Detection of Hydrogen Peroxide in Liquid and Vapors Using Titanium(IV)-Based Test Strips and Low-Cost Hardware.

Titanium(IV) solutions are known to detect hydrogen peroxide in solutions by a colorimetric method. Xplosafe's XploSens PS commercial titanium(IV)-based peroxide detection test strips are used to detect hydrogen peroxide in liquids. The use of these test strips as gas-phase detectors for peroxides was tested using low-cost hardware. The exposure of these strips to hydrogen peroxide liquid or gas leads to the development of an intense yellow color. For liquids, a digital single-lens reflex camera was used to quantify the color change using standardized solutions containing between 50 and 500 ppm peroxide by mass. Analysis of the images with color separation can provide a more quantitative determination than visual comparison to a color chart. For hydrogen peroxide gas, an inexpensive web camera and a tungsten lamp were used to measure the reflected light intensity as a function of exposure from a test strip held in a custom cell. First-order behavior in the color change with time was observed during the exposure to peroxide vapor over a range of peroxide concentrations from 2 and 30 ppm by volume. For a 1-min measurement, the gas-phase detection limit is estimated to be 1 ppm. A 0.01 ppm detection limit can be obtained with a 1-h exposure time. Titanium(IV)-based peroxide detection test strips are sensitive enough to work as a gas-phase hydrogen peroxide detector.

Application of Nanoconfinement Technology for Highly Effective Monitoring of Chemical Exposure During Military Service.

INTRODUCTION: There is myriad of volatile compounds to which military personnel are exposed that can potentially have negative effects on their health. Military service occurs in a broad array of environments so it is difficult to predict the hazardous compounds to which the personnel might be exposed. XploSafe is developing passive diffusive samplers to facilitate the sampling and quantification of a wide range of chemical vapor exposures that personnel may be exposed to in the workplace. MATERIALS AND METHODS: Passive diffusive samplers were constructed by filling porous Teflon tubes with OSU-6, a nanoporous silica sorbent, to produce sampler tokens.  Three of these tokens were placed within a badge to fabricate passive samplers. Absorption experiments were performed to determine linear exposure regimes, sampling rates, and limits of quantification for 11 compounds, representing 8 chemical classes. RESULTS: The sampling rates were determined for 11 compounds representing 8 chemical classes. The measured linear ranges for the studied compounds are sufficiently large to allow effective sampling for 8 hours or longer. Accurate dosimetry is possible even with exposure times of days or weeks. The samplers were able to detect the presence of five airborne compounds in a paint booth of a military contractor located in Bristow, Oklahoma, and determine their average exposure concentrations. CONCLUSIONS: OSU-6 based sampler badges were able to detect the presence and quantify the average exposures of five airborne compounds in a paint booth of a military contractor located in Bristow, Oklahoma. Experiments show that these samplers can adsorb and quantify a broad array of different volatile organic compounds whose high sampling rates coupled with high capacity provide both sensitivity and the ability to quantify over a large range of exposures. This technology can meet the requirements for personal samplers to create Individual Longitudinal Exposure Record for each military person.

Remediation of arsenic and lead with nanocrystalline zinc sulfide.

Nanocrystalline (1.7 ± 0.3 nm) zinc sulfide with a specific surface area up to 360 m(2) g(-1) was prepared from the thermal decomposition of a single-source precursor, zinc ethylxanthate. Zinc ethylxanthate decomposes to cubic zinc sulfide upon exposure to temperatures greater than or equal to 125 °C. The resulting zinc sulfide was tested as a water impurity extractant. The target impurities used in this study were As(5+), As(3+), and Pb(2+). The reaction of the nanocrystalline ZnS with Pb(2+) proceeds as a replacement reaction where solid PbS is formed and Zn(2+) is released into the aqueous system. Removal of lead to a level of less than two parts per billion is achievable. The results of a detailed kinetics experiment between the ZnS and Pb(2+) are included in this study. Unlike the instance of lead, both As(5+) and As(3+) adsorb on the surface of the ZnS extractant as opposed to an ion-exchange process. An uptake capacity of > 25 mg g(-1) for the removal of As(5+) is possible. The uptake of As(3+) appears to proceed by a slower process than that of the As(5+) with a capacity of nearly 20 mg g(-1). The nanocrystalline zinc sulfide was extremely successful for the removal of arsenic and lead from simulated oil sand tailing pond water.

Follow-up study on the effects on well chemistry from biological and chemical remediation of chlorinated solvents.

The enduring effects of injected materials used for the remediation of chlorinated solvents were examined. Approximately two years previous to this study, four different remediation methods were tested in an area located southeast of Oklahoma City, OK. These methods included bioremediation under both anaerobic and aerobic conditions and chemical remediation using Fenton's reagent or KMnO(4). A series of water quality tests performed in this investigation revealed that the bioremediation processes did not introduce any unexpected chemistry. However, the wells that were treated anaerobically still had water with a negative oxidation-reduction potential and had no recontamination with migrating trichloroethylene as opposed to the aerobic wells that had both positive redox potentials and trichloroethylene present. Also, chemical treatment using Fenton's reagent did not result in any long-term changes in the well chemistry, with the exception of inducing a slight acidity. This is due to the facts that addition of iron into the aquifer that is already in contact with iron-rich clay soil had little long-term effects and the radical chemistry with hydrogen peroxide is short-lived due to its reactivity. KMnO(4)-based remediation results in deposition of new materials containing manganese in elevated oxidation states that may provide long-term protection against the build up of chlorinated organic compounds.

Iron-rich Oklahoma clays as a natural source of chromium in monitoring wells.

Water samples, drawn from groundwater monitoring wells located southeast of Oklahoma City, OK, were found to contain elevated concentrations of total chromium with an apparent source localized to the area surrounding each well. Since these monitoring wells are located in areas with no historic chromium usage, industrial sources of chromium were ruled out. Water testing was performed on twelve monitoring wells in the area that historically had elevated total chromium concentrations ranging from 10-4900 micrograms per litre. Filtered water samples were found to be free of chromium contamination, indicating that the source of the chromium is the suspended solids. Analysis of these solids by acid digestion and a sequential extraction technique revealed that the chromium was primarily associated with iron-containing solids. X-ray diffraction identified goethite, an iron oxide hydroxide, as the dominant iron-containing phase in the suspended solids. The mineralogy in this region is dominated by interbedded red-bed sandstone and mudstone whose mineral content includes mixed-layer illite-smectite, hematite, goethite, gypsum and dolomite. Elemental analysis of soil samples collected as a function of depth in the locale of the monitoring wells indicated that the iron rich clays contain a natural source of chromium. The elevated levels of total chromium are most likely due to the dissolution of silica and alumina from the chromium containing iron clays in the basic well water, resulting in the release of fine suspended solids that naturally have high chromium concentrations. These results should be applicable to other areas containing iron-rich clays.

Superior Monitoring of Chemical Exposure Using Nanoconfinement Technology.

INTRODUCTION: Military personnel are exposed to a broad range of potentially toxic compounds that can affect their health. These hazards are unpredictable because military service occurs in a wide array of uncontrolled environments. Therefore, a novel sorbent was developed that allows the fabrication of lightweight personal samplers that are both capable of sorbing an extremely wide range of organic chemical types and able to stabilize reactive compounds. MATERIALS AND METHODS: OSU-6, a nanoporous silica, was provided by XploSafe LLC. The sorption capacity for several volatile organic compounds, the temperatures required for thermal desorption of adsorbed compounds, and the sampling rates for targeted analytes were determined. RESULTS: The uptake capacity was found to be on average 1.5 g/g of sorbent. Analytes were not only held tightly but also could be desorbed upon heating the sorbate to temperatures below 150°C. Sampling rates for volatile organic compound by an OSU-6 sampler badge were on average, 5.7 times higher than those for a commercially available activated carbon badge. Theoretical calculations showed that sorption of volatile organic compounds on the surface of the tightly curved pore walls in OSU-6 is because of exceptionally strong cumulative addition of Van der Waals forces. Analytes could readily be analyzed by either solvent extraction or thermal desorption gas chromatography/mass spectrometry techniques. Excellent sampling rates, high concentrations of analytes in the OSU-6 sorbent matrix, and high desorption efficiencies (recoveries) were obtained using the thermal desorption method. CONCLUSIONS: The performance of the OSU-6 sorbent makes it highly capable of meeting the need for personal samplers that enable Individual Longitudinal Exposure Records development. It can adsorb an extremely wide array of different volatile organic compounds, it can stabilize reactive compounds, it has high sampling rates coupled with high capacity that provide both sensitivity and resistance to saturation, and it is unique in being very amenable to thermal desorption in combination with having strong sorbate binding and high capacity and surface area.

Crystal structure of melaminium cyano-acetate monohydrate.

The asymmetric unit of the title compound, 2,4,6-tri-amino-1,3,5-triazin-1-ium cyano-acetate monohydrate, C3H7N6 +·NCCH2COO-·H2O, consists of a melaminium cation, a cyano-acetate anion and a water mol-ecule, which are connected to each other via N-H⋯O and O-H⋯O hydrogen bonds, generating an eight-membered ring. In the crystal, the melaminium cations are connected by two pairs of N-H⋯N hydrogen bonds, forming tapes along [110]. These tapes develop a three-dimensional network through N-H⋯O, O-H⋯O, N-H⋯N and C-H⋯O hydrogen bonds between the cations, anions and water mol-ecules.

Methods for the reaction of alkenes with activated tungstic acid.

In this study, we have synthesized activated tungstic acid by dehydration of tungstic acid as a highly efficient catalyst and employed it for the catalytic transformations of various alkenes. The importance of this series of studies is to help students to graphically visualize a diverse array of organic synthesis reactions. The alkenes react differently depending on their structure via mainly acid-catalyzed reactions that produce a whole range of products including coupled products (dimers). For example, Cyclopentene was transformed into 1,1'-bi (cyclopent-3-ene) in yield 100% at room temperature. Cyclohexene-3-cyclohexyl was form from Cyclohexene. The synthesized product was identified and confirmed by gas chromatography and mass spectroscopy, measuring the retention times of authentic samples of the compounds.

Catalytic co-pyrolysis of red cedar with methane to produce upgraded bio-oil.

Fast pyrolysis is a promising route to transform biomass into bio-oil for further refining into transportation fuels and chemicals. However, bio-oil applications suffer from several challenges due to its adverse properties. This study reports improving bio-oil properties through co-pyrolysis of biomass with methane over molybdenum/zinc (MoZn/ZHSM-5) and HZSM-5 catalysts that promote deoxygenation, decarbonylation, hydrogen transfer and aromatization reactions. The co-pyrolysis was conducted at 650 °C and 750 °C in a micro-scale reactor and a bench-scale reactor. The highest bio-oil yield, energy content, and energy yield of 53.4%, 10.2 MJ/kg, and 29.9%, respectively, were obtained with methane over MoZn/HZSM-5 at 650 °C. Acids, alcohols, aldehydes, benzene derivatives, BTEXs, furans, ketones, PAHs, and phenols were detected in bio-oils while phenols dominated under most conditions. Oxygenated compounds decreased using MoZn/HZSM-5 with methane at 750 °C. The results demonstrate that methane used with catalysts can reduce oxygenated compounds and improve properties and yield of bio-oil.

Titania-hydroxypropyl cellulose thin films for the detection of peroxide vapors.

Titania nanoparticles in a hydroxypropyl cellulose matrix produced using a sol-gel method were utilized to prepare films on polycarbonate slides and coatings on cellulose papers. The exposure of these materials to hydrogen peroxide gas leads to the development of an intense yellow color. By using an inexpensive web camera and a tungsten lamp to measure the reflected light, first-order behavior in the color change was observed when exposed to peroxide vapor of less than 50 ppm. For 50 mass percent titania nanoparticles in hydroxypropyl cellulose films on polycarbonate, the detection limit was estimated to be 90 ppm after a 1 min measurement and 1.5 ppm after a 1 h integration. The coatings on the filter paper had a 3-fold higher sensitivity compared to the films, with a detection limit of 5.4 ppm peroxide for a 1 min measurement and 0.09 ppm peroxide for a 1 h integration. The high sensitivity and rapid response of these films make them a promising material for use as a sensitive peroxide detector.

Metal ion adsorption using polyamine-functionalized mesoporous materials prepared from bromopropyl-functionalized mesoporous silica.

Mesoporous silicas carrying di-, tri-, or penta-amine functional groups were prepared by prior functionalization of a mesoporous silica with bromopropyl-functional groups followed by nucleophilic displacement of the bromine atoms by ethylenediamine, diethylenetriamine, or tetraethylenepentamine, respectively. A synthetic method was developed that gave a starting material with very high surface coverage by the 3-brompropyl groups. Batch tests were conducted to investigate the capabilities of the prepared adsorbents for the removal of copper, zinc, and cadmium from aqueous solutions. The metal adsorption capacities for these metals were determined as a function of the polyamine group used and the total nitrogen content. The tendency to chemisorb divalent metal ions was found to follow the order: Cu(2+)>Zn(2+)>Cd(2+). It was found that the ethylenediamine derivative unexpectedly exhibited the highest capacities. The metal sorption by the ethylenediamine functionalized silica was found to follow first order kinetics with rate constants for Cu(2+), Zn(2+) and Cd(2+) uptake of 0.028, 0.019, and 0.014 min(-1), respectively. The substituted mesoporous silicas showed high resistance to leaching of the grafted polyamine groups. Copper ions that were adsorbed at the surface of the mesoporous silicas can be recovered by washing with an aqueous solution of 1.0 M HNO(3). The activities of the recovered mesoporous silicas were between 80 and 90% of the original materials.