Experimental Study of the Roles of Mechanical and Hydrologic Properties in the Initiation of Natural Hydraulic Fractures

NASA Astrophysics Data System (ADS)

French, M. E.; Goodwin, L. B.; Boutt, D. F.; Lilydahl, H.

2008-12-01

Natural hydraulic fractures (NHFs) are inferred to form where pore fluid pressure exceeds the least compressive stress; i.e., where the hydraulic fracture criterion is met. Although it has been shown that mechanical heterogeneities serve as nuclei for NHFs, the relative roles of mechanical anisotropy and hydrologic properties in initiating NHFs in porous granular media have not been fully explored. We designed an experimental protocol that produces a pore fluid pressure high enough to exceed the hydraulic fracture criterion, allowing us to initiate NHFs in the laboratory. Initially, cylindrical samples 13 cm long and 5 cm in diameter are saturated, σ1 is radial, and σ3 is axial. By dropping the end load (σ3) and pore fluid pressure simultaneously at the end caps, we produce a large pore fluid pressure gradient parallel to the long axis of the sample. This allows us to meet the hydraulic fracture criterion without separating the sample from its end caps. The time over which the pore fluid remains elevated is a function of hydraulic diffusivity. An initial test with a low diffusivity sandstone produced NHFs parallel to bedding laminae that were optimally oriented for failure. To evaluate the relative importance of mechanical heterogeneities such as bedding versus hydraulic properties, we are currently investigating variably cemented St. Peter sandstone. This quartz arenite exhibits a wide range of primary structures, from well developed bedding laminae to locally massive sandstone. Diagenesis has locally accentuated these structures, causing degree of cementation to vary with bedding, and the sandstone locally exhibits concretions that form elliptical rather than tabular heterogeneities. Bulk permeability varies from k=10-12 m2 to k=10-15 m2 and porosity varies from 5% to 28% in this suite of samples. Variations in a single sample are smaller, with permeability varying no more than an order of magnitude within a single core. Air minipermeameter and tracer tests document this variability at the cm scale. Experiments will be performed with σ3 and the pore pressure gradient both perpendicular and parallel to sub-cm scale bedding. The results of these tests will be compared to those of structurally homogeneous samples and samples with elliptical heterogeneities.

Assessing Microbial Activity in Marcellus Shale Hydraulic Fracturing Fluids

NASA Astrophysics Data System (ADS)

Wishart, J. R.; Morono, Y.; Itoh, M.; Ijiri, A.; Hoshino, T.; Inagaki, F.; Verba, C.; Torres, M. E.; Colwell, F. S.

2014-12-01

Hydraulic fracturing (HF) produces millions of gallons of waste fluid which contains a microbial community adapted to harsh conditions such as high temperatures, high salinities and the presence of heavy metals and radionuclides. Here we present evidence for microbial activity in HF production fluids. Fluids collected from a Marcellus shale HF well were supplemented with 13C-labeled carbon sources and 15N-labeled ammonium at 25°C under aerobic or anaerobic conditions. Samples were analyzed for 13C and 15N incorporation at sub-micrometer scale by ion imaging with the JAMSTEC NanoSIMS to determine percent carbon and nitrogen assimilation in individual cells. Headspace CO2 and CH4 were analyzed for 13C enrichment using irm-GC/MS. At 32 days incubation carbon assimilation was observed in samples containing 1 mM 13C-labeled glucose under aerobic and anaerobic conditions with a maximum of 10.4 and 6.5% total carbon, respectively. Nitrogen assimilation of 15N ammonium observed in these samples were 0.3 and 0.8% of total nitrogen, respectively. Head space gas analysis showed 13C enrichment in CH4 in anaerobic samples incubated with 1mM 13C-labeled bicarbonate (2227 ‰) or methanol (98943 ‰). Lesser 13C enrichment of CO2 was observed in anaerobic samples containing 1 mM 13C-labeled acetate (13.7 ‰), methanol (29.9 ‰) or glucose (85.4 ‰). These results indicate metabolic activity and diversity in microbial communities present in HF flowback fluids. The assimilation of 13C-labeled glucose demonstrates the production of biomass, a critical part of cell replication. The production of 13CO2 and 13CH4 demonstrate microbial metabolism in the forms of respiration and methanogenesis, respectively. Methanogenesis additionally indicates the presence of an active archaeal community. This research shows that HF production fluid chemistry does not entirely inhibit microbial activity or growth and encourages further research regarding biogeochemical processes occurring in Marcellus shale HF wells. Biogeochemical activity may impact the efficacy of HF and natural gas production as well as the chemistry of produced fluids which have become an environmental and public health concern.

Predicting fetal lung maturity by visual assessment of amniotic fluid turbidity: comparison with fluorescence polarization assay.

PubMed

Adair, C D; Sanchez-Ramos, L; McDyer, D L; Gaudier, F L; Del Valle, G O; Delke, I

1995-10-01

We prospectively studied 159 patients having clinically indicated amniocentesis. Amniotic fluid (3 to 5 mL) was placed in a nonheparinized glass tube. This sample was then classified as turbid (indicating maturity) or clear (indicating immaturity) on the basis of a single examiner's ability to read newspaper print through the glass tube. These results were then compared with fluorescence polarization values for the same sample. A value of 70 mg/g was considered positive evidence of fetal lung maturity. By study criteria, 62 samples (39%) indicated immaturity and 97 (61%) indicated maturity. Turbidity correctly identified 89 samples that produced fluorescence polarization values of at least 70 mg/g. Turbidity as a predictor of fetal lung maturity when compared with fluorescence polarization assay has a 91% positive and 87% negative predictive value. Visual inspection of amniotic fluid may be of value in areas where sophisticated methods are unavailable.

Helium measurements of pore fluids obtained from the San Andreas Fault Observatory at Depth (SAFOD, USA) drill cores

NASA Astrophysics Data System (ADS)

Ali, S.; Stute, M.; Torgersen, T.; Winckler, G.; Kennedy, B. M.

2011-02-01

4He accumulated in fluids is a well established geochemical tracer used to study crustal fluid dynamics. Direct fluid samples are not always collectable; therefore, a method to extract rare gases from matrix fluids of whole rocks by diffusion has been adapted. Helium was measured on matrix fluids extracted from sandstones and mudstones recovered during the San Andreas Fault Observatory at Depth (SAFOD) drilling in California, USA. Samples were typically collected as subcores or from drillcore fragments. Helium concentration and isotope ratios were measured 4-6 times on each sample, and indicate a bulk 4He diffusion coefficient of 3.5 ± 1.3 × 10-8 cm2 s-1 at 21°C, compared to previously published diffusion coefficients of 1.2 × 10-18 cm2 s-1 (21°C) to 3.0 × 10-15 cm2 s-1 (150°C) in the sands and clays. Correcting the diffusion coefficient of 4Hewater for matrix porosity (˜3%) and tortuosity (˜6-13) produces effective diffusion coefficients of 1 × 10-8 cm2 s-1 (21°C) and 1 × 10-7 (120°C), effectively isolating pore fluid 4He from the 4He contained in the rock matrix. Model calculations indicate that <6% of helium initially dissolved in pore fluids was lost during the sampling process. Complete and quantitative extraction of the pore fluids provide minimum in situ porosity values for sandstones 2.8 ± 0.4% (SD, n = 4) and mudstones 3.1 ± 0.8% (SD, n = 4).

Characterizing the variability in chemical composition of flowback and produced waters - results from lab and field studies

NASA Astrophysics Data System (ADS)

Vieth-Hillebrand, Andrea; Wilke, Franziska D. H.; Schmid, Franziska E.; Zhu, Yaling; Lipińska, Olga; Konieczyńska, Monika

2017-04-01

The huge volumes and unknown composition of flowback and produced waters cause major public concerns about the environmental and social compatibility of hydraulic fracturing and the exploitation of gas from unconventional reservoirs. Flowback and produced waters contain not only residues of fracking additives but also chemical species that are dissolved from the target shales themselves. Shales are a heterogeneous mixture of minerals, organic matter, and formation water and little is actually understood about the fluid-rock interactions occurring during hydraulic fracturing of the shales and their effects on the chemical composition of flowback and produced water. To overcome this knowledge gap, interactions of different shales with different artificial stimulation fluids were studied in lab experiments under ambient and elevated temperature and pressure conditions. These lab experiments showed clearly that fluid-rock interactions change the chemical composition of the initial stimulation fluid and that geochemistry of the fractured shale is relevant for understanding flowback water composition. In addition, flowback water samples were taken after hydraulic fracturing of one horizontal well in Pomeranian region, Poland and investigated for their chemical composition. With this presentation, results from lab and field studies will be presented and compared to decipher possible controls on chemical compositions of flowback and produced water.

Oxygen and Hydrogen Isotope Values for Unaltered and Hydrothermally Altered Samples from the Cretaceous Linga Plutonic Complex of the Peruvian Coastal Batholith near Ica.

NASA Astrophysics Data System (ADS)

Gonzalez, L. U.; Holk, G. J.; Clausen, B. L.; Poma Porras, O. A.

2015-12-01

A portion of the Peruvian Coastal Batholith near Ica, Peru is being studied using stable isotopes to determine the source of hydrothermal fluids that caused propylitic, phyllic, and potassic alteration in the mineralized Linga plutonic complex. Sources of hydrothermal fluids and water/rock ratios are estimated to understand the role of such fluids in alteration during cooling. A set of 64 mineral analysis from 18 igneous samples, 7 unaltered and 11 altered, were analyzed for D/H and 18O/16O isotopes. The δ18O values for whole rocks with no apparent alteration vary from +6.8‰ to +7.9‰, with sets of δ18O mineral values indicating isotopic equilibrium at closure temperatures from 571°C to 651°C, and no interaction with meteoric water. This conclusion is bolstered by hornblende (-87‰ to -64‰) and biotite (-81‰ to -74‰) δD values Most δ18O values for samples with hydrothermal alteration suggest that alteration results from magmatic fluids; however, several analyses indicate interaction with other fluids. The high δ18O values for plagioclase (+9.3‰) and hornblende (+6.3‰) from a metamorphic aureole in volcanic host rock near a plutonic intrusion may be due to interaction with metamorphic or low temperature magmatic fluids. Plagioclase (+2.6‰) and biotite (+0.1‰) δ18O values in a sample from the Jurassic volcanic envelope indicate a significant effect from meteoric-hydrothermal fluids. An altered monzonite yielded δ18O values for quartz (+5.5‰), K-spar (+5.6‰), and magnetite (+0.4‰), also suggesting interaction with meteoric fluids. A diorite from an area with strong epidotization produced an epidote δD value of -25.8‰ and a monzonite from a highly veined area has an epidote δD value of -36.1‰ suggesting interaction with sea water. This new data indicate that the Linga complex was primarily influenced by magmatic hydrothermal fluids, but metamorphic, meteoric, and sea water may have had some influence in producing alteration assemblages and in cooling the magmatic complex.

Metagenomic and PCR-Based Diversity Surveys of [FeFe]-Hydrogenases Combined with Isolation of Alkaliphilic Hydrogen-Producing Bacteria from the Serpentinite-Hosted Prony Hydrothermal Field, New Caledonia.

PubMed

Mei, Nan; Postec, Anne; Monnin, Christophe; Pelletier, Bernard; Payri, Claude E; Ménez, Bénédicte; Frouin, Eléonore; Ollivier, Bernard; Erauso, Gaël; Quéméneur, Marianne

2016-01-01

High amounts of hydrogen are emitted in the serpentinite-hosted hydrothermal field of the Prony Bay (PHF, New Caledonia), where high-pH (~11), low-temperature (< 40°C), and low-salinity fluids are discharged in both intertidal and shallow submarine environments. In this study, we investigated the diversity and distribution of potentially hydrogen-producing bacteria in Prony hyperalkaline springs by using metagenomic analyses and different PCR-amplified DNA sequencing methods. The retrieved sequences of hydA genes, encoding the catalytic subunit of [FeFe]-hydrogenases and, used as a molecular marker of hydrogen-producing bacteria, were mainly related to those of Firmicutes and clustered into two distinct groups depending on sampling locations. Intertidal samples were dominated by new hydA sequences related to uncultured Firmicutes retrieved from paddy soils, while submarine samples were dominated by diverse hydA sequences affiliated with anaerobic and/or thermophilic submarine Firmicutes pertaining to the orders Thermoanaerobacterales or Clostridiales. The novelty and diversity of these [FeFe]-hydrogenases may reflect the unique environmental conditions prevailing in the PHF (i.e., high-pH, low-salt, mesothermic fluids). In addition, novel alkaliphilic hydrogen-producing Firmicutes (Clostridiales and Bacillales) were successfully isolated from both intertidal and submarine PHF chimney samples. Both molecular and cultivation-based data demonstrated the ability of Firmicutes originating from serpentinite-hosted environments to produce hydrogen by fermentation, potentially contributing to the molecular hydrogen balance in situ.

A colorimeter for measurement of picomole quantities of urea.

PubMed

Vurek, G G; Knepper, M A

1982-04-01

We described a new colorimeter for the measurement of picomole quantities of urea in nanoliter volume fluid samples. The diacetyl monoxime reaction was used to produce a colored product from urea. The method is capable of resolving differences of 10 pmoles between samples containing 0 to 225 pmoles.

Application of Oral Fluid Assays in Support of Mumps, Rubella and Varicella Control Programs.

PubMed

Maple, Peter A C

2015-12-09

Detection of specific viral antibody or nucleic acid produced by infection or immunization, using oral fluid samples, offers increased potential for wider population uptake compared to blood sampling. This methodology is well established for the control of HIV and measles infections, but can also be applied to the control of other vaccine preventable infections, and this review describes the application of oral fluid assays in support of mumps, rubella and varicella national immunization programs. In England and Wales individuals with suspected mumps or rubella, based on clinical presentation, can have an oral fluid swab sample taken for case confirmation. Universal varicella immunization of children has led to a drastic reduction of chickenpox in those countries where it is used; however, in England and Wales such a policy has not been instigated. Consequently, in England and Wales most children have had chickenpox by age 10 years; however, small, but significant, numbers of adults remain susceptible. Targeted varicella zoster virus (VZV) immunization of susceptible adolescents offers the potential to reduce the pool of susceptible adults and oral fluid determination of VZV immunity in adolescents is a potential means of identifying susceptible individuals in need of VZV vaccination. The main application of oral fluid testing is in those circumstances where blood sampling is deemed not necessary, or is undesirable, and when the documented sensitivity and specificity of the oral fluid assay methodology to be used is considered sufficient for the purpose intended.

Electrohydrodynamic distortion of sample streams in continuous flow electrophoresis

NASA Technical Reports Server (NTRS)

Rhodes, Percy H.; Snyder, Robert S.; Roberts, Glyn O.

1989-01-01

Continuous flow electrophoresis experiments were carried out, using an electrolyte and a sample both made of aqueous solutions of phosphate buffer (with polystyrene latex added for visibility), to investigate causes of the sample spreading in this procedure. It is shown theoretically that an electric field perpendicular to a circular filament of conducting fluid surrounded by a fluid of different conductivity produces an electrohydrodynamic flow, which distorts the filament into an ellipse. Experimental results were found to be fully consistent with theretical predictions. It was found that the rate of distortion of the sample stream into a ribbon was proportional to the square of the applied voltage gradient. Furthermore, the orientation of the ribbon depends on the ratios of dielectric constant and electrical conductivity between the buffer and the sample.

Automatic instrument for chemical processing to detect microorganism in biological samples by measuring light reactions

NASA Technical Reports Server (NTRS)

Kelbaugh, B. N.; Picciolo, G. L.; Chappelle, E. W.; Colburn, M. E. (Inventor)

1973-01-01

An automated apparatus is reported for sequentially assaying urine samples for the presence of bacterial adenosine triphosphate (ATP) that comprises a rotary table which carries a plurality of sample containing vials and automatically dispenses fluid reagents into the vials preparatory to injecting a light producing luciferase-luciferin mixture into the samples. The device automatically measures the light produced in each urine sample by a bioluminescence reaction of the free bacterial adenosine triphosphate with the luciferase-luciferin mixture. The light measured is proportional to the concentration of bacterial adenosine triphosphate which, in turn, is proportional to the number of bacteria present in the respective urine sample.

Microfluidic ultrasonic particle separators with engineered node locations and geometries

DOEpatents

Rose, Klint A.; Fisher, Karl A.; Wajda, Douglas A.; Mariella, Jr., Raymond P.; Bailey, Christopher; Dehlinger, Dietrich; Shusteff, Maxim; Jung, Byoungsok; Ness, Kevin D.

2016-04-26

An ultrasonic microfluidic system includes a separation channel for conveying a sample fluid containing small particles and large particles, flowing substantially parallel, adjacent to a recovery fluid, with which it is in contact. An acoustic transducer produces an ultrasound standing wave, that generates a pressure field having at least one node of minimum pressure amplitude. An acoustic extension structure is located proximate to said separation channel for positioning said acoustic node off center in said acoustic area and concentrating the large particles in said recovery fluid stream.

Microfluidic ultrasonic particle separators with engineered node locations and geometries

DOEpatents

Rose, Klint A; Fisher, Karl A; Wajda, Douglas A; Mariella, Jr., Raymond P; Bailey, Christopher; Dehlinger, Dietrich; Shusteff, Maxim; Jung, Byoungsok; Ness, Kevin D

2015-03-31

An ultrasonic microfluidic system includes a separation channel for conveying a sample fluid containing small particles and large particles, flowing substantially parallel, adjacent to a recovery fluid, with which it is in contact. An acoustic transducer produces an ultrasound standing wave, that generates a pressure field having at least one node of minimum, pressure amplitude. An acoustic extension structure is located proximate to said separation channel for positioning said acoustic node off center in said acoustic area and concentrating the large particles in said recovery fluid stream.

Microfluidic ultrasonic particle separators with engineered node locations and geometries

DOEpatents

Rose, Klint A; Fisher, Karl A; Wajda, Douglas A; Mariella, Jr., Raymond P; Bailey, Christoppher; Dehlinger, Dietrich; Shusteff, Maxim; Jung, Byoungsok; Ness, Kevin D

2014-05-20

An ultrasonic microfluidic system includes a separation channel for conveying a sample fluid containing small particles and large particles, flowing substantially parallel, adjacent to a recovery fluid, with which it is in contact. An acoustic transducer produces an ultrasound standing wave, that generates a pressure field having at least one node of minimum pressure amplitude. An acoustic extension structure is located proximate to said separation channel for positioning said acoustic node off center in said acoustic area and concentrating the large particles in said recovery fluid stream.

Analytical and toxicological evaluation of flavor chemicals in electronic cigarette refill fluids.

PubMed

Behar, Rachel Z; Luo, Wentai; McWhirter, Kevin J; Pankow, James F; Talbot, Prue

2018-05-29

Thousands of electronic cigarette refill fluids are commercially available. The concentrations of nicotine and the solvents, but not the flavor chemicals, are often disclosed on product labels. The purpose of this study was to identify and quantify flavor chemicals in 39 commercial refill fluids that were previously evaluated for toxicity. Twelve flavor chemicals were identified with concentrations ≥1 mg/ml: cinnamaldehyde, menthol, benzyl alcohol, vanillin, eugenol, p-anisaldehyde, ethyl cinnamate, maltol, ethyl maltol, triacetin, benzaldehyde, and menthone. Transfer of these flavor chemicals into aerosols made at 3V and 5V was efficient (mean transfer = 98%). We produced lab-made refill fluids containing authentic standards of each flavor chemical and analyzed the toxicity of their aerosols produced at 3V and 5V using a tank Box Mod device. Over 50% of the refill fluids in our sample contained high concentrations of flavor chemicals that transferred efficiently to aerosols at concentrations that produce cytotoxicity. When tested with two types of human lung cells, the aerosols made at 5V were generally more toxic than those made at 3V. These data will be valuable for consumers, physicians, public health officials, and regulatory agencies when discussing potential health concerns relating to flavor chemicals in electronic cigarette products.

EFFECT OF MENTAL EXERCISE ON PAROTID FLOW RATE IN THE HUMAN.

DTIC Science & Technology

Three experiments were carried out in which paired parotid fluid samples were collected from 225 healthy young adults in an effort to ascertain the...providing the initial sample. There was no indication in any of the 3 experiments that mental concentration produced a significant effect on the rate of parotid flow. (Author)

Apparatus for measuring resistance change only in a cell analyzer and method for calibrating it

DOEpatents

Hoffman, Robert A.

1980-01-01

The disclosure relates to resistance only monitoring and calibration in an electrical cell analyzer. Sample and sheath fluid flows of different salinities are utilized, the sample flow being diameter modulated to produce a selected pattern which is compared to the resistance measured across the flows.

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

Cooper, Clay A.; Thomas, James M.; Lyles, Brad F.

Samples from a well drilled in the Astor Pass area six-km north of the Needle Rocks area of Pyramid Lake indicate that the reservoir fluid is dominantly sodium, chloride, and sulfate, with a pH between 8.6 and 8.9. The total dissolved solids in the reservoir is approximately 1600 mg/l, about half that of the TDS of the fluids in the Needle Rocks area. One sample of dissolved gas from fluids produced during a well test in the reservoir had 4He value of 2.32 x 10 14 atoms 4He/g water, or approximately 100 times the value of atmospheric 4He. This measurement,more » in conjunction with a R/Ra measurement of 0.28, suggests that most of the reservoir helium is derived from the crust, with possibly a small value (~3.3 percent) derived from the mantle. Tritium concentration of the sample was 0.09 TU, indicating that the reservoir fluid was recharged more than 60 years ago; a simple model based upon carbon-14 suggests recharge has occurred within the past 1500 years.« less

Effect of synovial fluid, phosphate-buffered saline solution, and water on the dissolution and corrosion properties of CoCrMo alloys as used in orthopedic implants.

PubMed

Lewis, A C; Kilburn, M R; Papageorgiou, I; Allen, G C; Case, C P

2005-06-15

The corrosion and dissolution of high- and low-carbon CoCrMo alloys, as used in orthopedic joint replacements, were studied by immersing samples in phosphate-buffered saline (PBS), water, and synovial fluid at 37 degrees C for up to 35 days. Bulk properties were analyzed with a fine ion beam microscope. Surface analyses by X-ray photoelectron spectroscopy and Auger electron spectroscopy showed surprisingly that synovial fluid produced a thin oxide/hydroxide layer. Release of ions into solution from the alloy also followed an unexpected pattern where synovial fluid, of all the samples, had the highest Cr concentration but the lowest Co concentration. The presence of carbide inclusions in the alloy did not affect the corrosion or the dissolution mechanisms, although the carbides were a significant feature on the metal surface. Only one mechanism was recognized as controlling the thickness of the oxide/hydroxide interface. The analysis of the dissolved metal showed two mechanisms at work: (1) a protein film caused ligand-induced dissolution, increasing the Cr concentration in synovial fluid, and was explained by the equilibrium constants; (2) corrosion at the interface increased the Co in PBS. The effect of prepassivating the samples (ASTM F-86-01) did not always have the desired effect of reducing dissolution. The release of Cr into PBS increased after prepassivation. The metal-synovial fluid interface did not contain calcium phosphate as a deposit, typically found where samples are exposed to calcium rich bodily fluids. (c) 2005 Wiley Periodicals, Inc.

The John Charnley Award Paper. The role of joint fluid in the tribology of total joint arthroplasty.

PubMed

Mazzucco, Daniel; Spector, Myron

2004-12-01

The effect of joint fluid on the tribology (ie, lubrication, friction, and wear) of total hip arthroplasty has not yet been investigated adequately. In the current study, a friction assay was used to assess four hypotheses relating to the effect of human joint fluid and its principal components on the articulation of metal-on-polyethylene. First, joint fluid was found to produce a widely varying amount of friction between cobalt-chromium and polyethylene; this range exceeded the range produced when the articulation was lubricated by water or bovine serum. Second, it was shown that hyaluronic acid, phospholipid, albumin, and gamma-globulin were not acting as boundary lubricants, but that one or more other proteins (as yet unidentified) were responsible for reducing friction in this couple. Third, lower friction was found when oxidized zirconium alloy replaced cobalt-chromium as a bearing surface on polyethylene. Finally, a pilot study suggested that lubricin, which contributes to cartilage-on-cartilage lubrication, is not a protein responsible for the tribological variabiation found among joint fluid samples. The current study showed that joint fluid is a patient factor that influences the tribology of metal-on-polyethylene arthroplasty.

Direct 40Ar/39Ar age determination of fluid inclusions using in-vacuo¬ stepwise crushing - Example of garnet from the Cycladic Blueschist Unit on Syros

NASA Astrophysics Data System (ADS)

Uunk, Bertram; Postma, Onno; Wijbrans, Jan; Brouwer, Fraukje

2017-04-01

Metamorphic minerals and veins commonly trap attending hydrous fluids in fluid inclusions, which yield a wealth of information on the history of the hosting metamorphic system. When these fluids are sufficiently saline, the KCl in the inclusions can be used as a K/Ar geochronologic system, potentially dating inclusion incorporation. Whilst primary fluid inclusions (PFIs) can date fluid incorporation during mineral or vein growth, secondary fluid inclusion trails (SFIs) can provide age constraints on later fluid flow events. At VU Amsterdam, a new in-vacuo crushing apparatus has been designed to extract fluid inclusions from minerals for 40Ar/39Ar analysis. Separates are crushed inside a crusher tube connected to a purification line and a quadrupole mass spectrometer. In-vacuo crushing is achieved by lifting and dropping a steel pestle using an externally controlled magnetic field. As the gas can be analyzed between different crushing steps, the setup permits stepwise crushing experiments. Additionally, crushed powder can be heated by inserting the crusher tube in an externally controlled furnace. Dating by 40Ar/39Ar stepwise crushing has the added advantage that, during neutron irradiation to produce 39Ar from 39K, 38Ar and 37Ar are also produced from 38Cl and 40Ca, respectively. Simultaneous analysis of these argon isotopes permits constraining the chemistry of the argon source sampled during the experiment. This allows a distinction between different fluid or crystal lattice sources. Garnet from three samples of the HP metamorphic Cycladic Blueschist Unit on Syros, Greece was stepwise crushed to obtain fluid inclusion ages. Initial steps for all three experiments yield significant components of excess argon, which are interpreted to originate from grain boundary fluids and secondary fluid inclusions trails. During subsequent steps, age results stabilize to a plateau age. One garnet from North Syros yields an unusually old 80 Ma plateau age. However, isochrons indicate the presence of excess argon in the PFIs and isochron ages overlap with other isotopic constraints on the age of garnet growth during eclogite metamorphism (55-50 Ma) in the underlying metabasite. Garnet from two samples from the center of Syros yields younger ages overlapping with greenschist overprinting (25-30 Ma). Further studies will indicate whether these younger ages reflect a young garnet growth age or a young fluid flow event affecting older garnet crystals. The stepwise crushing and heating approach shows to be effective in dating fluid inclusions in natural mineral systems. As many metamorphic processes occur under influence or in the presence of fluids, this method should greatly expand our possibilities to date crustal processes.

Corrosion resistance and biological activity of TiO2 implant coatings produced in oxygen-rich environments.

PubMed

Zhang, Rui; Wan, Yi; Ai, Xing; Liu, Zhanqiang; Zhang, Dong

2017-01-01

The physical and chemical properties of bio-titanium alloy implant surfaces play an important role in their corrosion resistance and biological activity. New turning and turning-rolling processes are presented, employing an oxygen-rich environment in order to obtain titanium dioxide layers that can both protect implants from corrosion and also promote cell adhesion. The surface topographies, surface roughnesses and chemical compositions of the sample surfaces were obtained using scanning electron microscopy, a white light interferometer, and the Auger electron spectroscopy, respectively. The corrosion resistance of the samples in a simulated body fluid was determined using electrochemical testing. Biological activity on the samples was also analyzed, using a vitro cell culture system. The results show that compared with titanium oxide layers formed using a turning process in air, the thickness of the titanium oxide layers formed using turning and turning-rolling processes in an oxygen-rich environment increased by 4.6 and 7.3 times, respectively. Using an oxygen-rich atmosphere in the rolling process greatly improves the corrosion resistance of the resulting samples in a simulated body fluid. On samples produced using the turning-rolling process, cells spread quickly and exhibited the best adhesion characteristics.

Tuning Fork Oscillators as Downhole Viscometers in Oilfield Applications

NASA Astrophysics Data System (ADS)

Gonzalez, Miguel; Bernero, Greg; Alvarez, Oliverio; Ham, Gregory; Max, Deffenbaugh; Sensors Development Team

2015-03-01

The commerciality of oil wells is greatly influenced by the physical properties of the fluids being produced. A key parameter in determining how producible the hydrocarbons are is their viscosity. Pressure and temperature changes in recovering a downhole sample to the surface can alter viscosity while accurate downhole measurement of this critical property remains a rudimentary effort in the industry. In this presentation we describe the challenges of measuring and quantifying the viscosity of reservoir fluids in situ at downhole conditions, as well as present an overview of some of the different measurement techniques currently used. Additionally, we show our characterization of a piezoelectric tuning fork oscillator used as a viscosity sensor. In an attempt to recreate the environment found in oil wells, its mechanical and electrical properties were studied while the device was immersed in different fluids and, separately, under different conditions of pressure and temperature. This device is a first step toward the development of an inexpensive, integrated, and miniaturized sensing platform for the in situ characterization of reservoir fluids.

Organic compounds in produced waters from shale gas wells.

PubMed

Maguire-Boyle, Samuel J; Barron, Andrew R

2014-01-01

A detailed analysis is reported of the organic composition of produced water samples from typical shale gas wells in the Marcellus (PA), Eagle Ford (TX), and Barnett (NM) formations. The quality of shale gas produced (and frac flowback) waters is a current environmental concern and disposal problem for producers. Re-use of produced water for hydraulic fracturing is being encouraged; however, knowledge of the organic impurities is important in determining the method of treatment. The metal content was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Mineral elements are expected depending on the reservoir geology and salts used in hydraulic fracturing; however, significant levels of other transition metals and heavier main group elements are observed. The presence of scaling elements (Ca and Ba) is related to the pH of the water rather than total dissolved solids (TDS). Using gas chromatography mass spectrometry (GC/MS) analysis of the chloroform extracts of the produced water samples, a plethora of organic compounds were identified. In each water sample, the majority of organics are saturated (aliphatic), and only a small fraction comes under aromatic, resin, and asphaltene categories. Unlike coalbed methane produced water it appears that shale oil/gas produced water does not contain significant quantities of polyaromatic hydrocarbons reducing the potential health hazard. Marcellus and Barnett produced waters contain predominantly C6-C16 hydrocarbons, while the Eagle Ford produced water shows the highest concentration in the C17-C30 range. The structures of the saturated hydrocarbons identified generally follows the trend of linear > branched > cyclic. Heterocyclic compounds are identified with the largest fraction being fatty alcohols, esters, and ethers. However, the presence of various fatty acid phthalate esters in the Barnett and Marcellus produced waters can be related to their use in drilling fluids and breaker additives rather than their presence in connate fluids. Halogen containing compounds are found in each of the water samples, and although the fluorocarbon compounds identified are used as tracers, the presence of chlorocarbons and organobromides formed as a consequence of using chlorine containing oxidants (to remove bacteria from source water), suggests that industry should concentrate on non-chemical treatments of frac and produced waters.

Trace Metals in Saharan Dust: The Use of in Vitro Bioaccessibility Extractions To Assess Potential Health Risks in a Dustier World: Chapter 3

USGS Publications Warehouse

Morman, Suzette A.; Garrison, Virginia H.; Plumlee, Geoffrey S.

2013-01-01

Exposure to fine particulate matter (PM) is acknowledged as a risk factor for human morbidity and mortality. Epidemiology and toxicology studies have focused on anthropogenic sources of PM and few consider contributions produced by natural processes (geogenic), or PM produced from natural sources as a result of human activities (geoanthropogenic PM). The focus of this study was to elucidate relationships between human/ecosystem health and dusts produced by a system transitioning from a dominantly natural to a geoanthropogenic PM source. As part of a larger study investigating the relationship between atmospheric transportation of African dust, human health, and coral reef declines, we examined dust samples sourced in Mali, Africa, collected using high-volume samplers from three sites (Mali, Tobago and U.S. Virgin Islands). Inhalation and ingestion exposure pathways were explored by filter extractions using simulated lung and gastric fluids. Bioaccessibility varied by metal and extraction fluid. Although too few samples were analyzed for robust statistics, concentrations for several metals decreased slightly while bioaccessibility increased at downwind sites.

Using stepped anvils to make even insulation layers in laser-heated diamond-anvil cell samples

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

Du, Zhixue; Gu, Tingting; Dobrosavljevic, Vasilije

Here, we describe a method to make even insulation layers for high-pressure laser-heated diamond-anvil cell samples using stepped anvils. Moreover, the method works for both single-sided and double-sided laser heating using solid or fluid insulation. The stepped anvils are used as matched pairs or paired with a flat culet anvil to make gasket insulation layers and not actually used at high pressures; thus, their longevity is ensured. We also compare the radial temperature gradients and Soret diffusion of iron between self-insulating samples and samples produced with stepped anvils and find that less pronounced Soret diffusion occurs in samples with evenmore » insulation layers produced by stepped anvils.« less

Using stepped anvils to make even insulation layers in laser-heated diamond-anvil cell samples

DOE PAGES

Du, Zhixue; Gu, Tingting; Dobrosavljevic, Vasilije; ...

2015-09-01

Here, we describe a method to make even insulation layers for high-pressure laser-heated diamond-anvil cell samples using stepped anvils. Moreover, the method works for both single-sided and double-sided laser heating using solid or fluid insulation. The stepped anvils are used as matched pairs or paired with a flat culet anvil to make gasket insulation layers and not actually used at high pressures; thus, their longevity is ensured. We also compare the radial temperature gradients and Soret diffusion of iron between self-insulating samples and samples produced with stepped anvils and find that less pronounced Soret diffusion occurs in samples with evenmore » insulation layers produced by stepped anvils.« less

Analysis of sources of bulk conductivity change in saturated silica sand after unbuffered TCE oxidation by permanganate.

PubMed

Hort, Ryan D; Revil, André; Munakata-Marr, Junko

2014-09-01

Time lapse resistivity surveys could potentially improve monitoring of permanganate-based in situ chemical oxidation (ISCO) of organic contaminants such as trichloroethene (TCE) by tracking changes in subsurface conductivity that result from injection of permanganate and oxidation of the contaminant. Bulk conductivity and pore fluid conductivity changes during unbuffered TCE oxidation using permanganate are examined through laboratory measurements and conductivity modeling using PHREEQC in fluid samples and porous media samples containing silica sand. In fluid samples, oxidation of one TCE molecule produces three chloride ions and one proton, resulting in an increase in fluid electrical conductivity despite the loss of two permanganate ions in the reaction. However, in saturated sand samples in which up to 8mM TCE was oxidized, at least 94% of the fluid conductivity associated with the presence of protons was removed within 3h of sand contact, most likely through protonation of silanol groups found on the surface of the sand grains. Minor conductivity effects most likely associated with pH-dependent reductive dissolution of manganese dioxide were also observed but not accounted for in pore-fluid conductivity modeling. Unaccounted conductivity effects resulted in an under-calculation of post-reaction pore fluid conductivity of 2.1% to 5.5%. Although small increases in the porous media formation factor resulting from precipitation of manganese dioxide were detected (about 3%), these increases could not be confirmed to be statistically significant. Both injection of permanganate and oxidation of TCE cause increases in bulk conductivity that would be detectable through time-lapse resistivity surveys in field conditions. Copyright © 2014 Elsevier B.V. All rights reserved.

Detection of African Swine Fever Virus Antibodies in Serum and Oral Fluid Specimens Using a Recombinant Protein 30 (p30) Dual Matrix Indirect ELISA.

PubMed

Giménez-Lirola, Luis G; Mur, Lina; Rivera, Belen; Mogler, Mark; Sun, Yaxuan; Lizano, Sergio; Goodell, Christa; Harris, D L Hank; Rowland, Raymond R R; Gallardo, Carmina; Sánchez-Vizcaíno, José Manuel; Zimmerman, Jeff

2016-01-01

In the absence of effective vaccine(s), control of African swine fever caused by African swine fever virus (ASFV) must be based on early, efficient, cost-effective detection and strict control and elimination strategies. For this purpose, we developed an indirect ELISA capable of detecting ASFV antibodies in either serum or oral fluid specimens. The recombinant protein used in the ELISA was selected by comparing the early serum antibody response of ASFV-infected pigs (NHV-p68 isolate) to three major recombinant polypeptides (p30, p54, p72) using a multiplex fluorescent microbead-based immunoassay (FMIA). Non-hazardous (non-infectious) antibody-positive serum for use as plate positive controls and for the calculation of sample-to-positive (S:P) ratios was produced by inoculating pigs with a replicon particle (RP) vaccine expressing the ASFV p30 gene. The optimized ELISA detected anti-p30 antibodies in serum and/or oral fluid samples from pigs inoculated with ASFV under experimental conditions beginning 8 to 12 days post inoculation. Tests on serum (n = 200) and oral fluid (n = 200) field samples from an ASFV-free population demonstrated that the assay was highly diagnostically specific. The convenience and diagnostic utility of oral fluid sampling combined with the flexibility to test either serum or oral fluid on the same platform suggests that this assay will be highly useful under the conditions for which OIE recommends ASFV antibody surveillance, i.e., in ASFV-endemic areas and for the detection of infections with ASFV isolates of low virulence.

A New Method of Obtaining High-Resolution Paleoclimate Records from Speleothem Fluid Inclusions

NASA Astrophysics Data System (ADS)

Logan, A. J.; Horton, T. W.

2010-12-01

We present a new method for stable hydrogen and oxygen isotope analysis of ancient drip water trapped within cave speleothems. Our method improves on existing fluid inclusion isotopic analytical techniques in that it decreases the sample size by a factor of ten or more, dramatically improving the spatial and temporal precision of fluid inclusion-based paleoclimatology. Published thermal extraction methods require large samples (c. 150 mg) and temperatures high enough (c. 500-900°C) to cause calcite decomposition, which is also associated with isotopic fractionation of the trapped fluids. Extraction by crushing faces similar challenges, where the failure to extract all the trapped fluid can result in isotopic fractionation, and samples in excess of 500 mg are required. Our new method combines the strengths of these published thermal and crushing methods using continuous-flow isotope ratio analytical techniques. Our method combines relatively low-temperature (~250°C) thermal decrepitation with cryogenic trapping across a switching valve sample loop. In brief, ~20 mg carbonate samples are dried (75°C for >1 hour) and heated (250°C for >1 hour) in a quartz sample chamber under a continuously flowing stream of ultra-high purity helium. Heating of the sample chamber is achieved by use of a tube furnace. Fluids released during the heating step are trapped in a coiled stainless steel cold trap (~ -98°C) serving as the sample loop in a 6-way switching valve. Trapped fluids are subsequently injected into a high-temperature conversion elemental analyzer by switching the valve and rapidly thawing the trap. This approach yielded accurate and precise measurements of injected liquid water IAEA reference materials (GISP; SMOW2; SLAP2) for both hydrogen and oxygen isotopic compositions. Blanking tests performed on the extraction line demonstrate extremely low line-blank peak heights (<50mv). Our tests also demonstrate that complete recovery of liquid water is possible and that a minimum quantity of ~100nL water was required. In contrast to liquid water analyses, carbonate inclusion waters gave highly variable results. As plenty of signal was produced from relatively small sample sizes (~20 mg), the observed isotopic variation most likely reflects fractionation during fluid extraction, or natural isotopic variability. Additional tests and modifications to the extraction procedure are in progress, using a recently collected New Zealand stalagmite from a West Coast cave (DOC collection permit WC-27462-GEO). U-Th age data will accompany a paleoclimate record from this stalagmite obtained using standard carbonate analytical techniques, and compared to the results from our new fluid inclusion analyses.

Examination of Duct Physiology in the Human Mammary Gland

PubMed Central

Mills, Dixie; Gomberawalla, Ameer; Gordon, Eva J.; Tondre, Julie; Nejad, Mitra; Nguyen, Tinh; Pogoda, Janice M.; Rao, Jianyu; Chatterton, Robert; Henning, Susanne; Love, Susan M.

2016-01-01

Background The human breast comprise several ductal systems, or lobes, which contain a small amount of fluid containing cells, hormones, proteins and metabolites. The complex physiology of these ducts is likely a contributing factor to the development of breast cancer, especially given that the vast majority of breast cancers begin in a single lobular unit. Methods We examined the levels of total protein, progesterone, estradiol, estrone sulfate, dehydroepiandrosterone sulfate, and macrophages in ductal fluid samples obtained from 3 ducts each in 78 women, sampled twice over a 6 month period. Samples were processed for both cytological and molecular analysis. Intraclass correlation coefficients and mixed models were utilized to identify significant data. Results We found that the levels of these ductal fluid components were generally uncorrelated among ducts within a single breast and over time, suggesting that each lobe within the breast has a distinct physiology. However, we also found that estradiol was more correlated in women who were nulliparous or produced nipple aspirate fluid. Conclusions Our results provide evidence that the microenvironment of any given lobular unit is unique to that individual unit, findings that may provide clues about the initiation and development of ductal carcinomas. PMID:27073976

DNA methylation profiling for a confirmatory test for blood, saliva, semen, vaginal fluid and menstrual blood.

PubMed

Lee, Hwan Young; Jung, Sang-Eun; Lee, Eun Hee; Yang, Woo Ick; Shin, Kyoung-Jin

2016-09-01

The ability to predict the type of tissues or cells from molecular profiles of crime scene samples has important practical implications in forensics. A previously reported multiplex assay using DNA methylation markers could only discriminate between 4 types of body fluids: blood, saliva, semen, and the body fluid which originates from female reproductive organ. In the present study, we selected 15 menstrual blood-specific CpG marker candidates based on analysis of 12 genome-wide DNA methylation profiles of vaginal fluid and menstrual blood. The menstrual blood-specificity of the candidate markers was confirmed by comparison with HumanMethylation450 BeadChip array data obtained for 58 samples including 12 blood, 12 saliva, 12 semen, 3 vaginal fluid, and 19 skin epidermis samples. Among 15CpG marker candidates, 3 were located in the promoter region of the SLC26A10 gene, and 2 of them (cg09696411 and cg18069290) showed high menstrual blood specificity. DNA methylation at the 2CpG markers was further tested by targeted bisulfite sequencing of 461 additional samples including 49 blood, 52 saliva, 34 semen, 125 vaginal fluid, and 201 menstrual blood. Because the 2 markers showed menstrual blood-specific methylation patterns, we modified our previous multiplex methylation SNaPshot reaction to include these 2 markers. In addition, a blood marker cg01543184 with cross reactivity to semen was replaced with cg08792630, and a semen-specific unmethylation marker cg17621389 was removed. The resultant multiplex methylation SNaPshot allowed positive identification of blood, saliva, semen, vaginal fluid and menstrual blood using the 9CpG markers which show a methylation signal only in the target body fluids. Because of the complexity in cell composition, menstrual bloods produced DNA methylation profiles that vary with menstrual cycle and sample collection methods, which are expected to provide more insight into forensic menstrual blood test. Moreover, because the developed multiplex methylation SNaPshot reaction includes the 4CpG markers of which specificities have been confirmed by multiple studies, it will facilitate confirmatory tests for body fluids that are frequently observed in forensic casework. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Simultaneous Neutron and X-ray Tomography for Quantitative analysis of Geological Samples

NASA Astrophysics Data System (ADS)

LaManna, J.; Hussey, D. S.; Baltic, E.; Jacobson, D. L.

2016-12-01

Multiphase flow is a critical area of research for shale gas, oil recovery, underground CO2 sequestration, geothermal power, and aquifer management. It is critical to understand the porous structure of the geological formations in addition to the fluid/pore and fluid/fluid interactions. Difficulties for analyzing flow characteristics of rock cores are in obtaining 3D distribution information on the fluid flow and maintaining the cores in a state for other analysis methods. Two powerful non-destructive methods for obtaining 3D structural and compositional information are X-ray and neutron tomography. X-ray tomography produces information on density and structure while neutrons excel at acquiring the liquid phase and produces compositional information. These two methods can offer strong complementary information but are typically conducted at separate times and often at different facilities. This poses issues for obtaining dynamic and stochastic information as the sample will change between analysis modes. To address this, NIST has developed a system that allows for multimodal, simultaneous tomography using thermal neutrons and X-rays by placing a 90 keVp micro-focus X-ray tube 90° to the neutron beam. High pressure core holders that simulate underground conditions have been developed to facilitate simultaneous tomography. These cells allow for the control of confining pressure, axial load, temperature, and fluid flow through the core. This talk will give an overview the simultaneous neutron and x-ray tomography capabilities at NIST, the benefits of multimodal imaging, environmental equipment for geology studies, and several case studies that have been conducted at NIST.

Environmental consequences of shale gas exploitation and the crucial role of rock microfracturing

NASA Astrophysics Data System (ADS)

Renard, Francois

2015-04-01

The growing exploitation of unconventional gas and oil resources has dramatically changed the international market of hydrocarbons in the past ten years. However, several environmental concerns have also been identified such as the increased microseismicity, the leakage of gas into freshwater aquifers, and the enhanced water-rock interactions inducing the release of heavy metals and other toxic elements in the produced water. In all these processes, fluids are transported into a network of fracture, ranging from nanoscale microcracks at the interface between minerals and the kerogen of the source rock, to well-developed fractures at the meter scale. Characterizing the fracture network and the mechanisms of its formation remains a crucial goal. A major difficulty when analyzing fractures from core samples drilled at depth is that some of them are produced by the coring process, while some other are produced naturally at depth by the coupling between geochemical and mechanical forces. Here, I present new results of high resolution synchrotron 3D X-ray microtomography imaging of shale samples, at different resolutions, to characterize their microfractures and their mechanisms of formation. The heterogeneities of rock microstructure are also imaged, as they create local stress concentrations where cracks may nucleate or along which they propagate. The main results are that microcracks form preferentially along kerogen-mineral interfaces and propagate along initial heterogeneities according to the local stress direction, connecting to increase the total volume of fractured rock. Their lifetime is also an important parameter because they may seal by fluid circulation, fluid-rock interactions, and precipitation of a cement. Understanding the multi-scale processes of fracture network development in shales and the coupling with fluid circulation represents a key challenge for future research directions.

Unique microbial community in drilling fluids from Chinese continental scientific drilling

USGS Publications Warehouse

Zhang, Gengxin; Dong, Hailiang; Jiang, Hongchen; Xu, Zhiqin; Eberl, Dennis D.

2006-01-01

Circulating drilling fluid is often regarded as a contamination source in investigations of subsurface microbiology. However, it also provides an opportunity to sample geological fluids at depth and to study contained microbial communities. During our study of deep subsurface microbiology of the Chinese Continental Scientific Deep drilling project, we collected 6 drilling fluid samples from a borehole from 2290 to 3350 m below the land surface. Microbial communities in these samples were characterized with cultivation-dependent and -independent techniques. Characterization of 16S rRNA genes indicated that the bacterial clone sequences related to Firmicutes became progressively dominant with increasing depth. Most sequences were related to anaerobic, thermophilic, halophilic or alkaliphilic bacteria. These habitats were consistent with the measured geochemical characteristics of the drilling fluids that have incorporated geological fluids and partly reflected the in-situ conditions. Several clone types were closely related to Thermoanaerobacter ethanolicus, Caldicellulosiruptor lactoaceticus, and Anaerobranca gottschalkii, an anaerobic metal-reducer, an extreme thermophile, and an anaerobic chemoorganotroph, respectively, with an optimal growth temperature of 50–68°C. Seven anaerobic, thermophilic Fe(III)-reducing bacterial isolates were obtained and they were capable of reducing iron oxide and clay minerals to produce siderite, vivianite, and illite. The archaeal diversity was low. Most archaeal sequences were not related to any known cultivated species, but rather to environmental clone sequences recovered from subsurface environments. We infer that the detected microbes were derived from geological fluids at depth and their growth habitats reflected the deep subsurface conditions. These findings have important implications for microbial survival and their ecological functions in the deep subsurface.

Reduction of hexavalent chromium by fasted and fed human gastric fluid. I. Chemical reduction and mitigation of mutagenicity.

PubMed

De Flora, Silvio; Camoirano, Anna; Micale, Rosanna T; La Maestra, Sebastiano; Savarino, Vincenzo; Zentilin, Patrizia; Marabotto, Elisa; Suh, Mina; Proctor, Deborah M

2016-09-01

Evaluation of the reducing capacity of human gastric fluid from healthy individuals, under fasted and fed conditions, is critical for assessing the cancer hazard posed by ingested hexavalent chromium [Cr(VI)] and for developing quantitative physiologically-based pharmacokinetic models used in risk assessment. In the present study, the patterns of Cr(VI) reduction were evaluated in 16 paired pre- and post-meal gastric fluid samples collected from 8 healthy volunteers. Human gastric fluid was effective both in reducing Cr(VI), as measured by using the s-diphenylcarbazide colorimetric method, and in attenuating mutagenicity in the Ames test. The mean (±SE) Cr(VI)-reducing ability of post-meal samples (20.4±2.6μgCr(VI)/mL gastric fluid) was significantly higher than that of pre-meal samples (10.2±2.3μgCr(VI)/mL gastric fluid). When using the mutagenicity assay, the decrease of mutagenicity produced by pre-meal and post-meal samples corresponded to reduction of 13.3±1.9 and 25.6±2.8μgCr(VI)/mL gastric fluid, respectively. These data are comparable to parallel results conducted by using speciated isotope dilution mass spectrometry. Cr(VI) reduction was rapid, with >70% of total reduction occurring within 1min and 98% of reduction is achieved within 30min with post-meal gastric fluid at pH2.0. pH dependence was observed with decreasing Cr(VI) reducing capacity at higher pH. Attenuation of the mutagenic response is consistent with the lack of DNA damage observed in the gastrointestinal tract of rodents following administration of ≤180ppm Cr(VI) for up to 90days in drinking water. Quantifying Cr(VI) reduction kinetics in the human gastrointestinal tract is necessary for assessing the potential hazards posed by Cr(VI) in drinking water. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Micromachined chemical jet dispenser

DOEpatents

Swierkowski, S.P.

1999-03-02

A dispenser is disclosed for chemical fluid samples that need to be precisely ejected in size, location, and time. The dispenser is a micro-electro-mechanical systems (MEMS) device fabricated in a bonded silicon wafer and a substrate, such as glass or silicon, using integrated circuit-like fabrication technology which is amenable to mass production. The dispensing is actuated by ultrasonic transducers that efficiently produce a pressure wave in capillaries that contain the chemicals. The 10-200 {micro}m diameter capillaries can be arranged to focus in one spot or may be arranged in a larger dense linear array (ca. 200 capillaries). The dispenser is analogous to some ink jet print heads for computer printers but the fluid is not heated, thus not damaging certain samples. Major applications are in biological sample handling and in analytical chemical procedures such as environmental sample analysis, medical lab analysis, or molecular biology chemistry experiments. 4 figs.

Micromachined chemical jet dispenser

DOEpatents

Swierkowski, Steve P.

1999-03-02

A dispenser for chemical fluid samples that need to be precisely ejected in size, location, and time. The dispenser is a micro-electro-mechanical systems (MEMS) device fabricated in a bonded silicon wafer and a substrate, such as glass or silicon, using integrated circuit-like fabrication technology which is amenable to mass production. The dispensing is actuated by ultrasonic transducers that efficiently produce a pressure wave in capillaries that contain the chemicals. The 10-200 .mu.m diameter capillaries can be arranged to focus in one spot or may be arranged in a larger dense linear array (.about.200 capillaries). The dispenser is analogous to some ink jet print heads for computer printers but the fluid is not heated, thus not damaging certain samples. Major applications are in biological sample handling and in analytical chemical procedures such as environmental sample analysis, medical lab analysis, or molecular biology chemistry experiments.

The calculation of aquifer chemistry in hot-water geothermal systems

USGS Publications Warehouse

Truesdell, Alfred H.; Singers, Wendy

1974-01-01

The temperature and chemical conditions (pH, gas pressure, and ion activities) in a geothermal aquifer supplying a producing bore can be calculated from the enthalpy of the total fluid (liquid + vapor) produced and chemical analyses of water and steam separated and collected at known pressures. Alternatively, if a single water phase exists in the aquifer, the complete analysis (including gases) of a sample collected from the aquifer by a downhole sampler is sufficient to determine the aquifer chemistry without a measured value of the enthalpy. The assumptions made are that the fluid is produced from a single aquifer and is homogeneous in enthalpy and chemical composition. These calculations of aquifer chemistry involving large amounts of ancillary information and many iterations require computer methods. A computer program in PL-1 to perform these calculations is available from the National Technical Information Service as document PB-219 376.

Inorganic chemical composition and chemical reactivity of settled dust generated by the World Trade Center building collapse: Chapter 12

USGS Publications Warehouse

Plumlee, Geoffrey S.; Hageman, Philip L.; Lamothe, Paul J.; Ziegler, Thomas L.; Meeker, Gregory P.; Theodorakos, Peter M.; Brownfield, Isabelle; Adams, Monique G.; Swayze, Gregg A.; Hoefen, Todd M.; Taggart, Joseph E.; Clark, Roger N.; Wilson, S.; Sutley, Stephen J.

2009-01-01

Samples of dust deposited around lower Manhattan by the September 11, 2001, World Trade Center (WTC) collapse have inorganic chemical compositions that result in part from the variable chemical contributions of concrete, gypsum wallboard, glass fibers, window glass, and other materials contained in the buildings. The dust deposits were also modified chemically by variable interactions with rain water or water used in street washing and fire fighting. Chemical leach tests using deionized water as the extraction fluid show the dust samples can be quite alkaline, due primarily to reactions with calcium hydroxide in concrete particles. Calcium and sulfate are the most soluble components in the dust, but many other elements are also readily leached, including metals such as Al, Sb, Mo Cr, Cu, and Zn. Indoor dust samples produce leachates with higher pH, alkalinity, and dissolved solids than outdoor dust samples, suggesting most outdoor dust had reacted with water and atmospheric carbon dioxide prior to sample collection. Leach tests using simulated lung fluids as the extracting fluid suggest that the dust might also be quite reactive in fluids lining the respiratory tract, resulting in dissolution of some particles and possible precipitation of new phases such as phosphates, carbonates, and silicates. Results of these chemical characterization studies can be used by health scientists as they continue to track and interpret health effects resulting from the short-term exposure to the initial dust cloud and the longer-term exposure to dusts resuspended during cleanup.

Synthesis and characterization of low cost magnetorheological (MR) fluids

NASA Astrophysics Data System (ADS)

Sukhwani, V. K.; Hirani, H.

2007-04-01

Magnetorheological fluids have great potential for engineering applications due to their variable rheological behavior. These fluids find applications in dampers, brakes, shock absorbers, and engine mounts. However their relatively high cost (approximately US600 per liter) limits their wide usage. Most commonly used magnetic material "Carbonyl iron" cost more than 90% of the MR fluid cost. Therefore for commercial viability of these fluids there is need of alternative economical magnetic material. In the present work synthesis of MR fluid has been attempted with objective to produce low cost MR fluid with high sedimentation stability and greater yield stress. In order to reduce the cost, economical electrolytic Iron powder (US 10 per Kg) has been used. Iron powder of relatively larger size (300 Mesh) has been ball milled to reduce their size to few microns (1 to 10 microns). Three different compositions have been prepared and compared for MR effect produced and stability. All have same base fluid (Synthetic oil) and same magnetic phase i.e. Iron particles but they have different additives. First preparation involves organic additives Polydimethylsiloxane (PDMS) and Stearic acid. Other two preparations involve use of two environmental friendly low-priced green additives guar gum (US 2 per Kg) and xanthan gum (US 12 per Kg) respectively. Magnetic properties of Iron particles have been measured by Vibrating Sample Magnetometer (VSM). Morphology of Iron particles and additives guar gum and xanthan gum has been examined by Scanning Electron Microscopy (SEM) and Particles Size Distribution (PSD) has been determined using Particle size analyzer. Microscopic images of particles, MH plots and stability of synthesized MR fluids have been reported. The prepared low cost MR fluids showed promising performance and can be effectively used for engineering applications demanding controllability in operations.

Monitoring Fluid Flow in Fractured Carbonate Rocks Using Seismic Measurements

NASA Astrophysics Data System (ADS)

Li, W.; Pyrak-Nolte, L. J.

2008-12-01

The physical properties of carbonate rock are strongly influenced by the rock fabric which depends on the depositional environment, diagenetic and tectonic processes. The most common form of heterogeneity is layering caused by a variation in porosity among layers and within layers. The variation in porosity among layers leads to anisotropic behavior in the hydraulic, mechanical and seismic properties of carbonate rocks. We present the results of a laboratory study to examine the effect of fabric-controlled layering on fluid flow and seismic wave propagation through intact and fractured carbonate rock. Experiments were performed on cubic samples of Austin Chalk Cordova Cream. Samples AC1, AC5 and AC6 are cubic samples that measure 100 mm on edge. The samples were sealed and contained three inlet and three outlet ports for fluid invasion experiments. Two orthogonal seismic arrays were used to record both compressional and shear wave transmission through intact and fractured samples. The arrays used piezoelectric contact transducers with a central frequency 1.0 MHz. Between the two arrays, sixteen sources and sixteen receivers were used. Seismic measurements were made on the samples as a function of stress and during fluid saturation. The location of the invading fluid front as a function of time was monitored by using the peak-to-peak amplitude of the transmitted signals. The front was assumed to be between a source-receiver pair when the signal amplitude decreased by 50% over the initial value. The hydraulic gradient was parallel and perpendicular to the layers for AC5 and AC6, respectively. Sample AC1 was fractured and flow ports were established on the edges of the fracture plane. The weakly directed fabric controlled the rate at which fluid flowed through the samples. From the seismic data on AC6, the fluid first spread vertically along a layer before flowing across the layers. For AC6, it took the fluid two and half hours to flow between the inlet and the outlet across the layers. However, for AC5, the water flowed quickly along the layers and crossed the entire sample in one and a half hours. From the seismic data on fractured sample AC1, the water initially took more than 15 hours to transverse the sample though portions of the fracture were invaded after two hours. No water was produced at the outlet over a 15 hour period. Upon inspection, chemical precipitation was observed along the fracture plane and fracture- matrix interaction controlled the saturation of the matrix. Seismic monitoring of the fluid-front during saturation indicates that fine bedding affects the hydraulic properties of the sample while geochemical interactions in fractures affect fracture-matrix communication. Acknowledgments: The authors wish to acknowledge support of this work by the Geosciences Research Program, Office of Basic Energy Sciences US Department of Energy (DEFG02-97ER14785 08) and by Exxon Mobil Upstream Research Company.

The microscopic (optical and SEM) examination of putrefaction fluid deposits (PFD). Potential interest in forensic anthropology.

PubMed

Charlier, P; Georges, P; Bouchet, F; Huynh-Charlier, I; Carlier, R; Mazel, V; Richardin, P; Brun, L; Blondiaux, J; Lorin de la Grandmaison, G

2008-10-01

This article describes the potential interest in physical and forensic anthropology of the microscopic analysis of residues of putrefaction fluid, a calcified deposit frequently found associated with bone rests. Its sampling and analysis seem straightforward and relatively reproducible. Samples came from archeological material (Monterenzio Vecchia, an Etruscan necropolis from the north of Italy dated between the fifth and third century B.C.; body rests of Agnès Sorel, royal mistress died in 1450 A.D.; skull and grave of French King Louis the XI and Charlotte of Savoy dated from 1483 A.D.). All samples were studied by direct optical microscope and scanning electron microscopy. Many cytological, histological, and elemental analysis were possible, producing precious data for the identification of these remains and, in some cases, the cause of death.

Systems and methods for separating particles and/or substances from a sample fluid

DOEpatents

Mariella, Jr., Raymond P.; Dougherty, George M.; Dzenitis, John M.; Miles, Robin R.; Clague, David S.

2016-11-01

Systems and methods for separating particles and/or toxins from a sample fluid. A method according to one embodiment comprises simultaneously passing a sample fluid and a buffer fluid through a chamber such that a fluidic interface is formed between the sample fluid and the buffer fluid as the fluids pass through the chamber, the sample fluid having particles of interest therein; applying a force to the fluids for urging the particles of interest to pass through the interface into the buffer fluid; and substantially separating the buffer fluid from the sample fluid.

The presence of vaginal Lactobacillus species does not contribute to a measureable difference in amniotic fluid lactate levels collected from the vaginal tract of laboring women.

PubMed

Hall, Beverley; Wong, Diana; Healy, Clare; Tracy, Mark B; Tracy, Sally K; Rawlinson, William D

2017-04-01

Amniotic fluid lactate research is based on the hypothesis that a relationship exists between fatigued uterine muscles and raised concentrations of the metabolite lactate, which is excreted into the amniotic fluid during labor. To assess potentially confounding effects of lactate-producing organisms on amniotic fluid lactate measurements, we aimed to determine if the presence of vaginal Lactobacillus species was associated with elevated levels of amniotic fluid lactate, measured from the vaginal tract of women in labor. Results from this study contribute to a large prospective longitudinal study of amniotic fluid lactate at a teaching hospital in Sydney, Australia. Amniotic fluid lactate measurement was assessed at the time of routine vaginal examination, after membranes had ruptured, using a hand-held lactate meter StatStripXPress (Nova Biomedical). Vaginal swab samples were collected at the time of the first amniotic fluid lactate measurement and stored for later detection and quantification of Lactobacillus species using a TaqMan real-time PCR assay. Swab sample and amniotic fluid lactate results were paired and analyzed. The PCR assay detected Lactobacillus species in 48 of 388 (12%) vaginal swab specimens (8% positive, 4% low positive) collected from women in labor after membranes had ruptured. There was no significant difference in median and mean (respectively) amniotic fluid lactate levels with (8.35 mmol/L; 8.95 mmol/L) or without (8.5 mmol/L; 9.08 mmol/L) Lactobacillus species detected. There was no association between the presence or level of vaginal Lactobacillus species and the measurement of amniotic fluid lactate collected from the vaginal tract of women during labor. © 2017 Nordic Federation of Societies of Obstetrics and Gynecology.

Characterization of Radium and Radon Isotopes in Hydraulic Fracturing Flowback Fluid and Gas from the Marcellus Shale

NASA Astrophysics Data System (ADS)

Bardsley, A.

2015-12-01

High volume hydraulic fracturing of unconventional deposits has expanded rapidly over the past decade in the US, with much attention focused on the Marcellus Shale gas reservoir in the northeastern US. We use naturally occurring radium isotopes and 222Rn to explore changes in formation characteristics as a result of hydraulic fracturing. Gas and produced waters were analyzed from time series samples collected soon after hydraulic fracturing at three Marcellus Shale well sites in the Appalachian Basin, USA. Analyses of δ18O, Cl- , and 226Ra in flowback fluid are consistent with two end member mixing between injected slick water and formation brine. All three tracers indicate that the ratio of injected water to formation brine declines with time across both time series. Cl- concentration (max ~1.5-2.2 M) and 226Ra activity (max ~165-250 Bq/Kg) in flowback fluid are comparable at all three sites. There are differences evident in the stable isotopic composition (δ18O & δD) of injected slick water across the three sites, but all appear to mix with formation brine of similar isotopic composition. On a plot of water isotopes, δ18O in formation brine-dominated fluid is enriched by ~3-4 permille relative to the Global Meteoric Water Line, indicating oxygen exchange with shale. The ratio of 223Ra/226Ra and 228Ra/226Ra in produced waters is quite low relative to shale samples analyzed. This indicates that most of the 226Ra in the formation brine must be sourced from shale weathering or dissolution rather than emanation due to alpha recoil from the rock surface. During the first week of flowback, ratios of short lived isotopes 223Ra and 224Ra to longer lived radium isotopes change modestly, suggesting rock surface area per unit of produced water volume did not change substantially. For one well, longer term gas samples were collected. The 222Rn/methane ratio in produced gas from this site declines with time and may represent a decrease in the brine to gas ratio in the reservoir over the course of six months after initial fracturing. Naturally occurring radium and radon isotopes show promise in elucidating sub-surface dynamics following hydraulic fracturing plays.

On the Exploitation of Sensitivity Derivatives for Improving Sampling Methods

NASA Technical Reports Server (NTRS)

Cao, Yanzhao; Hussaini, M. Yousuff; Zang, Thomas A.

2003-01-01

Many application codes, such as finite-element structural analyses and computational fluid dynamics codes, are capable of producing many sensitivity derivatives at a small fraction of the cost of the underlying analysis. This paper describes a simple variance reduction method that exploits such inexpensive sensitivity derivatives to increase the accuracy of sampling methods. Three examples, including a finite-element structural analysis of an aircraft wing, are provided that illustrate an order of magnitude improvement in accuracy for both Monte Carlo and stratified sampling schemes.

Ultra‐high performance supercritical fluid chromatography of lignin‐derived phenols from alkaline cupric oxide oxidation

PubMed Central

Sun, Mingzhe; Lidén, Gunnar; Sandahl, Margareta

2016-01-01

Traditional chromatographic methods for the analysis of lignin‐derived phenolic compounds in environmental samples are generally time consuming. In this work, an ultra‐high performance supercritical fluid chromatography method with a diode array detector for the analysis of major lignin‐derived phenolic compounds produced by alkaline cupric oxide oxidation was developed. In an analysis of a collection of 11 representative monomeric lignin phenolic compounds, all compounds were clearly separated within 6 min with excellent peak shapes, with a limit of detection of 0.5–2.5 μM, a limit of quantification of 2.5–5.0 μM, and a dynamic range of 5.0–2.0 mM (R 2 > 0.997). The new ultra‐high performance supercritical fluid chromatography method was also applied for the qualitative and quantitative analysis of lignin‐derived phenolic compounds obtained upon alkaline cupric oxide oxidation of a commercial humic acid. Ten out of the previous eleven model compounds could be quantified in the oxidized humic acid sample. The high separation power and short analysis time obtained demonstrate for the first time that supercritical fluid chromatography is a fast and reliable technique for the analysis of lignin‐derived phenols in complex environmental samples. PMID:27452148

Role of water in the smectite-to-illite reaction

USGS Publications Warehouse

Whitney, Gene

1990-01-01

A series of hydrothermal experiments was performed to determine the effect of fluid abundance on the reaction of smectite to illite. Experiments were conducted on K-saturated montmorillonite (<0.1-µm fraction) in a closed system at 250° to 400°C using run times of 1, 7, 14, 30, and 60 days at 100 MPa (1 kbar) pressure. In fluid-deficient systems (pore spaces not saturated), the rate and extent of illitization was significantly inhibited. A rock:water ratio of 20:1 (mass:mass) produced an R0 illite/smectite (I/S) having 82% smectite layers after 60 days at 250°C, whereas a rock:water ratio of 1:1 produced an I/S having 57% smectite layers under the same conditions. The effect became less pronounced at higher temperatures, with the 20:1 and the 1:1 experimental products differing by only 11% expandability at 400°C after 60 days. In addition, the low-fluid experiments produced fewer crystalline byproducts (quartz, cristobalite, chlorite) than did the fluid-rich runs, and the I/S was more difficult to disperse and orient in the fluid-deficient samples, suggesting enhanced cementation at grain contacts or the production of particle morphologies that did not lend themselves to orientation. The difference in reactivity of the smectite and I/S as a function of water content appears to be attributable to the reduced capacity for low volumes of water to mediate the dissolution, solute transport, and precipitation reactions that make up the series of reactions collectively termed illitization. Of these variables, solute transport is likely to be affected most by reduction of fluid.

Exploring matrix effects and quantifying organic additives in hydraulic fracturing associated fluids using liquid chromatography electrospray ionization mass spectrometry.

PubMed

Nell, Marika; Helbling, Damian E

2018-05-23

Hydraulic fracturing (HF) operations utilize millions of gallons of water amended with chemical additives including biocides, corrosion inhibitors, and surfactants. Fluids injected into the subsurface return to the surface as wastewaters, which contain a complex mixture of additives, transformation products, and geogenic chemical constituents. Quantitative analytical methods are needed to evaluate wastewater disposal alternatives or to conduct adequate exposure assessments. However, our narrow understanding of how matrix effects change the ionization efficiency of target analytes limits the quantitative analysis of polar to semi-polar HF additives by means of liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS). To address this limitation, we explored the ways in which matrix chemistry influences the ionization of seventeen priority HF additives with a modified standard addition approach. We then used the data to quantify HF additives in HF-associated fluids. Our results demonstrate that HF additives generally exhibit suppressed ionization in HF-associated fluids, though HF additives that predominantly form sodiated adducts exhibit significantly enhanced ionization in produced water samples, which is largely the result of adduct shifting. In a preliminary screening, we identified glutaraldehyde and 2-butoxyethanol along with homologues of benzalkonium chloride (ADBAC), polyethylene glycol (PEG), and polypropylene glycol (PPG) in HF-associated fluids. We then used matrix recovery factors to provide the first quantitative measurements of individual homologues of ADBAC, PEG, and PPG in HF-associated fluids ranging from mg L-1 levels in hydraulic fracturing fluid to low μg L-1 levels in PW samples. Our approach is generalizable across sample types and shale formations and yields important data to evaluate wastewater disposal alternatives or implement exposure assessments.

Rapid variations in fluid chemistry constrain hydrothermal phase separation at the Main Endeavour Field

NASA Astrophysics Data System (ADS)

Love, Brooke; Lilley, Marvin; Butterfield, David; Olson, Eric; Larson, Benjamin

2017-02-01

Previous work at the Main Endeavour Field (MEF) has shown that chloride concentration in high-temperature vent fluids has not exceeded 510 mmol/kg (94% of seawater), which is consistent with brine condensation and loss at depth, followed by upward flow of a vapor phase toward the seafloor. Magmatic and seismic events have been shown to affect fluid temperature and composition and these effects help narrow the possibilities for sub-surface processes. However, chloride-temperature data alone are insufficient to determine details of phase separation in the upflow zone. Here we use variation in chloride and gas content in a set of fluid samples collected over several days from one sulfide chimney structure in the MEF to constrain processes of mixing and phase separation. The combination of gas (primarily magmatic CO2 and seawater-derived Ar) and chloride data, indicate that neither variation in the amount of brine lost, nor mixing of the vapor phase produced at depth with variable quantities of (i) brine or (ii) altered gas rich seawater that has not undergone phase separation, can explain the co-variation of gas and chloride content. The gas-chloride data require additional phase separation of the ascending vapor-like fluid. Mixing and gas partitioning calculations show that near-critical temperature and pressure conditions can produce the fluid compositions observed at Sully vent as a vapor-liquid conjugate pair or as vapor-liquid pair with some remixing, and that the gas partition coefficients implied agree with theoretically predicted values.