesity, little research has emphasized the complex interactions of numerous chemical and non-chemical stres...

An evaluation of surrogate chemical exposure measures and autism prevalence in Texas.

PubMed

Lewandowski, T A; Bartell, S M; Yager, J W; Levin, L

2009-01-01

There is currently considerable discussion in the scientific community as well as within the general public concerning the role mercury (Hg) exposures may play in the apparent increased incidence of neurodevelopmental disorders (particularly autism) in children. Although the primary focus of this debate has focused on ethylmercury from vaccinations, linkage to other sources of Hg has been proposed. An ecologic association between 2001 Toxic Release Inventory (TRI; www.epa.gov/tri) data for Hg and 2000-2001 school district autism prevalence was previously reported in Texas. Evaluations using industrial release data as surrogate exposure measures may be problematic, particularly for chemicals like Hg that have complex environmental fates. To explore the robustness of TRI-based analyses of the Hg-autism hypothesis in Texas, a detailed analysis was undertaken examining the extent of the ecological relationship during multiple years and examining whether surrogate exposure measures would yield similar conclusions. Using multilevel Poisson regression analysis and data obtained from a number of publicly available databases, it was found that air Hg release data were significantly associated with autism prevalence in Texas school districts when considering data for 2001 and 2002 (2001: RR = 4.45, 95% CI = 1.60-12.36, 2002: RR = 2.70, 95% CI = 1.17-6.15). Significant associations were not found using data from 2003 to 2005. A significant association was not observed when considering air Hg data for 2000 or 2001 and school district autism prevalence data for 2005-2006 or 2006-2007, an analysis allowing for a 5-yr time period between presumed exposure and entry into the public school system (2000: RR = 1.03, 95% CI = 0.59-1.83, 2001: RR = 0.94, 95% CI = 0.59-1.47). Significant associations were not observed for any year nor for the time lagged analyses when censored autism counts were replaced by threes instead of zeros. An evaluation of TRI air emissions data for several

Correlated Imaging – A Grand Challenge in Chemical Analysis

PubMed Central

Masyuko, Rachel; Lanni, Eric; Sweedler, Jonathan V.; Bohn, Paul W.

2013-01-01

Correlated chemical imaging is an emerging strategy for acquisition of images by combining information from multiplexed measurement platforms to track, visualize, and interpret in situ changes in the structure, organization, and activities of interesting chemical systems, frequently spanning multiple decades in space and time. Acquiring and correlating information from complementary imaging experiments has the potential to expose complex chemical behavior in ways that are simply not available from single methods applied in isolation, thereby greatly amplifying the information gathering power of imaging experiments. However, in order to correlate image information across platforms, a number of issues must be addressed. First, signals are obtained from disparate experiments with fundamentally different figures of merit, including pixel size, spatial resolution, dynamic range, and acquisition rates. In addition, images are often acquired on different instruments in different locations, so the sample must be registered spatially so that the same area of the sample landscape is addressed. The signals acquired must be correlated in both spatial and temporal domains, and the resulting information has to be presented in a way that is readily understood. These requirements pose special challenges for image cross-correlation that go well beyond those posed in single technique imaging approaches. The special opportunities and challenges that attend correlated imaging are explored by specific reference to correlated mass spectrometric and Raman imaging, a topic of substantial and growing interest. PMID:23431559

Experimental Measurements of the Chemical Reaction Zone of Detonating Liquid Explosives

NASA Astrophysics Data System (ADS)

Bouyer, Viviane; Sheffield, Stephen A.; Dattelbaum, Dana M.; Gustavsen, Richard L.; Stahl, David B.; Doucet, Michel

2009-06-01

We have a joint project between CEA-DAM Le Ripault and Los Alamos National Laboratory (LANL) to study the chemical reaction zone in detonating high explosives using several different laser velocimetry techniques. The short temporal duration of the features (von Neumann spike and sonic locus) of the reaction zone make these measurements difficult. Here, we report results obtained from using and PDV (photon Doppler velocimetry) methods to measure the particle velocity history at a detonating HE (nitromethane)/PMMA interface. Experiments done at CEA were high-explosive-plane-wave initiated and those at LANL were gas-gun-projectile initiated with a detonation run of about 6 charge diameters in all experiments, in either glass or brass confinement. Excellent agreement of the interface particle velocity measurements at both Laboratories were obtained even though the initiation systems and the velocimetry systems were different. Some differences were observed in the von Neumann spike height because of the approximately 2 nanosecond time resolution of the techniques -- in some or all cases the spike top was truncated.

Development and Validation of 2D Difference Intensity Analysis for Chemical Library Screening by Protein-Detected NMR Spectroscopy.

PubMed

Egner, John M; Jensen, Davin R; Olp, Michael D; Kennedy, Nolan W; Volkman, Brian F; Peterson, Francis C; Smith, Brian C; Hill, R Blake

2018-03-02

An academic chemical screening approach was developed by using 2D protein-detected NMR, and a 352-chemical fragment library was screened against three different protein targets. The approach was optimized against two protein targets with known ligands: CXCL12 and BRD4. Principal component analysis reliably identified compounds that induced nonspecific NMR crosspeak broadening but did not unambiguously identify ligands with specific affinity (hits). For improved hit detection, a novel scoring metric-difference intensity analysis (DIA)-was devised that sums all positive and negative intensities from 2D difference spectra. Applying DIA quickly discriminated potential ligands from compounds inducing nonspecific NMR crosspeak broadening and other nonspecific effects. Subsequent NMR titrations validated chemotypes important for binding to CXCL12 and BRD4. A novel target, mitochondrial fission protein Fis1, was screened, and six hits were identified by using DIA. Screening these diverse protein targets identified quinones and catechols that induced nonspecific NMR crosspeak broadening, hampering NMR analyses, but are currently not computationally identified as pan-assay interference compounds. The results established a streamlined screening workflow that can easily be scaled and adapted as part of a larger screening pipeline to identify fragment hits and assess relative binding affinities in the range of 0.3-1.6 mm. DIA could prove useful in library screening and other applications in which NMR chemical shift perturbations are measured. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Differential Dynamic Engagement within 24 SH3 Domain: Peptide Complexes Revealed by Co-Linear Chemical Shift Perturbation Analysis

PubMed Central

Stollar, Elliott J.; Lin, Hong; Davidson, Alan R.; Forman-Kay, Julie D.

2012-01-01

There is increasing evidence for the functional importance of multiple dynamically populated states within single proteins. However, peptide binding by protein-protein interaction domains, such as the SH3 domain, has generally been considered to involve the full engagement of peptide to the binding surface with minimal dynamics and simple methods to determine dynamics at the binding surface for multiple related complexes have not been described. We have used NMR spectroscopy combined with isothermal titration calorimetry to comprehensively examine the extent of engagement to the yeast Abp1p SH3 domain for 24 different peptides. Over one quarter of the domain residues display co-linear chemical shift perturbation (CCSP) behavior, in which the position of a given chemical shift in a complex is co-linear with the same chemical shift in the other complexes, providing evidence that each complex exists as a unique dynamic rapidly inter-converting ensemble. The extent the specificity determining sub-surface of AbpSH3 is engaged as judged by CCSP analysis correlates with structural and thermodynamic measurements as well as with functional data, revealing the basis for significant structural and functional diversity amongst the related complexes. Thus, CCSP analysis can distinguish peptide complexes that may appear identical in terms of general structure and percent peptide occupancy but have significant local binding differences across the interface, affecting their ability to transmit conformational change across the domain and resulting in functional differences. PMID:23251481

Different Models Used to Interpret Chemical Changes: Analysis of a Curriculum and Its Impact on French Students' Reasoning

ERIC Educational Resources Information Center

Kermen, Isabelle; Meheut, Martine

2009-01-01

We present an analysis of the new French curriculum on chemical changes describing the underlying models and highlighting their relations to the empirical level. The authors of the curriculum introduced a distinction between the chemical change of a chemical system and the chemical reactions that account for it. We specify the different roles of…

Controlling organic chemical hazards in food manufacturing: a hazard analysis critical control points (HACCP) approach.

PubMed

Ropkins, K; Beck, A J

2002-08-01

Hazard analysis by critical control points (HACCP) is a systematic approach to the identification, assessment and control of hazards. Effective HACCP requires the consideration of all hazards, i.e., chemical, microbiological and physical. However, to-date most 'in-place' HACCP procedures have tended to focus on the control of microbiological and physical food hazards. In general, the chemical component of HACCP procedures is either ignored or limited to applied chemicals, e.g., food additives and pesticides. In this paper we discuss the application of HACCP to a broader range of chemical hazards, using organic chemical contaminants as examples, and the problems that are likely to arise in the food manufacturing sector. Chemical HACCP procedures are likely to result in many of the advantages previously identified for microbiological HACCP procedures: more effective, efficient and economical than conventional end-point-testing methods. However, the high costs of analytical monitoring of chemical contaminants and a limited understanding of formulation and process optimisation as means of controlling chemical contamination of foods are likely to prevent chemical HACCP becoming as effective as microbiological HACCP.

Application of bioelectrical impedance analysis in prediction of light kid carcass and muscle chemical composition.

PubMed

Silva, S R; Afonso, J; Monteiro, A; Morais, R; Cabo, A; Batista, A C; Guedes, C M; Teixeira, A

2018-06-01

Carcass data were collected from 24 kids (average live weight of 12.5±5.5 kg; range 4.5 to 22.4 kg) of Jarmelista Portuguese native breed, to evaluate bioelectrical impedance analysis (BIA) as a technique for prediction of light kid carcass and muscle chemical composition. Resistance (Rs, Ω) and reactance (Xc, Ω), were measured in the cold carcasses with a single frequency bioelectrical impedance analyzer and, together with impedance (Z, Ω), two electrical volume measurements (VolA and VolB, cm2/Ω), carcass cold weight (CCW), carcass compactness and several carcass linear measurements were fitted as independent variables to predict carcass composition by stepwise regression analysis. The amount of variation explained by VolA and VolB only reached a significant level (P<0.01 and P<0.05, respectively) for muscle weight, moisture, protein and fat-free soft tissue content, even so with low accuracy, with VolA providing the best results (0.326⩽R 2⩽0.366). Quite differently, individual BIA parameters (Rs, Xc and Z) explained a very large amount of variation in dissectible carcass fat weight (0.814⩽R 2⩽0.862; P<0.01). These individual BIA parameters also explained a large amount of variation in subcutaneous and intermuscular fat weights (respectively 0.749⩽R 2⩽0.793 and 0.718⩽R 2⩽0.760; P<0.01), and in muscle chemical fat weight (0.663⩽R 2⩽0.684; P<0.01). Still significant but much lower was the variation in muscle, moisture, protein and fat-free soft tissue weights (0.344⩽R 2⩽0.393; P<0.01) explained by BIA parameters. Still, the best models for estimation of muscle, moisture, protein and fat-free soft tissue weights included Rs in addition to CCW, and accounted for 97.1% to 99.8% (P<0.01) of the variation observed, with CCW by itself accounting for 97.0% to 99.6% (P<0.01) of that variation. Resistance was the only independent variable selected for the best model predicting subcutaneous fat weight. It was also selected for the best models

An overview of human biomonitoring of environmental chemicals in the Canadian Health Measures Survey: 2007-2019.

PubMed

Haines, Douglas A; Saravanabhavan, Gurusankar; Werry, Kate; Khoury, Cheryl

2017-03-01

Human biomonitoring (HBM) is used to indicate and quantify exposure by measuring environmental chemicals, their metabolites or reaction products in biological specimens. The biomonitoring component of the Canadian Health Measures Survey (CHMS) is the most comprehensive initiative providing general population HBM data in Canada. The CHMS is an ongoing cross-sectional direct measures survey implemented in 2-year cycles. It provides nationally-representative data on health, nutritional status, environmental exposures, and related risks and protective characteristics. The survey follows a robust planning, design and sampling protocol as well as a comprehensive quality assurance and quality control regime implemented for all aspect of the survey to ensure the validity of the HBM results. HBM blood and urine data are available for CHMS cycles 1 (2007-2009), 2 (2009-2011) and 3 (2012-2013). Field collection has been completed for cycle 4 (2014-2015), with cycle 5 (2016-2017) in progress and cycle 6 planning (2018-2019) being finalized. Biomonitoring results for 279 chemicals are expected over the six cycles of the CHMS (220 in individual blood, urine or hair samples, and 59 in pooled serum samples). The chemicals include metals and trace elements, polychlorinated biphenyls (PCBs), organochlorines, flame retardants, perfluoroalkyl substances, volatile organic compounds (VOCs) and metabolites, environmental phenols, triclocarban, acrylamide, pesticides (e.g., triazines, carbamates, organophosphates, phenoxy, pyrethroids) and/or their metabolites, chlorophenols, polycyclic aromatic hydrocarbon (PAH) metabolites, phthalates and alternate plasticizer metabolites, and tobacco biomarkers. Approximately one half of the chemicals measured in individual blood and urine samples over the first three cycles were detected in more than 60% of samples. CHMS biomonitoring data have been used to establish baseline HBM concentrations in Canadians; inform public health, regulatory risk

Measurements of HO2 chemical kinetics with a new detection method

NASA Technical Reports Server (NTRS)

Lee, L. C.; Suto, M.

1986-01-01

Research for the period from December 1, 1985 to May 31, 1986 is discussed, i.e., the reaction rate constant of HO2+O3 has been measured with a discharge-flow-tube apparatus. The HO2 radical was detected by the OH(A-X) photofragment emission produced from photodissociative excitation of HO2 at 147 nm. In the meantime, the optical emissions produced by the vacuum ultraviolet excitation of chemical species in the flow tube were investigated and used to examine the possibility for their interference with the HO2 detection. The research results are summarized below.

Chemical bonding analysis on amphoteric hydrogen - alkaline earth ammine borohydrides

NASA Astrophysics Data System (ADS)

Kiruthika, S.; Ravindran, P.

2018-04-01

Usually the ions in solid are in the positive oxidation states or in the negative oxidation state depending upon the chemical environment. It is highly unusual for an ion having both positive as well as negative oxidation state in a particular compound. Structural analysis suggest that the alkaline earth ammine borohydrides (AABH) with the chemical formula M (BH4)2(NH3)2 (M = Mg, Ca, or Sr) where hydrogen is present in +1 and -1 oxidation states. In order to understand the oxidation states of hydrogen and also the character of chemical bond present in AABH we have made charge density, electron localization function, Born effective charge, Bader effective charge, and density of states analyses using result from the density functional calculations. Our detailed analyses show that hydrogen is in amphoteric behavior with hydrogen closer to boron is in negative oxidation state and that closer to nitrogen is in the positive oxidation state. Due to the presence of finite covalent bonding between the consitutents in AABH the oxidation state of hydrogen is non-interger value. The confirmation of the presence of amphtoric behavior of hydrogen in AABH has implication in hydrogen storage applications.

Laboratory measurements. [chemical and photochemical data relative to stratospheric modeling

NASA Technical Reports Server (NTRS)

1977-01-01

A compilation of chemical and photochemical data that are relevant to stratospheric modeling is presented. There are three broad categories of data: (1) rate constants for chemical reactions, including temperature and pressure dependencies along with product distributions; (2) absorption cross sections, photodissociation quantum yield, and photolysis; (3) heterogeneous chemical processes.

Standardization of Cassia spectabilis with respect to authenticity, assay and chemical constituent analysis.

PubMed

Torey, Angeline; Sasidharan, Sreenivasan; Yeng, Chen; Latha, Lachimanan Yoga

2010-05-10

Quality control standardizations of the various medicinal plants used in traditional medicine is becoming more important today in view of the commercialization of formulations based on these plants. An attempt at standardization of Cassia spectabilis leaf has been carried out with respect to authenticity, assay and chemical constituent analysis. The authentication involved many parameters, including gross morphology, microscopy of the leaves and functional group analysis by Fourier Transform Infrared (FTIR) spectroscopy. The assay part of standardization involved determination of the minimum inhibitory concentration (MIC) of the extract which could help assess the chemical effects and establish curative values. The MIC of the C. spectabilis leaf extracts was investigated using the Broth Dilution Method. The extracts showed a MIC value of 6.25 mg/mL, independent of the extraction time. The chemical constituent aspect of standardization involves quantification of the main chemical components in C. spectabilis. The GCMS method used for quantification of 2,4-(1H,3H)-pyrimidinedione in the extract was rapid, accurate, precise, linear (R(2) = 0.8685), rugged and robust. Hence this method was suitable for quantification of this component in C. spectabilis. The standardization of C. spectabilis is needed to facilitate marketing of medicinal plants, with a view to promoting the export of valuable Malaysian Traditional Medicinal plants such as C. spectabilis.

Shoe contact dermatitis from dimethyl fumarate: clinical manifestations, patch test results, chemical analysis, and source of exposure.

PubMed

Giménez-Arnau, Ana; Silvestre, Juan Francisco; Mercader, Pedro; De la Cuadra, Jesus; Ballester, Isabel; Gallardo, Fernando; Pujol, Ramón M; Zimerson, Erik; Bruze, Magnus

2009-11-01

The methyl ester form of fumaric acid named dimethyl fumarate (DMF) is an effective mould-growth inhibitor. Its irritating and sensitizing properties were demonstrated in animal models. Recently, DMF has been identified as responsible for furniture contact dermatitis in Europe. To describe the clinical manifestations, patch test results, shoe chemical analysis, and source of exposure to DMF-induced shoe contact dermatitis. Patients with suspected shoe contact dermatitis were studied in compliance with the Declaration of Helsinki. Patch test results obtained with their own shoe and the European baseline series, acrylates and fumaric acid esters (FAE), were recorded according to international guidelines. The content of DMF in shoes was analysed with gas chromatography and mass spectrometry. Acute, immediate irritant contact dermatitis and non-immunological contact urticaria were observed in eight adults and two children, respectively. All the adult patients studied developed a delayed sensitization demonstrated by a positive patch testing to DMF < or = 0.1% in pet. Cross-reactivity with other FAEs and acrylates was observed. At least 12 different shoe brands were investigated. The chemical analysis from the available shoes showed the presence of DMF. DMF in shoes was responsible for severe contact dermatitis. Global preventive measures for avoiding contact with DMF are necessary.

Advancing the Selection of Neurodevelopmental Measures in Epidemiological Studies of Environmental Chemical Exposure and Health Effects

PubMed Central

Youngstrom, Eric; LaKind, Judy S.; Kenworthy, Lauren; Lipkin, Paul H.; Goodman, Michael; Squibb, Katherine; Mattison, Donald R.; Anthony, Bruno J.; Anthony, Laura Gutermuth

2010-01-01

With research suggesting increasing incidence of pediatric neurodevelopmental disorders, questions regarding etiology continue to be raised. Neurodevelopmental function tests have been used in epidemiology studies to evaluate relationships between environmental chemical exposures and neurodevelopmental deficits. Limitations of currently used tests and difficulties with their interpretation have been described, but a comprehensive critical examination of tests commonly used in studies of environmental chemicals and pediatric neurodevelopmental disorders has not been conducted. We provide here a listing and critical evaluation of commonly used neurodevelopmental tests in studies exploring effects from chemical exposures and recommend measures that are not often used, but should be considered. We also discuss important considerations in selecting appropriate tests and provide a case study by reviewing the literature on polychlorinated biphenyls. PMID:20195443

Laser applications to chemical, security, and environmental analysis: introduction to the feature issue.

PubMed

Seeger, Thomas; Dreier, Thomas; Chen, Weidong; Kearny, Sean; Kulatilaka, Waruna

2017-04-10

This Applied Optics feature issue on laser applications to chemical, security, and environmental analysis (LACSEA) highlights papers presented at the LACSEA 2016 Fifteenth Topical Meeting sponsored by the Optical Society of America.

Using chemical benchmarking to determine the persistence of chemicals in a Swedish lake.

PubMed

Zou, Hongyan; Radke, Michael; Kierkegaard, Amelie; MacLeod, Matthew; McLachlan, Michael S

2015-02-03

It is challenging to measure the persistence of chemicals under field conditions. In this work, two approaches for measuring persistence in the field were compared: the chemical mass balance approach, and a novel chemical benchmarking approach. Ten pharmaceuticals, an X-ray contrast agent, and an artificial sweetener were studied in a Swedish lake. Acesulfame K was selected as a benchmark to quantify persistence using the chemical benchmarking approach. The 95% confidence intervals of the half-life for transformation in the lake system ranged from 780-5700 days for carbamazepine to <1-2 days for ketoprofen. The persistence estimates obtained using the benchmarking approach agreed well with those from the mass balance approach (1-21% difference), indicating that chemical benchmarking can be a valid and useful method to measure the persistence of chemicals under field conditions. Compared to the mass balance approach, the benchmarking approach partially or completely eliminates the need to quantify mass flow of chemicals, so it is particularly advantageous when the quantification of mass flow of chemicals is difficult. Furthermore, the benchmarking approach allows for ready comparison and ranking of the persistence of different chemicals.

Molecular similarity measures.

PubMed

Maggiora, Gerald M; Shanmugasundaram, Veerabahu

2011-01-01

Molecular similarity is a pervasive concept in chemistry. It is essential to many aspects of chemical reasoning and analysis and is perhaps the fundamental assumption underlying medicinal chemistry. Dissimilarity, the complement of similarity, also plays a major role in a growing number of applications of molecular diversity in combinatorial chemistry, high-throughput screening, and related fields. How molecular information is represented, called the representation problem, is important to the type of molecular similarity analysis (MSA) that can be carried out in any given situation. In this work, four types of mathematical structure are used to represent molecular information: sets, graphs, vectors, and functions. Molecular similarity is a pairwise relationship that induces structure into sets of molecules, giving rise to the concept of chemical space. Although all three concepts - molecular similarity, molecular representation, and chemical space - are treated in this chapter, the emphasis is on molecular similarity measures. Similarity measures, also called similarity coefficients or indices, are functions that map pairs of compatible molecular representations that are of the same mathematical form into real numbers usually, but not always, lying on the unit interval. This chapter presents a somewhat pedagogical discussion of many types of molecular similarity measures, their strengths and limitations, and their relationship to one another. An expanded account of the material on chemical spaces presented in the first edition of this book is also provided. It includes a discussion of the topography of activity landscapes and the role that activity cliffs in these landscapes play in structure-activity studies.

Meta-analysis of studies on chemical, physical and biological agents in the control of Aedes aegypti.

PubMed

Lima, Estelita Pereira; Goulart, Marília Oliveira Fonseca; Rolim Neto, Modesto Leite

2015-09-04

Aedes aegypti is a vector of international concern because it can transmit to humans three important arboviral diseases: yellow fever, dengue and chikungunya. Epidemics that are repeated year after year in a variety of urban centers indicate that there are control failures, allowing the vector to continue expanding. To identify the most effective vector control strategies and the factors that contributed to the success or failure of each strategy, we carried out a systematic review with meta-analysis of articles published in 12 databases, from 1974 to the month of December 2013. We evaluated the association between the use of whatever chemical substance, mechanical agent, biological or integrated actions against A. aegypti and the control of the vector, as measured by 10 indicators. We found 2,791 articles, but after careful selection, only 26 studies remained for analysis related to control interventions implemented in 15 countries, with 5 biological, 5 chemical, 3 mechanical and 13 integrated strategies. The comparison among all of them, indicated that the control of A. aegypti is significantly associated with the type of strategy used, and that integrated interventions consist of the most effective method for controlling A. aegypti. The most effective control method was the integrated approach, considering the influence of eco-bio-social determinants in the virus-vector-man epidemiological chain, and community involvement, starting with community empowerment as active agents of vector control.

Hazard Assessment of Chemical Air Contaminants Measured in Residences

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

Logue, J.M.; McKone, T.E.; Sherman, M. H.

2010-05-10

Identifying air pollutants that pose a potential hazard indoors can facilitate exposure mitigation. In this study, we compiled summary results from 77 published studies reporting measurements of chemical pollutants in residences in the United States and in countries with similar lifestyles. These data were used to calculate representative mid-range and upper bound concentrations relevant to chronic exposures for 267 pollutants and representative peak concentrations relevant to acute exposures for 5 activity-associated pollutants. Representative concentrations are compared to available chronic and acute health standards for 97 pollutants. Fifteen pollutants appear to exceed chronic health standards in a large fraction of homes.more » Nine other pollutants are identified as potential chronic health hazards in a substantial minority of homes and an additional nine are identified as potential hazards in a very small percentage of homes. Nine pollutants are identified as priority hazards based on the robustness of measured concentration data and the fraction of residences that appear to be impacted: acetaldehyde; acrolein; benzene; 1,3-butadiene; 1,4-dichlorobenzene; formaldehyde; naphthalene; nitrogen dioxide; and PM{sub 2.5}. Activity-based emissions are shown to pose potential acute health hazards for PM{sub 2.5}, formaldehyde, CO, chloroform, and NO{sub 2}.« less

A chemical proteomics approach for global analysis of lysine monomethylome profiling.

PubMed

Wu, Zhixiang; Cheng, Zhongyi; Sun, Mingwei; Wan, Xuelian; Liu, Ping; He, Tieming; Tan, Minjia; Zhao, Yingming

2015-02-01

Methylation of lysine residues on histone proteins is known to play an important role in chromatin structure and function. However, non-histone protein substrates of this modification remain largely unknown. An effective approach for system-wide analysis of protein lysine methylation, particularly lysine monomethylation, is lacking. Here we describe a chemical proteomics approach for global screening for monomethyllysine substrates, involving chemical propionylation of monomethylated lysine, affinity enrichment of the modified monomethylated peptides, and HPLC/MS/MS analysis. Using this approach, we identified with high confidence 446 lysine monomethylation sites in 398 proteins, including three previously unknown histone monomethylation marks, representing the largest data set of protein lysine monomethylation described to date. Our data not only confirms previously discovered lysine methylation substrates in the nucleus and spliceosome, but also reveals new substrates associated with diverse biological processes. This method hence offers a powerful approach for dynamic study of protein lysine monomethylation under diverse cellular conditions and in human diseases. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Neurons as sensors: individual and cascaded chemical sensing.

PubMed

Prasad, Shalini; Zhang, Xuan; Yang, Mo; Ozkan, Cengiz S; Ozkan, Mihrimah

2004-07-15

A single neuron sensor has been developed based on the interaction of gradient electric fields and the cell membrane. Single neurons are rapidly positioned over individual microelectrodes using positive dielectrophoretic traps. This enables the continuous extracellular electrophysiological measurements from individual neurons. The sensor developed using this technique provides the first experimental method for determining single cell sensitivity; the speed of response and the associated physiological changes to a broad spectrum of chemical agents. Binding of specific chemical agents to a specific combination of receptors induces changes to the extracellular membrane potential of a single neuron, which can be translated into unique "signature patterns" (SP), which function as identification tags. Signature patterns are derived using Fast Fourier Transformation (FFT) analysis and Wavelet Transformation (WT) analysis of the modified extracellular action potential. The validity and the sensitivity of the system are demonstrated for a variety of chemical agents ranging from behavior altering chemicals (ethanol), environmentally hazardous agents (hydrogen peroxide, EDTA) to physiologically harmful agents (pyrethroids) at pico- and femto-molar concentrations. The ability of a single neuron to selectively identify specific chemical agents when injected in a serial manner is demonstrated in "cascaded sensing".

Exploring the Potential for Using Inexpensive Natural Reagents Extracted from Plants to Teach Chemical Analysis

ERIC Educational Resources Information Center

Hartwell, Supaporn Kradtap

2012-01-01

A number of scientific articles report on the use of natural extracts from plants as chemical reagents, where the main objective is to present the scientific applications of those natural plant extracts. The author suggests that natural reagents extracted from plants can be used as alternative low cost tools in teaching chemical analysis,…

Environmental Risk Assessment: Spatial Analysis of Chemical Hazards and Risks in South Korea

NASA Astrophysics Data System (ADS)

Yu, H.; Heo, S.; Kim, M.; Lee, W. K.; Jong-Ryeul, S.

2017-12-01

This study identified chemical hazard and risk levels in Korea by analyzing the spatial distribution of chemical factories and accidents. The number of chemical factories and accidents in 5-km2 grids were used as the attribute value for spatial analysis. First, semi-variograms were conducted to examine spatial distribution patterns and to identify spatial autocorrelation of chemical factories and accidents. Semi-variograms explained that the spatial distribution of chemical factories and accidents were spatially autocorrelated. Second, the results of the semi-variograms were used in Ordinary Kriging to estimate chemical hazard and risk level. The level values were extracted from the Ordinary Kriging result and their spatial similarity was examined by juxtaposing the two values with respect to their location. Six peaks were identified in both the hazard and risk estimation result, and the peaks correlated with major cities in Korea. Third, the estimated hazard and risk levels were classified with geometrical interval and could be classified into four quadrants: Low Hazard and Low Risk (LHLR), Low Hazard and High Risk (LHHR), High Hazard and Low Risk (HHLR), and High Hazard and High Risk (HHHR). The 4 groups identified different chemical safety management issues in Korea; relatively safe LHLR group, many chemical reseller factories were found in HHLR group, chemical transportation accidents were in the LHHR group, and an abundance of factories and accidents were in the HHHR group. Each quadrant represented different safety management obstacles in Korea, and studying spatial differences can support the establishment of an efficient risk management plan.

The chemical composition and mineralogy of meteorites measured with very high spatial resolution by a laser mass spectrometer for in situ planetary research

NASA Astrophysics Data System (ADS)

Brigitte Neuland, Maike; Mezger, Klaus; Tulej, Marek; Frey, Samira; Riedo, Andreas; Wurz, Peter; Wiesendanger, Reto

2017-04-01

The knowledge of the chemical composition of moons, comets, asteroids or other planetary bodies is of particular importance for the investigation of the origin and evolution of the Solar System. High resolution in situ studies on planetary surfaces can yield important information on surface heterogeneity, basic grain mineralogy and chemical composition of surface and subsurface. In turn, these data are the basis for our understanding of the physical and chemical processes which led to the formation and alteration of planetary material [1]. We investigated samples of Allende and Sayh al Uhaymir with a highly miniaturised laser mass spectrometer (LMS), which has been designed and built for in situ space research [2,3]. Both meteorite samples were investigated with a spatial resolution of about 10μm in lateral direction. The high sensitivity and high dynamic range of the LMS allow for quantitative measurements of the abundances of the rock-forming and minor and trace elements with high accuracy [4]. From the data, the modal mineralogy of micrometre-sized chondrules can be inferred [5], conclusions about the condensation sequence of the material are possible and the sensitivity for radiogenic elements allows for dating analyses of the investigated material. We measured the composition of various chondrules in Allende, offering valuable clues about the condensation sequence of the different components of the meteorite. We explicitly investigated the chemical composition and heterogeneity of the Allende matrix with an accuracy that cannot be reached by the mechanical analysis methods that were and are widely used in meteoritic research. We demonstrate the capabilities for dating analyses with the LMS. By applying the U-Th-dating method, the age of the SaU169 sample could be determined. Our analyses show that the LMS would be a suitable instrument for high-quality quantitative chemical composition measurements on the surface of a celestial body like a planet, moon or

Chemical Fingerprint Analysis and Quantitative Analysis of Rosa rugosa by UPLC-DAD.

PubMed

Mansur, Sanawar; Abdulla, Rahima; Ayupbec, Amatjan; Aisa, Haji Akbar

2016-12-21

A method based on ultra performance liquid chromatography with a diode array detector (UPLC-DAD) was developed for quantitative analysis of five active compounds and chemical fingerprint analysis of Rosa rugosa . Ten batches of R. rugosa collected from different plantations in the Xinjiang region of China were used to establish the fingerprint. The feasibility and advantages of the used UPLC fingerprint were verified for its similarity evaluation by systematically comparing chromatograms with professional analytical software recommended by State Food and Drug Administration (SFDA) of China. In quantitative analysis, the five compounds showed good regression (R² = 0.9995) within the test ranges, and the recovery of the method was in the range of 94.2%-103.8%. The similarities of liquid chromatography fingerprints of 10 batches of R. rugosa were more than 0.981. The developed UPLC fingerprint method is simple, reliable, and validated for the quality control and identification of R. rugosa . Additionally, simultaneous quantification of five major bioactive ingredients in the R. rugosa samples was conducted to interpret the consistency of the quality test. The results indicated that the UPLC fingerprint, as a characteristic distinguishing method combining similarity evaluation and quantification analysis, can be successfully used to assess the quality and to identify the authenticity of R. rugosa .

Chemical Differentiation of Osseous, Dental, and Non-skeletal Materials in Forensic Anthropology using Elemental Analysis.

PubMed

Zimmerman, Heather A; Meizel-Lambert, Cayli J; Schultz, John J; Sigman, Michael E

2015-03-01

Forensic anthropologists are generally able to identify skeletal materials (bone and tooth) using gross anatomical features; however, highly fragmented or taphonomically altered materials may be problematic to identify. Several chemical analysis techniques have been shown to be reliable laboratory methods that can be used to determine if questionable fragments are osseous, dental, or non-skeletal in nature. The purpose of this review is to provide a detailed background of chemical analysis techniques focusing on elemental compositions that have been assessed for use in differentiating osseous, dental, and non-skeletal materials. More recently, chemical analysis studies have also focused on using the elemental composition of osseous/dental materials to evaluate species and provide individual discrimination, but have generally been successful only in small, closed groups, limiting their use forensically. Despite significant advances incorporating a variety of instruments, including handheld devices, further research is necessary to address issues in standardization, error rates, and sample size/diversity. Copyright © 2014 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

A decision analysis framework for estimating the potential hazards for drinking water resources of chemicals used in hydraulic fracturing fluids.

PubMed

Yost, Erin E; Stanek, John; Burgoon, Lyle D

2017-01-01

Despite growing concerns over the potential for hydraulic fracturing to impact drinking water resources, there are limited data available to identify chemicals used in hydraulic fracturing fluids that may pose public health concerns. In an effort to explore these potential hazards, a multi-criteria decision analysis (MCDA) framework was employed to analyze and rank selected subsets of these chemicals by integrating data on toxicity, frequency of use, and physicochemical properties that describe transport in water. Data used in this analysis were obtained from publicly available databases compiled by the United States Environmental Protection Agency (EPA) as part of a larger study on the potential impacts of hydraulic fracturing on drinking water. Starting with nationwide hydraulic fracturing chemical usage data from EPA's analysis of the FracFocus Chemical Disclosure Registry 1.0, MCDAs were performed on chemicals that had either noncancer toxicity values (n=37) or cancer-specific toxicity values (n=10). The noncancer MCDA was then repeated for subsets of chemicals reported in three representative states (Texas, n=31; Pennsylvania, n=18; and North Dakota, n=20). Within each MCDA, chemicals received scores based on relative toxicity, relative frequency of use, and physicochemical properties (mobility in water, volatility, persistence). Results show a relative ranking of these chemicals based on hazard potential, and provide preliminary insight into chemicals that may be more likely than others to impact drinking water resources. Comparison of nationwide versus state-specific analyses indicates regional differences in the chemicals that may be of more concern to drinking water resources, although many chemicals were commonly used and received similar overall hazard rankings. Several chemicals highlighted by these MCDAs have been reported in groundwater near areas of hydraulic fracturing activity. This approach is intended as a preliminary analysis, and represents one

Thermal, Mechanical and Chemical Analysis for VELOX -Verification Experiments for Lunar Oxygen Production

NASA Astrophysics Data System (ADS)

Lange, Caroline; Ksenik, Eugen; Braukhane, Andy; Richter, Lutz

One major aspect for the development of a long-term human presence on the moon will be sustainability and autonomy of any kind of a permanent base. Important resources, such as breathable air and water for the survival of the crew on the lunar surface will have to be extracted in-situ from the lunar regolith, the major resource on the Moon, which covers the first meter of the lunar surface and contains about 45 At the DLR Bremen we are interested in a compact and flexible lab experimenting facility, which shall demonstrate the feasibility of this process by extracting oxygen out of lunar Regolith, respectively soil simulants and certain minerals in the laboratory case. For this purpose, we have investigated important boundary conditions such as temperatures during the process, chemical reaction characteristics and material properties for the buildup of the facility and established basic requirements which shall be analyzed within this paper. These requirements have been used for the concept development and outline of the facility, which is currently under construction and will be subject to initial tests in the near future. This paper will focus mainly on the theoretical aspects of the facility development. Great effort has been put into the thermal and mechanical outline and pre-analysis of components and the system in a whole. Basic aspects that have been investigated are: 1. Selection of suitable materials for the furnace chamber configuration to provide a high-temperature capable operating mode. 2. Theoretical heat transfer analysis of the designed furnace chamber assembly with subsequent validation with the aid of measured values of the constructed demonstration plant. 3. Description of chemical conversion processes for Hydrogen reduction of Lunar Regolith with corresponding analysis of thermal and reaction times under different boundary conditions. 4. Investigation of the high-temperature mechanical behavior of the constructed furnace chamber with regard to

Experimental Measurements of the Chemical Reaction Zone of Detonating Liquid Explosives

NASA Astrophysics Data System (ADS)

Bouyer, Viviane; Sheffield, Stephen A.; Dattelbaum, Dana M.; Gustavsen, Richard L.; Stahl, David B.; Doucet, Michel; Decaris, Lionel

2009-12-01

We have a joint project between CEA-DAM Le Ripault and Los Alamos National Laboratory (LANL) to study the chemical reaction zone in detonating high explosives using several different laser velocimetry techniques. The short temporal duration of the von Neumann spike and early part of the reaction zone make these measurements difficult. Here, we report results obtained from detonation experiments using VISAR (velocity interferometer system for any reflector) and PDV (photon Doppler velocimetry) methods to measure the particle velocity history at a detonating nitromethane/PMMA interface. Experiments done at CEA were high-explosive-plane-wave initiated and those at LANL were gas-gun-projectile initiated with a detonation run of about 6 charge diameters in all experiments. The experiments had either glass or brass confinement. Excellent agreement of the interface particle velocity measurements at both Laboratories were obtained even though the initiation methods and the velocimetry systems were somewhat different. Some differences were observed in the peak particle velocity because of the ˜2 ns time resolution of the techniques—in all cases the peak was lower than the expected von Neumann spike. This is thought to be because the measurements were not high enough time resolution to resolve the spike.

A reference electrode based on polyvinyl butyral (PVB) polymer for decentralized chemical measurements.

PubMed

Guinovart, Tomàs; Crespo, Gastón A; Rius, F Xavier; Andrade, Francisco J

2014-04-22

A new solid-state reference electrode using a polymeric membrane of polyvinyl butyral (PVB), Ag/AgCl and NaCl to be used in decentralized chemical measurements is presented. The electrode is made by drop-casting the membrane cocktail onto a glassy carbon (GC) substrate. A stable potential (less than 1 mV dec(-1)) over a wide range of concentrations for the several chemical species tested is obtained. No significant influence to changes in redox potential, light and pH are observed. The response of this novel electrode shows good correlation when compared with a conventional double-junction reference electrode. Also good long-term stability (90±33 μV/h) and a lifetime of approximately 4 months are obtained. Aspects related to the working mechanisms are discussed. Atomic Force Microscopy (AFM) studies reveal the presence of nanopores and channels on the surface, and electrochemical impedance spectroscopy (EIS) of optimized electrodes show low bulk resistances, usually in the kΩ range, suggesting that a nanoporous polymeric structure is formed in the interface with the solution. Future applications of this electrode as a disposable device for decentralized measurements are discussed. Examples of the utilization on wearable substrates (tattoos, fabrics, etc) are provided. Copyright © 2014 Elsevier B.V. All rights reserved.

A Magic-Angle Spinning NMR Method for the Site-Specific Measurement of Proton Chemical-Shift Anisotropy in Biological and Organic Solids.

PubMed

Hou, Guangjin; Gupta, Rupal; Polenova, Tatyana; Vega, Alexander J

2014-02-01

Proton chemical shifts are a rich probe of structure and hydrogen bonding environments in organic and biological molecules. Until recently, measurements of 1 H chemical shift tensors have been restricted to either solid systems with sparse proton sites or were based on the indirect determination of anisotropic tensor components from cross-relaxation and liquid-crystal experiments. We have introduced an MAS approach that permits site-resolved determination of CSA tensors of protons forming chemical bonds with labeled spin-1/2 nuclei in fully protonated solids with multiple sites, including organic molecules and proteins. This approach, originally introduced for the measurements of chemical shift tensors of amide protons, is based on three RN -symmetry based experiments, from which the principal components of the 1 H CS tensor can be reliably extracted by simultaneous triple fit of the data. In this article, we expand our approach to a much more challenging system involving aliphatic and aromatic protons. We start with a review of the prior work on experimental-NMR and computational-quantum-chemical approaches for the measurements of 1 H chemical shift tensors and for relating these to the electronic structures. We then present our experimental results on U- 13 C, 15 N-labeled histdine demonstrating that 1 H chemical shift tensors can be reliably determined for the 1 H 15 N and 1 H 13 C spin pairs in cationic and neutral forms of histidine. Finally, we demonstrate that the experimental 1 H(C) and 1 H(N) chemical shift tensors are in agreement with Density Functional Theory calculations, therefore establishing the usefulness of our method for characterization of structure and hydrogen bonding environment in organic and biological solids.

Estimation of environment-related properties of chemicals for design of sustainable processes: development of group-contribution+ (GC+) property models and uncertainty analysis.

PubMed

Hukkerikar, Amol Shivajirao; Kalakul, Sawitree; Sarup, Bent; Young, Douglas M; Sin, Gürkan; Gani, Rafiqul

2012-11-26

The aim of this work is to develop group-contribution(+) (GC(+)) method (combined group-contribution (GC) method and atom connectivity index (CI) method) based property models to provide reliable estimations of environment-related properties of organic chemicals together with uncertainties of estimated property values. For this purpose, a systematic methodology for property modeling and uncertainty analysis is used. The methodology includes a parameter estimation step to determine parameters of property models and an uncertainty analysis step to establish statistical information about the quality of parameter estimation, such as the parameter covariance, the standard errors in predicted properties, and the confidence intervals. For parameter estimation, large data sets of experimentally measured property values of a wide range of chemicals (hydrocarbons, oxygenated chemicals, nitrogenated chemicals, poly functional chemicals, etc.) taken from the database of the US Environmental Protection Agency (EPA) and from the database of USEtox is used. For property modeling and uncertainty analysis, the Marrero and Gani GC method and atom connectivity index method have been considered. In total, 22 environment-related properties, which include the fathead minnow 96-h LC(50), Daphnia magna 48-h LC(50), oral rat LD(50), aqueous solubility, bioconcentration factor, permissible exposure limit (OSHA-TWA), photochemical oxidation potential, global warming potential, ozone depletion potential, acidification potential, emission to urban air (carcinogenic and noncarcinogenic), emission to continental rural air (carcinogenic and noncarcinogenic), emission to continental fresh water (carcinogenic and noncarcinogenic), emission to continental seawater (carcinogenic and noncarcinogenic), emission to continental natural soil (carcinogenic and noncarcinogenic), and emission to continental agricultural soil (carcinogenic and noncarcinogenic) have been modeled and analyzed. The application

Single Particle Analysis by Combined Chemical Imaging to Study Episodic Air Pollution Events in Vienna

NASA Astrophysics Data System (ADS)

Ofner, Johannes; Eitenberger, Elisabeth; Friedbacher, Gernot; Brenner, Florian; Hutter, Herbert; Schauer, Gerhard; Kistler, Magdalena; Greilinger, Marion; Lohninger, Hans; Lendl, Bernhard; Kasper-Giebl, Anne

2017-04-01

The aerosol composition of a city like Vienna is characterized by a complex interaction of local emissions and atmospheric input on a regional and continental scale. The identification of major aerosol constituents for basic source appointment and air quality issues needs a high analytical effort. Exceptional episodic air pollution events strongly change the typical aerosol composition of a city like Vienna on a time-scale of few hours to several days. Analyzing the chemistry of particulate matter from these events is often hampered by the sampling time and related sample amount necessary to apply the full range of bulk analytical methods needed for chemical characterization. Additionally, morphological and single particle features are hardly accessible. Chemical Imaging evolved to a powerful tool for image-based chemical analysis of complex samples. As a complementary technique to bulk analytical methods, chemical imaging can address a new access to study air pollution events by obtaining major aerosol constituents with single particle features at high temporal resolutions and small sample volumes. The analysis of the chemical imaging datasets is assisted by multivariate statistics with the benefit of image-based chemical structure determination for direct aerosol source appointment. A novel approach in chemical imaging is combined chemical imaging or so-called multisensor hyperspectral imaging, involving elemental imaging (electron microscopy-based energy dispersive X-ray imaging), vibrational imaging (Raman micro-spectroscopy) and mass spectrometric imaging (Time-of-Flight Secondary Ion Mass Spectrometry) with subsequent combined multivariate analytics. Combined chemical imaging of precipitated aerosol particles will be demonstrated by the following examples of air pollution events in Vienna: Exceptional episodic events like the transformation of Saharan dust by the impact of the city of Vienna will be discussed and compared to samples obtained at a high alpine

Effects of glycolic acid chemical peeling on facial pigment deposition: evaluation using novel computer analysis of digital-camera-captured images.

PubMed

Kakudo, Natsuko; Kushida, Satoshi; Suzuki, Kenji; Kusumoto, Kenji

2013-12-01

Chemical peeling is becoming increasingly popular for skin rejuvenation in dermatological cosmetic medicine. However, the improvements seen with chemical peeling are often very minor, and it is difficult to conduct a quantitative assessment of pre- and post-treatment appearance. We report the pre- and postpeeling effects for facial pigment deposition using a novel computer analysis method for digital-camera-captured images. Glycolic acid chemical peeling was performed a total of 5 times at 2-week intervals in 23 healthy women. We conducted a computer image analysis by utilizing Robo Skin Analyzer CS 50 and Clinical Suite 2.1 and then reviewed each parameter for the area of facial pigment deposition pre- and post-treatment. Parameters were pigmentation size and four pigmentation categories: little pigmentation and three levels of marked pigmentation (Lv1, 2, and 3) based on detection threshold. Each parameter was measured, and the total area of facial pigmentation was calculated. The total area of little pigmentation and marked pigmentation (Lv1) was significantly reduced. On the other hand, a significant difference was not observed for the total area of marked pigmentation Lv2 and Lv3. This suggests that glycolic acid chemical peeling has an effect on small facial pigment disposition or has an effect on light pigment deposition. As the Robo Skin Analyzer is useful for objectively quantifying and analyzing minor changes in facial skin, it is considered to be an effective tool for accumulating treatment evidence in the cosmetic and esthetic skin field. © 2013 Wiley Periodicals, Inc.

Lessons learned from non-medical industries: root cause analysis as culture change at a chemical plant

PubMed Central

Carroll, J; Rudolph, J; Hatakenaka, S

2002-01-01



 Root cause analysis was introduced to a chemical plant as a way of enhancing performance and safety, exemplified by the investigation of an explosion. The cultural legacy of the root cause learning intervention was embodied in managers' increased openness to new ideas, individuals' questioning attitude and disciplined thinking, and a root cause analysis process that provided continual opportunities to learn and improve. Lessons for health care are discussed, taking account of differences between the chemical and healthcare industries. PMID:12486993

Chemical purity using quantitative 1H-nuclear magnetic resonance: a hierarchical Bayesian approach for traceable calibrations

NASA Astrophysics Data System (ADS)

Toman, Blaza; Nelson, Michael A.; Lippa, Katrice A.

2016-10-01

Chemical purity assessment using quantitative 1H-nuclear magnetic resonance spectroscopy is a method based on ratio references of mass and signal intensity of the analyte species to that of chemical standards of known purity. As such, it is an example of a calculation using a known measurement equation with multiple inputs. Though multiple samples are often analyzed during purity evaluations in order to assess measurement repeatability, the uncertainty evaluation must also account for contributions from inputs to the measurement equation. Furthermore, there may be other uncertainty components inherent in the experimental design, such as independent implementation of multiple calibration standards. As such, the uncertainty evaluation is not purely bottom up (based on the measurement equation) or top down (based on the experimental design), but inherently contains elements of both. This hybrid form of uncertainty analysis is readily implemented with Bayesian statistical analysis. In this article we describe this type of analysis in detail and illustrate it using data from an evaluation of chemical purity and its uncertainty for a folic acid material.

Miniaturised wireless smart tag for optical chemical analysis applications.

PubMed

Steinberg, Matthew D; Kassal, Petar; Tkalčec, Biserka; Murković Steinberg, Ivana

2014-01-01

A novel miniaturised photometer has been developed as an ultra-portable and mobile analytical chemical instrument. The low-cost photometer presents a paradigm shift in mobile chemical sensor instrumentation because it is built around a contactless smart card format. The photometer tag is based on the radio-frequency identification (RFID) smart card system, which provides short-range wireless data and power transfer between the photometer and a proximal reader, and which allows the reader to also energise the photometer by near field electromagnetic induction. RFID is set to become a key enabling technology of the Internet-of-Things (IoT), hence devices such as the photometer described here will enable numerous mobile, wearable and vanguard chemical sensing applications in the emerging connected world. In the work presented here, we demonstrate the characterisation of a low-power RFID wireless sensor tag with an LED/photodiode-based photometric input. The performance of the wireless photometer has been tested through two different model analytical applications. The first is photometry in solution, where colour intensity as a function of dye concentration was measured. The second is an ion-selective optode system in which potassium ion concentrations were determined by using previously well characterised bulk optode membranes. The analytical performance of the wireless photometer smart tag is clearly demonstrated by these optical absorption-based analytical experiments, with excellent data agreement to a reference laboratory instrument. © 2013 Elsevier B.V. All rights reserved.

Evaluation of alternative approaches for measuring n-octanol/water partition coefficients for methodologically challenging chemicals (MCCs)

EPA Science Inventory

Measurements of n-octanol/water partition coefficients (KOW) for highly hydrophobic chemicals, i.e., greater than 108, are extremely difficult and are rarely made, in part because the vanishingly small concentrations in the water phase require extraordinary analytical sensitivity...

Photoacoustic physio-chemical analysis for prostate cancer diagnosis (Conference Presentation)

NASA Astrophysics Data System (ADS)

Xu, Guan; Cheng, Qian; Huang, Shengsong; Qin, Ming; Hopkins, Thomas; Lee, Chang H.; Kopelman, Raoul; Chao, Wan-yu; Keller, Evan T.; Wu, Denglong; Wang, Xueding

2017-03-01

Photoacoustic physio-chemical analysis (PAPCA) is a recently developed technology capable of simultaneously quantifying the content of molecular components and the corresponding microarchitectures in biological tissue. We have successfully quantified the diagnostic information in livers with PAPCA. In this study, we implemented PAPCA to the diagnosis of prostate cancers. 4 human prostates were scanned ex vivo. The PA signals from normal and cancerous regions in the prostates were acquired by an interstitial needle PA probe. A total of 14 interstitial measurements, including 6 within the normal regions and 8 in the cancerous regions, were acquired. The observed changes in molecular components, including lipid, collagen and hemoglobin were consistent with the findings by other research groups. The changes were quantified by PA spectral analysis (PASA) at wavelengths where strong optical absorption of the relevant molecular components was found. Statistically significant differences among the PASA parameters were observed (p=0.025 at significance of 0.05). A support vector machine model for differentiating the normal and cancerous tissue was established. With the limited number of samples, an 85% diagnostic accuracy was found. The diagnostic information in the PCPCA can be further enriched by targeted optical contrast agents visualizing the microarchitecture in PCa tissues. F3 PAA-PEG nanoparticles was employed to stain the PCa cells in a transgenic mouse model, in which the microarchitectures of normal and cancerous prostate tissues are comparable to that in human. Statistically significant differences were observed between the contrast-enhanced normal and cancerous regions (p=0.038 at a significance of 0.05).

Chemical facility vulnerability assessment project.

PubMed

Jaeger, Calvin D

2003-11-14

Sandia National Laboratories, under the direction of the Office of Science and Technology, National Institute of Justice, conducted the chemical facility vulnerability assessment (CFVA) project. The primary objective of this project was to develop, test and validate a vulnerability assessment methodology (VAM) for determining the security of chemical facilities against terrorist or criminal attacks (VAM-CF). The project also included a report to the Department of Justice for Congress that in addition to describing the VAM-CF also addressed general observations related to security practices, threats and risks at chemical facilities and chemical transport. In the development of the VAM-CF Sandia leveraged the experience gained from the use and development of VAs in other areas and the input from the chemical industry and Federal agencies. The VAM-CF is a systematic, risk-based approach where risk is a function of the severity of consequences of an undesired event, the attack potential, and the likelihood of adversary success in causing the undesired event. For the purpose of the VAM-CF analyses Risk is a function of S, L(A), and L(AS), where S is the severity of consequence of an event, L(A) is the attack potential and L(AS) likelihood of adversary success in causing a catastrophic event. The VAM-CF consists of 13 basic steps. It involves an initial screening step, which helps to identify and prioritize facilities for further analysis. This step is similar to the prioritization approach developed by the American Chemistry Council (ACC). Other steps help to determine the components of the risk equation and ultimately the risk. The VAM-CF process involves identifying the hazardous chemicals and processes at a chemical facility. It helps chemical facilities to focus their attention on the most critical areas. The VAM-CF is not a quantitative analysis but, rather, compares relative security risks. If the risks are deemed too high, recommendations are developed for

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.

Precession technique and electron diffractometry as new tools for crystal structure analysis and chemical bonding determination.

PubMed

Avilov, A; Kuligin, K; Nicolopoulos, S; Nickolskiy, M; Boulahya, K; Portillo, J; Lepeshov, G; Sobolev, B; Collette, J P; Martin, N; Robins, A C; Fischione, P

2007-01-01

We have developed a new fast electron diffractometer working with high dynamic range and linearity for crystal structure determinations. Electron diffraction (ED) patterns can be scanned serially in front of a Faraday cage detector; the total measurement time for several hundred ED reflections can be tens of seconds having high statistical accuracy for all measured intensities (1-2%). This new tool can be installed to any type of TEM without any column modification and is linked to a specially developed electron beam precession "Spinning Star" system. Precession of the electron beam (Vincent-Midgley technique) reduces dynamical effects allowing also use of accurate intensities for crystal structure analysis. We describe the technical characteristics of this new tool together with the first experimental results. Accurate measurement of electron diffraction intensities by electron diffractometer opens new possibilities not only for revealing unknown structures, but also for electrostatic potential determination and chemical bonding investigation. As an example, we present detailed atomic bonding information of CaF(2) as revealed for the first time by precise electron diffractometry.

Chemical hazards analysis of resilient flooring for healthcare.

PubMed

Lent, Tom; Silas, Julie; Vallette, Jim

2010-01-01

This article addresses resilient flooring, evaluating the potential health effects of vinyl flooring and the leading alternatives-synthetic rubber, polyolefin, and linoleum-currently used in the healthcare marketplace. The study inventories chemicals incorporated as components of each of the four material types or involved in their life cycle as feedstocks, intermediary chemicals, or emissions. It then characterizes those chemicals using a chemical hazard-based framework that addresses persistence and bioaccumulation, human toxicity, and human exposures.

Proteomic Analysis of Metabolic Responses to Biofuels and Chemicals in Photosynthetic Cyanobacteria.

PubMed

Sun, T; Chen, L; Zhang, W

2017-01-01

Recent progresses in various "omics" technologies have enabled quantitative measurements of biological molecules in a high-throughput manner. Among them, high-throughput proteomics is a rapidly advancing field that offers a new means to quantify metabolic changes at protein level, which has significantly facilitated our understanding of cellular process, such as protein synthesis, posttranslational modifications, and degradation in responding to environmental perturbations. Cyanobacteria are autotrophic prokaryotes that can perform oxygenic photosynthesis and have recently attracted significant attentions as one promising alternative to traditionally biomass-based "microbial cell factories" to produce green fuels and chemicals. However, early studies have shown that the low tolerance to toxic biofuels and chemicals represented one major hurdle for further improving productivity of the cyanobacterial production systems. To address the issue, metabolic responses and their regulation of cyanobacterial cells to toxic end-products need to be defined. In this chapter, we discuss recent progresses in interpreting cyanobacterial responses to biofuels and chemicals using high-throughput proteomics approach, aiming to provide insights and guidelines on how to enhance tolerance and productivity of biofuels or chemicals in the renewable cyanobacteria systems in the future. © 2017 Elsevier Inc. All rights reserved.

Laws of organization and chemical analysis: Blainville and Müller.

PubMed

Duchesneau, François

2016-12-01

When "general physiology" emerged as a basic field of research within biology in the early nineteenth century, Henri Ducrotay de Blainville (1777-1850) on the one hand and Johannes Peter Müller (1801-1858) on the other appealed to chemical analysis to account for the properties and operations of organisms that were observed to differ from what was found in inorganic compounds. Their aim was to establish laws of vital organization that would be based on organic chemical processes, but would also be of use to explain morphological and functional differences among life forms. The intent of this paper is to specify for each of these leading physiologists the different presuppositions that provided theoretical frameworks for their interpretation of what they conceived of as laws of organization underpinning the dynamics of vital phenomena. Blainville presumed that the properties of organic compounds depended on the chemical properties of their constitutive molecules, but combined according to patterns of functional development, and that the latter could only be inferred from an empirical survey of modes of organization across the spectrum of life forms. For Müller, while all vital processes involved chemical reactions, in the formative and functional operations of organisms, these reactions would result from the action of life forces that were responsible for the production of organic combinations and thus for vital and animal functions. As both physiologists set significant methodological patterns for their many disciples and followers, their respective quasi-reductionist and anti-reductionist positions need to be accounted for.

Miniature near-infrared spectrometer for point-of-use chemical analysis

NASA Astrophysics Data System (ADS)

Friedrich, Donald M.; Hulse, Charles A.; von Gunten, Marc; Williamson, Eric P.; Pederson, Christopher G.; O'Brien, Nada A.

2014-03-01

Point-of-use chemical analysis holds tremendous promise for a number of industries, including agriculture, recycling, pharmaceuticals and homeland security. Near infrared (NIR) spectroscopy is an excellent candidate for these applications, with minimal sample preparation for real-time decision-making. We will detail the development of a golf ball-sized NIR spectrometer developed specifically for this purpose. The instrument is based upon a thin-film dispersive element that is very stable over time and temperature, with less than 2 nm change expected over the operating temperature range and lifetime of the instrument. This filter is coupled with an uncooled InGaAs detector array in a small, rugged, environmentally stable optical bench ideally suited to unpredictable environments. The resulting instrument weighs less than 60 grams, includes onboard illumination and collection optics for diffuse reflectance applications in the 900-1700 nm wavelength range, and is USB-powered. It can be driven in the field by a laptop, tablet or even a smartphone. The software design includes the potential for both on-board and cloud-based storage, analysis and decision-making. The key attributes of the instrument and the underlying design tradeoffs will be discussed, focusing on miniaturization, ruggedization, power consumption and cost. The optical performance of the instrument, as well as its fit-for purpose will be detailed. Finally, we will show that our manufacturing process has enabled us to build instruments with excellent unit-to-unit reproducibility. We will show that this is a key enabler for instrumentindependent chemical analysis models, a requirement for mass point-of-use deployment.

The Stanford-U.S. Geological Survey SHRIMP ion microprobe--a tool for micro-scale chemical and isotopic analysis

USGS Publications Warehouse

Bacon, Charles R.; Grove, Marty; Vazquez, Jorge A.; Coble, Matthew A.

2012-01-01

Answers to many questions in Earth science require chemical analysis of minute volumes of minerals, volcanic glass, or biological materials. Secondary Ion Mass Spectrometry (SIMS) is an extremely sensitive analytical method in which a 5–30 micrometer diameter "primary" beam of charged particles (ions) is focused on a region of a solid specimen to sputter secondary ions from 1–5 nanograms of the sample under high vacuum. The elemental abundances and isotopic ratios of these secondary ions are determined with a mass spectrometer. These results can be used for geochronology to determine the age of a region within a crystal thousands to billions of years old or to precisely measure trace abundances of chemical elements at concentrations as low as parts per billion. A partnership of the U.S. Geological Survey and the Stanford University School of Earth Sciences operates a large SIMS instrument, the Sensitive High-Resolution Ion Microprobe with Reverse Geometry (SHRIMP–RG) on the Stanford campus.

Chemical, biochemical, and environmental fiber sensors III; Proceedings of the Meeting, Boston, MA, Sept. 4, 5, 1991

NASA Astrophysics Data System (ADS)

Lieberman, Robert A.

Various papers on chemical, biochemical, and environmental fiber sensors are presented. Individual topics addressed include: fiber optic pressure sensor for combustion monitoring and control, viologen-based fiber optic oxygen sensors, renewable-reagent fiber optic sensor for ocean pCO2, transition metal complexes as indicators for a fiber optic oxygen sensor, fiber optic pH measurements using azo indicators, simple reversible fiber optic chemical sensors using solvatochromic dyes, totally integrated optical measuring sensors, integrated optic biosensor for environmental monitoring, radiation dosimetry using planar waveguide sensors, optical and piezoelectric analysis of polymer films for chemical sensor characterization, source polarization effects in an optical fiber fluorosensor, lens-type refractometer for on-line chemical analysis, fiber optic hydrocarbon sensor system, chemical sensors for environmental monitoring, optical fibers for liquid-crystal sensing and logic devices, suitability of single-mode fluoride fibers for evanescent-wave sensing, integrated modules for fiber optic sensors, optoelectronic sensors based on narrowband A3B5 alloys, fiber Bragg grating chemical sensor.

CHEMICAL ANALYSIS OF SIMULATED HIGH LEVEL WASTE GLASSES TO SUPPORT SULFATE SOLUBILITY MODELING

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

Fox, K.; Marra, J.

2014-08-14

The U.S. Department of Energy (DOE), Office of Environmental Management (EM) is sponsoring an international, collaborative project to develop a fundamental model for sulfate solubility in nuclear waste glass. The solubility of sulfate has a significant impact on the achievable waste loading for nuclear waste forms both within the DOE complex and to some extent at U.K. sites. The development of enhanced borosilicate glass compositions with improved sulfate solubility will allow for higher waste loadings and accelerated cleanup missions. Much of the previous work on improving sulfate retention in waste glasses has been done on an empirical basis, making itmore » difficult to apply the findings to future waste compositions despite the large number of glass systems studied. A more fundamental, rather than empirical, model of sulfate solubility in glass, under development at Sheffield Hallam University (SHU), could provide a solution to the issues of sulfate solubility. The model uses the normalized cation field strength index as a function of glass composition to predict sulfate capacity, and has shown early success for some glass systems. The objective of the current scope is to mature the sulfate solubility model to the point where it can be used to guide glass composition development for DOE waste vitrification efforts, allowing for enhanced waste loadings and waste throughput. A series of targeted glass compositions was selected to resolve data gaps in the current model. SHU fabricated these glasses and sent samples to the Savannah River National Laboratory (SRNL) for chemical composition analysis. SHU will use the resulting data to enhance the sulfate solubility model and resolve any deficiencies. In this report, SRNL provides chemical analyses for simulated waste glasses fabricated SHU in support of sulfate solubility model development. A review of the measured compositions revealed that there are issues with the B{sub 2}O{sub 3} and Fe{sub 2}O{sub 3

Analysis of LDEF experiment AO187-2: Chemically and isotopic measurements of micrometeoroids by secondary ion mass spectrometry

NASA Technical Reports Server (NTRS)

1992-01-01

Numerous 'extended impacts' found in both leading and trailing edge capture cells have been successfully analyzed for the chemical composition of projectile residues by secondary ion mass spectrometry (SIMS). Most data have been obtained from the trailing edge cells where 45 of 58 impacts have been classified as 'probably natural' and the remainder as 'possibly man-made debris.' This is in striking contrast to leading edge cells where 9 of 11 impacts so far measured are definitely classified as orbital debris. Although all the leading edge cells had lost their plastic entrance foils during flight, the rate of foil failure was similar to that of the trailing edge cells, 10 percent of which were recovered intact. Ultra-violet embrittlement is suspected as the major cause of failure on both leading and trailing edges. The major impediment to the accurate determination of projectile chemistry is the fractionation of volatile and refractory elements in the hypervelocity impact and redeposition processes. This effect had been noticed in simulation experiment but is more pronounced in the Long Duration Exposure Facility (LDEF) capture cells, probably due to the higher average velocities of the space impacts. Surface contamination of the pure Ge surfaces with a substance rich in Si but also containing Mg and Al provides an additional problem for the accurate determination of impactor chemistry. The effect is variable, being much larger on surfaces that were exposed to space than in those cells that remained intact. Future work will concentrate on the analyses of more leading edge impacts and the development of new SIMS techniques for the measurement of elemental abundances in extended impacts.

A detailed pathway analysis of the chemical reaction system generating the Martian vertical ozone profile

NASA Astrophysics Data System (ADS)

Stock, Joachim W.; Blaszczak-Boxe, Christopher S.; Lehmann, Ralph; Grenfell, J. Lee; Patzer, A. Beate C.; Rauer, Heike; Yung, Yuk L.

2017-07-01

Atmospheric chemical composition is crucial in determining a planet's atmospheric structure, stability, and evolution. Attaining a quantitative understanding of the essential chemical mechanisms governing atmospheric composition is nontrivial due to complex interactions between chemical species. Trace species, for example, can participate in catalytic cycles - affecting the abundance of major and other trace gas species. Specifically, for Mars, such cycles dictate the abundance of its primary atmospheric constituent, carbon dioxide (CO2), but also for one of its trace gases, ozone (O3). The identification of chemical pathways/cycles by hand is extremely demanding; hence, the application of numerical methods, such as the Pathway Analysis Program (PAP), is crucial to analyze and quantitatively exemplify chemical reaction networks. Here, we carry out the first automated quantitative chemical pathway analysis of Mars' atmosphere with respect to O3. PAP was applied to JPL/Caltech's 1-D updated photochemical Mars model's output data. We determine all significant chemical pathways and their contribution to O3 production and consumption (up to 80 km) in order to investigate the mechanisms causing the characteristic shape of the O3 volume mixing ratio profile, i.e. a ground layer maximum and an ozone layer at ∼50 km. These pathways explain why an O3 layer is present, why it is located at that particular altitude and what the different processes forming the near-surface and middle atmosphere O3 maxima are. Furthermore, we show that the Martian atmosphere can be divided into two chemically distinct regions according to the O(3P):O3 ratio. In the lower region (below approximately 24 km altitude) O3 is the most abundant Ox (= O3 + O(3P)) species. In the upper region (above approximately 24 km altitude), where the O3 layer is located, O(3P) is the most abundant Ox species. Earlier results concerning the formation of O3 on Mars can now be explained with the help of chemical

Physical and chemical analysis of a Ni/H2 cell

NASA Technical Reports Server (NTRS)

Vaidyanathan, H.; Earl, M. W.; Kirkendall, T. D.

1991-01-01

A cycled aerospace nickel hydrogen (Ni/H2) cell was subjected to destructive physical analysis to determine the reason for a capacity loss after 5,967 cycles at 60 percent depth of discharge. The positive plates in the cell were analyzed in terms of chemical composition, active material utilization, charge efficiency, and thickness increase. The microstructure of a cross section of the positive plate was determined by backscattered electron image analysis. The results suggest that the capacity loss in the cell is caused by low charge acceptance and low active material utilization at the positive plate. The oxidized nickel species content of the positive plate increased due to corrosion of the nickel sintered skeleton. This appears to circumvent the orderly reaction of the active material. Microstructural analysis has indicated that a new phase of active material is formed with cycling.

SIMS chemical and isotopic analysis of impact features from LDEF experiments AO187-1 and AO187-2

NASA Technical Reports Server (NTRS)

Stadermann, Frank J.; Amari, Sachiko; Foote, John; Swan, Pat; Walker, Robert M.; Zinner, Ernst

1995-01-01

Previous secondary ion mass spectrometry (SIMS) studies of extended impact features from LDEF capture cell experiment AO187-2 showed that it is possible to distinguish natural and man-made particle impacts based on the chemical composition of projectile residues. The same measurement technique has now been applied to specially prepared gold target impacts from experiment AO187-1 in order to identify the origins of projectiles that left deposits too thin to be analyzed by conventional energy-dispersive x-ray (EDX) spectroscopy. The results indicate that SIMS may be the method of choice for the analysis of impact deposits on a variety of sample surfaces. SIMS was also used to determine the isotopic compositions of impact residues from several natural projectiles. Within the precision of the measurements all analyzed residues show isotopically normal compositions.

Chemical Fingerprint and Quantitative Analysis for the Quality Evaluation of Docynia dcne Leaves by High-Performance Liquid Chromatography Coupled with Chemometrics Analysis.

PubMed

Zhang, Xiaoyu; Mei, Xueran; Wang, Zhanguo; Wu, Jing; Liu, Gang; Hu, Huiling; Li, Qijuan

2018-05-24

Docynia dcne leaf from the genus of Docynia Dcne (including three species of Docynia delavayi, Docynia indica and Docynia longiunguis.) is an important raw material of local ethnic minority tea, ethnomedicines and food supplements in southwestern areas of China. However, D. dcne leaves from these three species are usually used confusingly, which could influence the therapeutic effect of it. A rapid and effective method for the chemical fingerprint and quantitative analysis to evaluate the quality of D. dcne leaves was established. The chemometric methods, including similarity analysis, hierarchical cluster analysis and partial least-squares discrimination analysis, were applied to distinguish 30 batches of D. dcne leaf samples from these three species. The above results could validate each other and successfully group these samples into three categories which were closely related to the species of D. dcne leaves. Moreover, isoquercitrin and phlorizin were screened as the chemical markers to evaluate the quality of D. dcne leaves from different species. And the contents of isoquercitrin and phlorizin varied remarkably in these samples, with ranges of 6.41-38.84 and 95.73-217.76 mg/g, respectively. All the results indicated that an integration method of chemical fingerprint couple with chemometrics analysis and quantitative assessment was a powerful and beneficial tool for quality control of D. dcne leaves, and could be applied also for differentiation and quality control of other herbal preparations.

Chemical composition of scales generated from oil industry and correlation to radionuclide contents and gamma-ray measurements of (210)Pb.

PubMed

Al Attar, Lina; Safia, Bassam; Abdul Ghani, Basem

2016-03-01

Scale generated from the maintenance of equipment contaminated by naturally occurring radioactive materials may contain also chemical components that cause hazardous pollution to human health and the environment. This study spotlights the characterisation of chemical pollutants in scales in relation to home-made comparison samples as no reference material for such waste exists. Analysis by energy dispersive x-ray fluorescence, with accuracy and precision better than 90%, revealed that barium was the most abundant element in scale samples, ranging from 1.4 to 38.2%. The concentrations of the toxic elements such as lead and chromium were as high as 2.5 and 1.2% respectively. Statistically, high correlation was observed between the concentration of Ba and Sr, sample density, radionuclide contents ((210)Pb and (226)Ra) and self-attenuation factor used for the radio-measurements. However, iron showed a reverse correlation. Interpretation of data with regards to the mineralogical components indicated that (226)Ra and (210)Pb co-precipitated with the insoluble salt Ba0.75Sr0.25SO4. Since both Ba and Sr have high Z, samples of high density (ρ) were accompanied with high values of self-attenuation correction factors (Cf) for the emitted radiation; correlation matrix of Pearson reached 0.935 between ρ and Cf. An attempt to eliminate the effect of the elemental composition and improve gamma measurements of (210)Pb activity concentration in scale samples was made, which showed no correction for self-attenuation was needed when sample densities were in the range 1.0-1.4 g cm(-3). For denser samples, a mathematical model was developed. Accurate determinations of radionuclide and chemical contents of scale would facilitate future Environmental Impact Assessment for the petroleum industry. Copyright © 2015 Elsevier Ltd. All rights reserved.

Surface-enhanced Raman sensor for trace chemical detection in water

NASA Astrophysics Data System (ADS)

Lee, Vincent Y.; Farquharson, Stuart; Rainey, Petrie M.

1999-11-01

Surface-enhanced Raman spectroscopy (SERS) promises to be one of the most sensitive methods for chemical detection and in recent years SERS has been used for chemical, biochemical, environmental, and physiological applications. A variety of methods using various media (electrodes, colloids, and substrates) have been successfully developed to enhance Raman signals by six orders of magnitude and more. However, SERS has not become a routine analytical technique because these methods are unable to provide quantitative measurements. This is largely due to the inability to fabricate a sampling medium that provides reversible chemical adsorption, analysis-to-analysis reproducibility, unrestricted solution requirements (reagent concentration and pH) or sample phase (liquid or solid). In an effort to overcome these restrictions, we have developed metal-doped sol-gels to provide surface-enhancement of Raman scattering.

Semi-Continuous Measurements of Aerosol Chemical Composition During the Summer 2002 Yosemite National Park Special Study

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

Collette, J; Lee, T; Heath, J

2003-02-16

Semi-continuous measurements of fine particle composition were made over a period of several weeks in summer 2002 in Yosemite National Park, California. These included measurement of aerosol ionic composition (by PILS- Particle-Into-Liquid System) and aerosol carbon (by dual wavelength aethalometer and an R&P particulate carbon monitor). The data reveal that aerosol composition at the site is highly :variable in time, with a strong diurnal cycle. Interestingly, however, different diurnal cycles were sometimes observed for different chemical constituents of the particles. Organic carbon was observed to dominate fine particle mass, with some periods apparently associated with influx of smoke from wildfiresmore » in the western U.S. Measurements of fine particle carbon isotopes revealed the fraction of carbon from biogenic sources to range from approximately 73 to 95%. The ionic fraction of the aerosol was usually dominated by ammoniated sulfate. During most periods, PM{sub 2.5} nitrate was found primarily in sea salt particles from which chloride had been displaced. Strong variations in the extent of ammonia neutralization of sulfate were also observed. The ability to observe rapid changes in aerosol composition using these semi-continuous aerosol composition measurements is helpful for understanding the dynamic chemical composition of fine particles responsible for regional haze.« less

Pediatric susceptibility to 18 industrial chemicals: a comparative analysis of newborn with young animals.

PubMed

Hasegawa, R; Hirata-Koizumi, M; Dourson, M; Parker, A; Hirose, A; Nakai, S; Kamata, E; Ema, M

2007-04-01

We comprehensively re-analyzed the toxicity data for 18 industrial chemicals from repeated oral exposures in newborn and young rats, which were previously published. Two new toxicity endpoints specific to this comparative analysis were identified, the first, the presumed no observed adverse effect level (pNOAEL) was estimated based on results of both main and dose-finding studies, and the second, the presumed unequivocally toxic level (pUETL) was defined as a clear toxic dose giving similar severity in both newborn and young rats. Based on the analyses of both pNOAEL and pUETL ratios between the different ages, newborn rats demonstrated greater susceptibility (at most 8-fold) to nearly two thirds of these 18 chemicals (mostly phenolic substances), and less or nearly equal sensitivity to the other chemicals. Exceptionally one chemical only showed toxicity in newborn rats. In addition, Benchmark Dose Lower Bound (BMDL) estimates were calculated as an alternative endpoint. Most BMDLs were comparable to their corresponding pNOAELs and the overall correlation coefficient was 0.904. We discussed how our results can be incorporated into chemical risk assessment approaches to protect pediatric health from direct oral exposure to chemicals.

Uses of NHANES Biomarker Data for Chemical Risk Assessment: Trends, Challenges, and Opportunities

PubMed Central

DeWoskin, Robert S.; Tan, Yu-Mei; Pleil, Joachim D.; Phillips, Martin Blake; George, Barbara Jane; Christensen, Krista; Schreinemachers, Dina M.; Williams, Marc A.; Hubal, Elaine A. Cohen; Edwards, Stephen W.

2015-01-01

Background Each year, the U.S. NHANES measures hundreds of chemical biomarkers in samples from thousands of study participants. These biomarker measurements are used to establish population reference ranges, track exposure trends, identify population subsets with elevated exposures, and prioritize research needs. There is now interest in further utilizing the NHANES data to inform chemical risk assessments. Objectives This article highlights a) the extent to which U.S. NHANES chemical biomarker data have been evaluated, b) groups of chemicals that have been studied, c) data analysis approaches and challenges, and d) opportunities for using these data to inform risk assessments. Methods A literature search (1999–2013) was performed to identify publications in which U.S. NHANES data were reported. Manual curation identified only the subset of publications that clearly utilized chemical biomarker data. This subset was evaluated for chemical groupings, data analysis approaches, and overall trends. Results A small percentage of the sampled NHANES-related publications reported on chemical biomarkers (8% yearly average). Of 11 chemical groups, metals/metalloids were most frequently evaluated (49%), followed by pesticides (9%) and environmental phenols (7%). Studies of multiple chemical groups were also common (8%). Publications linking chemical biomarkers to health metrics have increased dramatically in recent years. New studies are addressing challenges related to NHANES data interpretation in health risk contexts. Conclusions This article demonstrates growing use of NHANES chemical biomarker data in studies that can impact risk assessments. Best practices for analysis and interpretation must be defined and adopted to allow the full potential of NHANES to be realized. Citation Sobus JR, DeWoskin RS, Tan YM, Pleil JD, Phillips MB, George BJ, Christensen K, Schreinemachers DM, Williams MA, Cohen Hubal EA, Edwards SW. 2015. Uses of NHANES biomarker data for chemical risk

Intercomparisons of airborne measurements of aerosol ionic chemical composition during TRACE-P and ACE-Asia

NASA Astrophysics Data System (ADS)

Ma, Y.; Weber, R. J.; Maxwell-Meier, K.; Orsini, D. A.; Lee, Y.-N.; Huebert, B. J.; Howell, S. G.; Bertram, T.; Talbot, R. W.; Dibb, J. E.; Scheuer, E.

2004-08-01

As part of the two field studies, Transport and Chemical Evolution over the Pacific (TRACE-P) and the Asian Aerosol Characterization Experiment (ACE-Asia), the inorganic chemical composition of tropospheric aerosols was measured over the western Pacific from three separate aircraft using various methods. Comparisons are made between the rapid online techniques of the particle into liquid sampler (PILS) for measurement of a suite of fine particle a mist chamber/ion chromatograph (MC/IC) measurement of fine sulfate, and the longer time-integrated filter and micro-orifice impactor (MOI) measurements. Comparisons between identical PILS on two separate aircraft flying in formation showed that they were highly correlated (e.g., sulfate r2 of 0.95), but were systematically different by 10 ± 5% (linear regression slope and 95% confidence bounds), and had generally higher concentrations on the aircraft with a low-turbulence inlet and shorter inlet-to-instrument transmission tubing. Comparisons of PILS and mist chamber measurements of fine sulfate on two different aircraft during formation flying had an r2 of 0.78 and a relative difference of 39% ± 5%. MOI ionic data integrated to the PILS upper measurement size of 1.3 μm sampling from separate inlets on the same aircraft showed that for sulfate, PILS and MOI were within 14% ± 6% and correlated with an r2 of 0.87. Most ionic compounds were within ±30%, which is in the range of differences reported between PILS and integrated samplers from ground-based comparisons. In many cases, direct intercomparison between the various instruments is difficult due to differences in upper-size detection limits. However, for this study, the results suggest that the fine particle mass composition measured from aircraft agree to within 30-40%.

Intercomparisons of Airborne Measurements of Aerosol Ionic Chemical Composition during TRACE-P and ACE-Asia

NASA Technical Reports Server (NTRS)

Ma, Y.; Weber, R. J.; Maxwell-Meier, K.; Orsini, D. A.; Lee, Y.-N.; Huebert, B. J.; Howell, S. G.; Bertram, T.; Talbot, R. W.

2003-01-01

As part of the two field studies, Transport and Chemical Evolution over the Pacific (TRACE-P), and the Asian Aerosol Characterization Experiment (ACEAsia), the inorganic chemical composition of tropospheric aerosols was measured over the western Pacific from three separate aircraft using various methods. Comparisons are made between the rapid online techniques of the Particle Into Liquid Sampler (PILS) for measurement of a suite of fine particle ionic compounds and a mist chamber (MC/IC) measurement of fine sulfate, and the longer time-integrated filter and multi-orifice impactor (MOI) measurements. Comparisons between identical PILS on two separate aircraft flying in formation showed that they were highly correlated (e.g., sulfate r(sup 2) of 0.95), but were systematically different by 10 +/- 5% (linear regression slope and 95% confidence bounds), and had generally higher concentrations on the aircraft with a low turbulence inlet and shorter inlet-to-instrument transmission tubing. Comparisons of PILS and mist chamber measurements of fine sulfate on two different aircraft during formation flying had an 3 of 0.78 and a relative difference of 39% +/- 5%. MOI ionic data integrated to the PILS upper measurement size of 1.3 pm sampling from separate inlets on the same aircraft showed that for sulfate, PILS and MOI were within 14% +/- 6% and correlated with an r(sup 2) of 0.87. Most ionic compounds were within f 30%, which is in the range of differences reported between PILS and integrated samplers from ground-based comparisons. In many cases, direct intercomparison between the various instruments is difficult due to differences in upper-size detection limits. However, for this study, the results suggest that the fine particle mass composition measured from aircraft agree to within 30-40%.

Collision-induced dissociative chemical cross-linking reagents and methodology: Applications to protein structural characterization using tandem mass spectrometry analysis.

PubMed

Soderblom, Erik J; Goshe, Michael B

2006-12-01

Chemical cross-linking combined with mass spectrometry is a viable approach to study the low-resolution structure of protein and protein complexes. However, unambiguous identification of the residues involved in a cross-link remains analytically challenging. To enable a more effective analysis across various MS platforms, we have developed a novel set of collision-induced dissociative cross-linking reagents and methodology for chemical cross-linking experiments using tandem mass spectrometry (CID-CXL-MS/MS). These reagents incorporate a single gas-phase cleavable bond within their linker region that can be selectively fragmented within the in-source region of the mass spectrometer, enabling independent MS/MS analysis for each peptide. Initial design concepts were characterized using a synthesized cross-linked peptide complex. Following verification and subsequent optimization of cross-linked peptide complex dissociation, our reagents were applied to homodimeric glutathione S-transferase and monomeric bovine serum albumin. Cross-linked residues identified by our CID-CXL-MS/MS method were in agreement with published crystal structures and previous cross-linking studies using conventional approaches. Common LC/MS/MS acquisition approaches such as data-dependent acquisition experiments using ion trap mass spectrometers and product ion spectral analysis using SEQUEST were shown to be compatible with our CID-CXL-MS/MS reagents, obviating the requirement for high resolution and high mass accuracy measurements to identify both intra- and interpeptide cross-links.

Analysis of air-, moisture- and solvent-sensitive chemical compounds by mass spectrometry using an inert atmospheric pressure solids analysis probe.

PubMed

Mosely, Jackie A; Stokes, Peter; Parker, David; Dyer, Philip W; Messinis, Antonis M

2018-02-01

A novel method has been developed that enables chemical compounds to be transferred from an inert atmosphere glove box and into the atmospheric pressure ion source of a mass spectrometer whilst retaining a controlled chemical environment. This innovative method is simple and cheap to implement on some commercially available mass spectrometers. We have termed this approach inert atmospheric pressure solids analysis probe ( iASAP) and demonstrate the benefit of this methodology for two air-/moisture-sensitive chemical compounds whose characterisation by mass spectrometry is now possible and easily achieved. The simplicity of the design means that moving between iASAP and standard ASAP is straightforward and quick, providing a highly flexible platform with rapid sample turnaround.

Reduction and Uncertainty Analysis of Chemical Mechanisms Based on Local and Global Sensitivities

NASA Astrophysics Data System (ADS)

Esposito, Gaetano

Numerical simulations of critical reacting flow phenomena in hypersonic propulsion devices require accurate representation of finite-rate chemical kinetics. The chemical kinetic models available for hydrocarbon fuel combustion are rather large, involving hundreds of species and thousands of reactions. As a consequence, they cannot be used in multi-dimensional computational fluid dynamic calculations in the foreseeable future due to the prohibitive computational cost. In addition to the computational difficulties, it is also known that some fundamental chemical kinetic parameters of detailed models have significant level of uncertainty due to limited experimental data available and to poor understanding of interactions among kinetic parameters. In the present investigation, local and global sensitivity analysis techniques are employed to develop a systematic approach of reducing and analyzing detailed chemical kinetic models. Unlike previous studies in which skeletal model reduction was based on the separate analysis of simple cases, in this work a novel strategy based on Principal Component Analysis of local sensitivity values is presented. This new approach is capable of simultaneously taking into account all the relevant canonical combustion configurations over different composition, temperature and pressure conditions. Moreover, the procedure developed in this work represents the first documented inclusion of non-premixed extinction phenomena, which is of great relevance in hypersonic combustors, in an automated reduction algorithm. The application of the skeletal reduction to a detailed kinetic model consisting of 111 species in 784 reactions is demonstrated. The resulting reduced skeletal model of 37--38 species showed that the global ignition/propagation/extinction phenomena of ethylene-air mixtures can be predicted within an accuracy of 2% of the full detailed model. The problems of both understanding non-linear interactions between kinetic parameters and

Chemical Stockpile Disposal Program. Risk Analysis of the Disposal of Chemical Munitions at Regional or National Sites.

DTIC Science & Technology

1987-08-01

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Some aspects of mathematical and chemical modeling of complex chemical processes

NASA Technical Reports Server (NTRS)

Nemes, I.; Botar, L.; Danoczy, E.; Vidoczy, T.; Gal, D.

1983-01-01

Some theoretical questions involved in the mathematical modeling of the kinetics of complex chemical process are discussed. The analysis is carried out for the homogeneous oxidation of ethylbenzene in the liquid phase. Particular attention is given to the determination of the general characteristics of chemical systems from an analysis of mathematical models developed on the basis of linear algebra.

FREE INVENTORY PLATFORM MANAGES CHEMICAL RISKS, ADDRESSES CHEMICAL ACCOUNTABILITY, AND MEASURES COST-EFFECTIVENESS

PubMed Central

D’Souza, Malcolm J.; Roeske, Kristopher P.; Neff, Lily S.

2017-01-01

To develop best practices for laboratory safety and for chemical product and supplies management accountability, the freely-available online platform, Quartzy, was integrated within an interdisciplinary science department at a small Mid-Atlantic liberal-arts college. This was done to ensure the accuracy of purchase records, the appropriate use of storage and handling protocols, and for a continually updated chemical inventory system. Quartzy also facilitated the digital tracking and dispersal of the College’s hazardous waste inventory. Since the implementation of the Quartzy platform, the science department achieved significant cost-savings during the procurement of laboratory supplies and equipment, and it developed a sense of ownership towards the common goal of lowering the College's environmental impact as it relates to its managing of laboratory-generated hazardous wastes. PMID:29251298

Shift in Chemical Potential of Superconducting Bi2212 Measured by Ultrafast Photoemission Spectroscopy

NASA Astrophysics Data System (ADS)

Miller, Tristan; Smallwood, Chris; Zhang, Wentao; Eisaki, Hiroshi; Lee, Dung-Hai; Lanzara, Alessandra

2015-03-01

Time- and Angle-resolved photoemission spectroscopy (tr-ARPES) has been used to directly measure the dynamics of many different properties of high-temperature superconductors, including the quasiparticle relaxation, cooper pair recombination, and many-body interactions. There have also been several intriguing results on several materials showing how laser pulses can manipulate their chemical potential on ultrafast timescales, and it's been suggested that these effects could find applications in optoelectronic devices. Studies on GaAs have also found that laser pulses may induce a surface voltage effect. Here, we extend these studies for the first time to a Bi2212 sample in the superconducting state, and disentangle the shift in chemical potential from surface voltage effects. This work was supported by Berkeley Lab's program on Quantum Materials, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under Contract No. DE-AC02-05CH11231.

Changes in chemical composition of bone matrix in ovariectomized (OVX) rats detected by Raman spectroscopy and multivariate analysis

NASA Astrophysics Data System (ADS)

Oshima, Yusuke; Iimura, Tadahiro; Saitou, Takashi; Imamura, Takeshi

2015-02-01

Osteoporosis is a major bone disease that connotes the risk of fragility fractures resulting from alterations to bone quantity and/or quality to mechanical competence. Bone strength arises from both bone quantity and quality. Assessment of bone quality and bone quantity is important for prediction of fracture risk. In spite of the two factors contribute to maintain the bone strength, only one factor, bone mineral density is used to determine the bone strength in the current diagnosis of osteoporosis. On the other hand, there is no practical method to measure chemical composition of bone tissue including hydroxyapatite and collagen non-invasively. Raman spectroscopy is a powerful technique to analyze chemical composition and material properties of bone matrix non-invasively. Here we demonstrated Raman spectroscopic analysis of the bone matrix in osteoporosis model rat. Ovariectomized (OVX) rat was made and the decalcified sections of tibias were analyzed by a Raman microscope. In the results, Raman bands of typical collagen appeared in the obtained spectra. Although the typical mineral bands at 960 cm-1 (Phosphate) was absent due to decalcified processing, we found that Raman peak intensities of amide I and C-C stretching bands were significantly different between OVX and sham-operated specimens. These differences on the Raman spectra were statistically compared by multivariate analyses, principal component analysis (PCA) and liner discrimination analysis (LDA). Our analyses suggest that amide I and C-C stretching bands can be related to stability of bone matrix which reflects bone quality.

Spectroscopic analysis of cinnamic acid using quantum chemical calculations

NASA Astrophysics Data System (ADS)

Vinod, K. S.; Periandy, S.; Govindarajan, M.

2015-02-01

In this present study, FT-IR, FT-Raman, 13C NMR and 1H NMR spectra for cinnamic acid have been recorded for the vibrational and spectroscopic analysis. The observed fundamental frequencies (IR and Raman) were assigned according to their distinctiveness region. The computed frequencies and optimized parameters have been calculated by using HF and DFT (B3LYP) methods and the corresponding results are tabulated. On the basis of the comparison between computed and experimental results assignments of the fundamental vibrational modes are examined. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by HF and DFT methods. The alternation of the vibration pattern of the pedestal molecule related to the substitutions was analyzed. The 13C and 1H NMR spectra have been recorded and the chemical shifts have been calculated using the gauge independent atomic orbital (GIAO) method. The Mulliken charges, UV spectral analysis and HOMO-LUMO analysis of have been calculated and reported. The molecular electrostatic potential (MEP) was constructed.

The Gas-Absorption/Chemical-Reaction Method for Measuring Air-Water Interfacial Area in Natural Porous Media

NASA Astrophysics Data System (ADS)

Lyu, Ying; Brusseau, Mark L.; El Ouni, Asma; Araujo, Juliana B.; Su, Xiaosi

2017-11-01

The gas-absorption/chemical-reaction (GACR) method used in chemical engineering to quantify gas-liquid interfacial area in reactor systems is adapted for the first time to measure the effective air-water interfacial area of natural porous media. Experiments were conducted with the GACR method, and two standard methods (X-ray microtomographic imaging and interfacial partitioning tracer tests) for comparison, using model glass beads and a natural sand. The results of a series of experiments conducted under identical conditions demonstrated that the GACR method exhibited excellent repeatability for measurement of interfacial area (Aia). Coefficients of variation for Aia were 3.5% for the glass beads and 11% for the sand. Extrapolated maximum interfacial areas (Am) obtained with the GACR method were statistically identical to independent measures of the specific solid surface areas of the media. For example, the Am for the glass beads is 29 (±1) cm-1, compared to 32 (±3), 30 (±2), and 31 (±2) cm-1 determined from geometric calculation, N2/BET measurement, and microtomographic measurement, respectively. This indicates that the method produced accurate measures of interfacial area. Interfacial areas determined with the GACR method were similar to those obtained with the standard methods. For example, Aias of 47 and 44 cm-1 were measured with the GACR and XMT methods, respectively, for the sand at a water saturation of 0.57. The results of the study indicate that the GACR method is a viable alternative for measuring air-water interfacial areas. The method is relatively quick, inexpensive, and requires no specialized instrumentation compared to the standard methods.

Evaluation of C60 secondary ion mass spectrometry for the chemical analysis and imaging of fingerprints.

PubMed

Sisco, Edward; Demoranville, Leonard T; Gillen, Greg

2013-09-10

The feasibility of using C60(+) cluster primary ion bombardment secondary ion mass spectrometry (C60(+) SIMS) for the analysis of the chemical composition of fingerprints is evaluated. It was found that C60(+) SIMS could be used to detect and image the spatial localization of a number of sebaceous and eccrine components in fingerprints. These analyses were also found to not be hindered by the use of common latent print powder development techniques. Finally, the ability to monitor the depth distribution of fingerprint constituents was found to be possible - a capability which has not been shown using other chemical imaging techniques. This paper illustrates a number of strengths and potential weaknesses of C60(+) SIMS as an additional or complimentary technique for the chemical analysis of fingerprints. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Correction to: Top Down Tandem Mass Spectrometric Analysis of a Chemically Modified Rough-Type Lipopolysaccharide Vaccine Candidate

NASA Astrophysics Data System (ADS)

Oyler, Benjamin L.; Khan, Mohd M.; Smith, Donald F.; Harberts, Erin M.; Kilgour, David P. A.; Ernst, Robert K.; Cross, Alan S.; Goodlett, David R.

2018-04-01

In the preceding article "Top Down Tandem Mass Spectrometric Analysis of a Chemically Modified Rough-Type Lipopolysaccharide Vaccine Candidate" by Oyler et al., an error in the J5 E. coli LPS chemical structure (Figs. 2 and 4) was introduced and propagated into the final revision.

Isolation and chemical analysis of nanoparticles from English ivy (Hedera helix L.)

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

Lenaghan, Scott C; Burris, Jason N; Chourey, Karuna

It was discovered that adventitious roots of English ivy secreted a high strength adhesive containing uniform nanoparticles. These nanoparticles were hypothesized to be organic in nature. Subsequent studies have revealed several applications for these nanoparticles, but their chemical composition remained unknown. Here, we describe an isolation procedure to obtain gram quantities of ivy nanoparticles from adventitious roots. In addition, ultraviolet/visible (UV/Vis) spectroscopy, inductively coupled plasma mass spectrometry (ICP-MS), elemental analysis, fourier transform infrared spectroscopy (FTIR), and gel electrophoresis were conducted to identify the chemical nature of the ivy nanoparticles. Based on this comprehensive analysis, we conclude that the ivy nanoparticlesmore » are proteinaceous consisting of 51.77% carbon, 4.72% nitrogen, and 0.32% sulfur, without the presence of metals. Liquid chromatography tandem mass spectrometry (LC-MS/MS) based protein profiling revealed the presence of at least 6 proteins, including heat shock proteins and other large molecular weight proteins. Identification of these protein candidates will facilitate gene discovery and bioproduction of ivy nanoparticles.« less

Methods of chemical and phase composition analysis of gallstones

NASA Astrophysics Data System (ADS)

Suvorova, E. I.; Pantushev, V. V.; Voloshin, A. E.

2017-11-01

This review presents the instrumental methods used for chemical and phase composition investigation of gallstones. A great body of data has been collected in the literature on the presence of elements and their concentrations, obtained by fluorescence microscopy, X-ray fluorescence spectroscopy, neutron activation analysis, proton (particle) induced X-ray emission, atomic absorption spectroscopy, high-resolution gamma-ray spectrometry, electron paramagnetic resonance. Structural methods—powder X-ray diffraction, infrared spectroscopy, Raman spectroscopy—provide information about organic and inorganic phases in gallstones. Stone morphology was studied at the macrolevel with optical microscopy. Results obtained by analytical scanning and transmission electron microscopy with X-ray energy dispersive spectrometry are discussed. The chemical composition and structure of gallstones determine the strategy of removing stone from the body and treatment of patients: surgery or dissolution in the body. Therefore one chapter of the review describes the potential of dissolution methods. Early diagnosis and appropriate treatment of the disease depend on the development of clinical methods for in vivo investigation, which gave grounds to present the main characteristics and potential of ultrasonography (ultrasound scanning), magnetic resonance imaging, and X-ray computed tomography.

Supersonic Flow of Chemically Reacting Gas-Particle Mixtures. Volume 2: RAMP - A Computer Code for Analysis of Chemically Reacting Gas-Particle Flows

NASA Technical Reports Server (NTRS)

Penny, M. M.; Smith, S. D.; Anderson, P. G.; Sulyma, P. R.; Pearson, M. L.

1976-01-01

A computer program written in conjunction with the numerical solution of the flow of chemically reacting gas-particle mixtures was documented. The solution to the set of governing equations was obtained by utilizing the method of characteristics. The equations cast in characteristic form were shown to be formally the same for ideal, frozen, chemical equilibrium and chemical non-equilibrium reacting gas mixtures. The characteristic directions for the gas-particle system are found to be the conventional gas Mach lines, the gas streamlines and the particle streamlines. The basic mesh construction for the flow solution is along streamlines and normals to the streamlines for axisymmetric or two-dimensional flow. The analysis gives detailed information of the supersonic flow and provides for a continuous solution of the nozzle and exhaust plume flow fields. Boundary conditions for the flow solution are either the nozzle wall or the exhaust plume boundary.

[Nursing workers' perceptions regarding the handling of hazardous chemical waste].

PubMed

Costa, Taiza Florêncio; Felli, Vanda Elisa Andres; Baptista, Patrícia Campos Pavan

2012-12-01

The objectives of this study were to identify the perceptions of nursing workers regarding the handling of hazardous chemical waste at the University of São Paulo University Hospital (HU-USP), and develop a proposal to improve safety measures. This study used a qualitative approach and a convenience sample consisting of eighteen nursing workers. Data collection was performed through focal groups. Thematic analysis revealed four categories that gave evidence of training deficiencies in terms of the stages of handling waste. Difficulties that emerged included a lack of knowledge regarding exposure and its impact, the utilization of personal protective equipment versus collective protection, and suggestions regarding measures to be taken by the institution and workers for the safe handling of hazardous chemical waste. The present data allowed for recommending proposals regarding the safe management of hazardous chemical waste by the nursing staff.

Portfolio analysis of layered security measures.

PubMed

Chatterjee, Samrat; Hora, Stephen C; Rosoff, Heather

2015-03-01

Layered defenses are necessary for protecting the public from terrorist attacks. Designing a system of such defensive measures requires consideration of the interaction of these countermeasures. In this article, we present an analysis of a layered security system within the lower Manhattan area. It shows how portfolios of security measures can be evaluated through portfolio decision analysis. Consideration is given to the total benefits and costs of the system. Portfolio diagrams are created that help communicate alternatives among stakeholders who have differing views on the tradeoffs between security and economic activity. © 2014 Society for Risk Analysis.

Linking performance benchmarking of refinery process chemicals to refinery key performance indicators

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

Cook, J.M.; Nieman, L.D.

In 1977 Solomon Associates, Inc. issued its first study of refining in the US entitled, Comparative Performance Analysis for Fuel Product Refineries, most commonly referred to as the Solomon Study, or the Fuels Study. In late 1993, both the Water and Waste Water Management, and Petroleum Divisions of Nalco Chemical Company came to the same conclusion; that they must have a better understanding of the Solomon Study process, and have some input to this system of measurement. The authors first approached Solomon Associates with the idea that a specific study should be done of specialty chemicals used in the refinery.more » They felt that this would result in two studies, one for water treatment applications, and one for process. The water treatment study came first, and was completed in 1993 with the United States Petroleum Refineries Water Treatment Performance Analysis for Operating Year 1993. The process study, entitled United States Petroleum Refinery Process Treatment Performance Analysis for Operating Years 1994--95 will be issued in the 2nd quarter of this year by Nalco/Exxon Energy Chemicals, L.P, which includes the combined resources of the former Petroleum Division of Nalco Chemical Company (including the petroleum related portions of most of its overseas companies), and the petroleum related specialty chemical operations of Exxon Chemical on a global basis. What follows is a recap of the process study focus, some examples of output, and comment on both the linkage to key refinery operating indicators, as well as the perception of the effect of such measurement on the supplier relationship of the future.« less

129 Xe chemical shift in human blood and pulmonary blood oxygenation measurement in humans using hyperpolarized 129 Xe NMR.

PubMed

Norquay, Graham; Leung, General; Stewart, Neil J; Wolber, Jan; Wild, Jim M

2017-04-01

To evaluate the dependency of the 129 Xe-red blood cell (RBC) chemical shift on blood oxygenation, and to use this relation for noninvasive measurement of pulmonary blood oxygenation in vivo with hyperpolarized 129 Xe NMR. Hyperpolarized 129 Xe was equilibrated with blood samples of varying oxygenation in vitro, and NMR was performed at 1.5 T and 3 T. Dynamic in vivo NMR during breath hold apnea was performed at 3 T on two healthy volunteers following inhalation of hyperpolarized 129 Xe. The 129 Xe chemical shift in RBCs was found to increase nonlinearly with blood oxygenation at 1.5 T and 3 T. During breath hold apnea, the 129 Xe chemical shift in RBCs exhibited a periodic time modulation and showed a net decrease in chemical shift of ∼1 ppm over a 35 s breath hold, corresponding to a decrease of 7-10 % in RBC oxygenation. The 129 Xe-RBC signal amplitude showed a modulation with the same frequency as the 129 Xe-RBC chemical shift. The feasibility of using the 129 Xe-RBC chemical shift to measure pulmonary blood oxygenation in vivo has been demonstrated. Correlation between 129 Xe-RBC signal and 129 Xe-RBC chemical shift modulations in the lung warrants further investigation, with the aim to better quantify temporal blood oxygenation changes in the cardiopulmonary vascular circuit. Magn Reson Med 77:1399-1408, 2017. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine.

CONTRIBUTIONS OF CHEMICAL AND DIFFUSIVE EXCHANGE TO T1ρ DISPERSION

PubMed Central

Cobb, Jared Guthrie; Xie, Jingping; Gore, John C.

2012-01-01

Variations in local magnetic susceptibility may induce magnetic field gradients that affect the signals acquired for MR imaging. Under appropriate diffusion conditions, such fields produce effects similar to slow chemical exchange. These effects may also be found in combination with other chemical exchange processes at multiple time scales. We investigate these effects with simulations and measurements to determine their contributions to rotating frame (R1ρ) relaxation in model systems. Simulations of diffusive and chemical exchange effects on R1ρ dispersion were performed using the Bloch equations. Additionally, R1ρ dispersion was measured in suspensions of Sephadex and latex beads with varying spin locking fields at 9.4T. A novel analysis method was used to iteratively fit for apparent chemical and diffusive exchange rates with a model by Chopra et al. Single- and double-inflection points in R1ρ dispersion profiles were observed, respectively, in simulations of slow diffusive exchange alone and when combined with rapid chemical exchange. These simulations were consistent with measurements of R1ρ in latex bead suspensions and small-diameter Sephadex beads that showed single- and double-inflection points, respectively. These observations, along with measurements following changes in temperature and pH, are consistent with the combined effects of slow diffusion and rapid −OH exchange processes. PMID:22791589