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.

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.

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.

Sensor array for wireless remote monitoring of carbon dioxide and methane near carbon sequestration and oil recovery sites.

Carbon sequestration and enhanced oil recovery are two important geochemical applications currently deployed using carbon dioxide (CO2), a prevalent greenhouse gas. Despite the push to find ways to use and store excess CO2, the development of a large-area monitoring system is lacking. For these applications, there is little literature reporting the development and testing of sensor systems capable of operating in remote areas without maintenance and having significantly low cost to allow their deployment across a large land area. This paper presents the design and validation of a low-cost solar-power distributed sensing architecture using a wireless mesh network integrated, at selective nodes, into a cellular network. This combination allows an "internet of things" approach in remote locations and the integration of a large number of sensor units to monitor CO2 and methane (CH4). This system will allow efficient large area monitoring of both rare catastrophic leaks along with the common micro-seepage of greenhouse gas near carbon sequestration and oil recovery sites. The deployment and testing of the sensor system was performed in an open field at Oklahoma State University. The two-tear network functionality and robustness were determined from a multi-year field study. The reliability of the system was benchmarked by correlating the measured temperature, pressure, and humidity measurement by the network of devices to existing weather data. The CO2 and CH4 gas concentration tracked their expected daily and seasonal cycles. This multi-year field study established that this system can operate in remote areas with minimal human interactions.

Precision and Limits of Detection for Selected Commercially Available, Low-Cost Carbon Dioxide and Methane Gas Sensors.

The performance of a sensor platform for environmental or industrial monitoring is sensitive to the cost and performance of the individual sensor elements. Thus, the detection limits, accuracy, and precision of commercially available, low-cost carbon dioxide and methane gas concentration sensors were evaluated by precise measurements at known gas concentrations. Sensors were selected based on market availability, cost, power consumption, detection range, and accuracy. A specially constructed gas mixing chamber, coupled to a precision bench-top analyzer, was used to characterize each sensor during a controlled exposure to known gas concentrations. For environmental monitoring, the selected carbon dioxide sensors were characterized around 400 ppm. For methane, the sensor response was first monitored at 0 ppm, close to the typical environmental background. The selected sensors were then evaluated at gas concentrations of several thousand ppm. The determined detection limits accuracy, and precision provides a set of matrices that can be used to evaluate and select sensors for integration into a sensor platform for specific applications.

A simple construction of electrochemical liver microsomal bioreactor for rapid drug metabolism and inhibition assays.

In order to design a green microsomal bioreactor on suitably identified carbon electrodes, it is important to understand the direct electrochemical properties at the interfaces between various carbon electrode materials and human liver microsomes (HLM). The novelty of this work is on the investigation of directly adsorbed HLM on different carbon electrodes with the goal to develop a simple, rapid, and new bioanalytical platform of HLM useful for drug metabolism and inhibition assays. These novel biointerfaces are designed in this study by a one step adsorption of HLM directly onto polished basal plane pyrolytic graphite (BPG), edge plane pyrolytic graphite (EPG), glassy carbon (GC), or high-purity graphite (HPG) electrodes. The estimated direct electron transfer (ET) rate constant of HLM on the smooth GC surface was significantly greater than that of the other electrodes. On the other hand, the electroactive surface coverage and stability of microsomal films were greater on highly surface defective, rough EPG and HPG electrodes compared to the smooth GC and less defective hydrophobic BPG surfaces. The presence of significantly higher oxygen functionalities and flatness of the GC surface is attributed to favoring faster ET rates of the coated layer of thin HLM film compared to other electrodes. The cytochrome P450 (CYP)-specific bioactivity of the liver microsomal film on the catalytically superior, stable HPG surface was confirmed by monitoring the electrocatalytic conversion of testosterone to 6ß-hydroxytestosterone and its inhibition by the CYP-specific ketoconazole inhibitor. The identification of optimal HPG and EPG electrodes to design biologically active interfaces with liver microsomes is suggested to have immense significance in the design of one-step, green bioreactors for stereoselective drug metabolite synthesis and drug metabolism and inhibition assays.

Edge-to-edge interaction between carbon nanotube-pyrene complexes and electrodes for biosensing and electrocatalytic applications.

We demonstrate here that the edge-to-edge interaction between carbon nanotubes (CNTs) and edge plane electrodes plays an important role in exposing a large proportion of the basal planes of the CNTs to allow enhanced π-π stacking of a pyrenyl compound and subsequent high density protein immobilization yielding large electrocatalytic currents.

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.

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.

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.

CdS nanoparticles modified to chalcogen sites: new supramolecular complexes, butterfly bridging, and related optical effects.

All present approaches to surface modification of nanoparticles (NPs) with organic ligands exploit metal (cadmium) sites as anchor points. To obtain efficient interaction of NP surface with p-orbitals of organic chromophores, we utilize the chalcogen (sulfur) sites on the NP surface. These sites present several advantages stemming from a stronger interaction of their atomic orbitals with both modifier and NP core. The chalcogen modification of CdS was achieved by using a mixed ligand (2,2'-bipyridyl-N,N')(malonato-O,O')-copper(II) monohydrate complex. The weak monodentate ligands (water) are replaced by a copper-sulfur bond during the modification reaction. The structure of the product was investigated by optical spectroscopy, electron spin resonance, and nuclear magnetic resonance. The modified NP can be described as a few tens (<40) of (2,2'-bipyridyl-N,N')(malonato-O,O')-copper units attached to the CdS core. Steady-state and time-resolved luminescence measurements, molecular orbital calculations, and UPS data indicate that delocalized surface states enveloping the surface chalcogen atoms of NP, transition metal, and p-orbitals of the bipyridine ligand are present in the synthesized species. The delocalized states are made possible due to the bridging of p-levels of sulfur and pi-orbitals of bipyridine by butterfly d-orbitals of the transition metal atom placed between them. Chalcogen-modified NP can be considered as a new member of the family of supramolecular compounds based on transition metal complexes. Both NP and metal complex parts of the prepared supramolecules are very versatile structural units, and new molecular constructs of similar design, in which quantum effects of NPs are combined with optical properties of transition metal complexes, can be obtained with different NPs and metal complexes.