Ultrasensitive methyl salicylate gas sensing determined by Pd-doped SnO2

Efficient chemical warfare agents (CWAs) detection is required to protect people from the CWAs in war and terrorism. In this work, a Pd-doped SnO₂ nanoparticles-based gas sensor was developed to detect a nerve agent simulant named methyl salicylate. The sensing measurements of methyl salicylate under different Pd doping amounts found that the 0.5 at.% Pd-doped SnO₂ exhibited a significant improvement in the detection of methyl salicylate at the ppb (1 ppb = 10⁻⁹) level, and the response value to 160 ppb methyl salicylate is 0.72 at 250 °C. Compared with the pure SnO₂, the response value is increased by 4.5 times, which could be attributed to the influence of the noble metal Pd on the oxygen state and its catalytic effect. In addition, the 0.5 at.% Pd-doped SnO₂ sensor still has an obvious response to 16 ppb methyl salicylate with a response value of 0.13, indicating the lower detection limit of the sensor.     

Determination of trace amounts of chemical warfare agent degradation products in decontamination solutions with NMR spectroscopy

Decontamination solutions are used for an efficient detoxification of chemical warfare agents (CWAs). As these solutions can be composed of strong alkaline chemicals with hydrolyzing and oxidizing properties, the analysis of CWA degradation products in trace levels from these solutions imposes a challenge for any analytical technique. Here, we present results of application of nuclear magnetic resonance spectroscopy for analysis of trace amounts of CWA degradation products in several untreated decontamination solutions. Degradation products of the nerve agents sarin, soman, and VX were selectively monitored with substantially reduced interference of background signals by 1D 1H-31P heteronuclear single quantum coherence (HSQC) spectrometry. The detection limit of the chemicals was at the low part-per-million level (2-10 microg/mL) in all studied solutions. In addition, the concentration of the degradation products was obtained with sufficient confidence with external standards.     

Metal Oxide Nanowire and Thin-Film-Based Gas Sensors for Chemical Warfare Simulants Detection

This work concerns with metal oxide (MOX) gas sensors based on nanowires and thin films. We focus on chemical warfare agents (CWAs) detection to compare these materials from the functional point-of-view. We work with different chemicals including simulants for Sarin nerve agents, vescicant gases, cyanide agents, and analytes such as ethanol, acetone, ammonia, and carbon monoxide that can be produced by everyday activities causing false alarms. Explorative data analysis has been used to demonstrate the different sensing performances of nanowires and thin films. Within the chosen application, our analysis reveal that the introduction of nanowires inside the array composed by thin films can improve its sensing capability. Cyanide simulants have been detected at concentrations close to 1 ppm, lower than the Immediately Dangerous for Life and Health (IDLH) value of the respective warfare agent. Higher sensitivity has been obtained to simulants for Sarin and vescicant gases, which have been detected at concentrations close or even lower than 100 ppb. Results demonstrate the suitability of the proposed array to selectively detect CWA simulants with respect to some compounds produced by everyday activities.     

Human health risk screening due to consumption of fish contaminated with chemical warfare agents in the Baltic Sea

Chemical warfare agents (CWAs) have been disposed of in various fashions over the past decades. Significant amounts of CWA, roughly 11,000 ton, have been dumped in the Baltic Sea east of the island Bornholm following the disarmament of Germany after World War II. This has caused concerns over potential human and environmental health risks, and resulted in restrictions on fishing in the dumpsite area. The purpose of this paper is to assess the potential indirect human health risks due to consumption of CWA-contaminated fish from the dumpsite area east of Bornholm. Earlier studies suggest that the fish community may be at risk from CWA exposure in the Bornholm basin. Moreover, elevated frequencies of lesions on fish caught in a CWA dumpsite in the Mediterranean Sea have been observed. The fish at the Mediterranean dumpsite had elevated total arsenic (As) concentrations in their tissue, and elevated total As levels were also observed in the sediment. Elevated total sediment As concentrations have also been recorded in CWA dumpsites in the Skagerrak and the Baltic Sea. Triphenylarsine and sulfur mustard gas (Yperite) are the CWAs with the greatest indirect human health risk potential. There are recognized uncertainties concerning Yperite's and CWA-derived arsenical's fate and speciation in the environment, as well as their inherent toxicity, warranting caution and further site-specific environmental and human health risk assessments of CWAs dumped in the Bornholm basin.     

Single-particle aerosol mass spectrometry for the detection and identification of chemical warfare agent simulants

Single-particle aerosol mass spectrometry (SPAMS) was used for the real-time detection of liquid nerve agent simulants. A total of 1000 dual-polarity time-of-flight mass spectra were obtained for micrometer-sized single particles each of dimethyl methyl phosphonate, diethyl ethyl phosphonate, diethyl phosphoramidate, and diethyl phthalate using laser fluences between 0.58 and 7.83 nJ/microm2, and mass spectral variation with laser fluence was studied. The mass spectra obtained allowed identification of single particles of the chemical warfare agent (CWA) simulants at each laser fluence used although lower laser fluences allowed more facile identification. SPAMS is presented as a promising real-time detection system for the presence of CWAs.     

Screening level fish community risk assessment of chemical warfare agents in the Baltic Sea

Chemical warfare agents (CWAs) have been disposed of in various fashions over the past decades. Significant amounts (approximately 11,000 tonnes) have been dumped in the Baltic Sea east of the island Bornholm following the disarmament of Germany after World War II, causing concerns over potential environmental risks. Absence of risk based on assumptions of extremely low solubility of CWAs cannot alone dismiss these concerns. Existing and modelled fate and effects data were used in the analysis to assess the fish community risk level. The most realistic and also conservative assessment result is the scenario describing 70 m water depth for the most realistic dump-site area with a focus on chronic toxicity, at 0-20 cm above the sediment, yielding a total mixture toxic unit (TU) of 0.62. Triphenylarsine is the CWA with the highest realistic risk profile at 0.2 TU for the fish community followed by Adamsite (0.17), Clark I (0.086) and Yperite (0.083) TU. Adamsite is more persistent and constitutes a potential risk for a longer period than triphenylarsine. The seawater volume potentially at risk is <4 m above sediment and <58 km down current of dump sites. Further risk assessment of dumped CWAs in the Baltic Sea is warranted.     

PBT screening profile of chemical warfare agents (CWAs)

Chemical warfare agents (CWAs) have been used and disposed of in various fashions over the past decades. Significant amounts have been dumped in the Baltic Sea following the disarmament of Germany after World War II causing environmental concerns. There is a data gap pertaining to chemical warfare agents, environmental properties not the least their aquatic toxicities. Given this gap and the security limitations relating to working with these agents we applied Quantitative Structure-Activity Relationship ((Q)SAR) models in accordance with the European Technical Guidance Document (2003) to 22 parent CWA compounds and 27 known hydrolysis products. It was concluded that conservative use of EPI Suite (Q)SAR models can generate reliable and conservative estimations of chemical warfare agents acute aquatic toxicity. From an environmental screening point of view the organoarsenic chemical warfare agents Clark I and Adamsite comprise the most problematic of the screened CWA compounds warranting further investigation in relation to a site specific environmental risk assessment. The mustard gas agents (sulphur and nitrogen) and the organophosphorous CWAs (in particular Sarin and Soman) are a secondary category of concern based upon their toxicity alone. The undertaken approach generates reliable and conservative estimations for most of the studied chemicals but with some exceptions (e.g. the organophosphates).     

Detection of chemical weapon agents and simulants using chemical ionization reaction time-of-flight mass spectrometry

Chemical ionization reaction time-of-flight mass spectrometry (CIR-TOF-MS) has been used for the analysis of prepared mixtures of chemical weapon agents (CWAs) sarin and sulfur mustard. Detection of the CWA simulants 2-chloroethyl ethyl sulfide, triethyl phosphate, and dimethyl methyl phosphonate has also been investigated. Chemical ionization of all the agents and simulants was shown to be possible using the CIR-TOF-MS technique with a variety of reagent ions, and the sensitivity was optimized by variation of instrument parameters. The ionization process was found to be largely unaffected by sample humidity levels, demonstrating the potential suitability of the method to a range of environmental conditions, including the analysis of CWAs in air and in the breath of exposed individuals.     

Application of single drop microextraction for analysis of chemical warfare agents and related compounds in water by gas chromatography/mass spectrometry

Retrospective detection and identification of chemical warfare agents (CWAs) is important from the verification point of view of the Chemical Weapons Convention. In the present work, a novel method for determination of CWAs and their markers in water has been described. It is based on a single drop micro extraction (SDME) of analytes and gas chromatography/mass spectrometric identification. Extraction conditions, such as solvent selection, agitation, extraction time, and salt content, were found to have significant influence on SDME. The conditions optimized for extraction of CWAs were 1 microL CH2Cl2/CCl4 (3:1 v/v), 30-min extraction time, 300-rpm stirring rate, and with or without NaCl addition. Under optimized conditions, comparison of SDME, solid-phase microextraction, and liquid-liquid extraction was also made. The limit of detection by SDME ranged from 75 to 10 microg L(-1) at a signal-to-noise ratio of 10:1.     

Efficiency of ground granulated blast-furnace slag replacement in ceramic waste aggregate mortar

From our previous findings, the recycling of ceramic waste aggregate (CWA) in mortar has been proved an ecological means plus an excellent outcome against chloride ingress. The CWAs were porcelain insulator wastes supplied from an electric power company, which were crushed and ground to fine aggregate sizes. In this study, to further develop the CWA mortar as an eco-efficient construction material, ground granulated blast-furnace slag (GGBS) was incorporated. The slag (having the Blaine fineness of 6230 cm²/g) was utilized as a supplementary cementitious material (SCM) at three different replacement levels of 15%, 30%, and 45% of cement by weight. The efficiency of the GGBS on enhancing chloride resistance in the CWA mortars was experimentally assessed by using a silver nitrate solution spray method and an electron probe microanalysis (EPMA). The tests were carried out on mortar samples after immersed in a 5.0% NaCl solution for 24 weeks. Another set of the mortar samples was exposed to a laboratory ambient condition for 24 weeks and then followed with a carbonation test. The test results indicated that the resistance to the chloride ingress of the CWA mortar becomes more effective in proportion to the replacement level of the GGBS. In contrast, the carbonation depth of the CWA mortar increases with the increase of the GGBS. The activeness of the GGBS was also evaluated on the basis of the compressive strength development up to 91 days. Due to its high fineness, the GGBS can be used up to 30% while the high relative strength (more than 1.0) is achieved at all ages.     

Detection of a chemical warfare agent simulant in various aerosol matrixes by ion mobility time-of-flight mass spectrometry

For the first time, a traditional radioactive nickel (63Ni) beta emission ionization source for ion mobility spectrometry was employed with an atmospheric pressure ion mobility orthogonal reflector time-of-flight mass spectrometer (IM(tof)MS) to detect a chemical warfare agent (CWA) simulant from aerosol samples. Aerosol-phase sampling employed a quartz cyclonic chamber for sample introduction. The simulant reference material, which closely mimicked the characteristic chemical structure of CWAs as defined and described by Schedule 1, 2, or 3 of the Chemical Warfare Convention treaty verification, was used in this study. An overall elevation in arbitrary signal intensity of approximately 1.0 orders of magnitude was obtained by the progressive increase of the thermal AP-IMS temperature from 75 to 275 degrees C. A mixture of one G-type nerve simulant (dimethyl methylphosphonate (DMMP)) in four (water, kerosene, gasoline, diesel) matrixes was found in each case (AP-IMS temperature 75-275 degrees C) to be clearly resolved in less than 2.20 x 10(4) micros using the IM(tof)MS instrument. Corresponding ions, masses, drift times, K(o) values, and arbitrary signal intensities for each of the sample matrixes are reported for the CWA simulant DMMP.     

Noncovalent modification of carbon nanotubes with ferrocene-amino acid conjugates for electrochemical sensing of chemical warfare agent mimics

The electrochemical detection of chemical warfare agent (CWA) mimics was explored using multiwalled carbon nanotubes (MWCNTs) on indium tin oxide (ITO) surfaces in connection with ferrocene-amino acid conjugates. Various ferrocene-amino acid conjugates were synthesized and utilized as the recognition layer for the detection of CWA mimics. The ferrocene-amino acid conjugates were noncovalently attached to the pretreated MWCNTs on the ITO surface and reacted with CWA mimics, upon which the electrical properties of the MWCNTs and the Fc group were affected significantly. Alternating current voltammetry and capacitance-based detection offered large dynamic ranges for the detection of methylphosphonic acid, diethyl cyanophosphonate, ethylmethylphosphonate, and pinacolyl methylphosphonate in water. Electrochemical measurements showed dramatic changes upon the electrostatic interaction between the CWA mimics and the ferrocene-amino acid conjugates immobilized on MWCNTs on ITO surfaces. Electrochemical sensing in connection with MWCNTs is shown to be a promising analytical tool for the trace-level detection of CWA mimics in aqueous solutions.     

Mid-infrared spectroscopic investigation of methylamines by a continuous-wave difference-frequency-generation-based system

A laser spectroscopic system based on a cw difference-frequency generation source with a ratiometric multipass absorption detection scheme was employed for high-resolution spectroscopic investigation of gas-phase monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA). Possible application of the system as a noninvasive human breath analyzer for renal and liver diseases is targeted. The system operates in the fundamental C-H stretch absorption region around 2740-2860 cm(-1). A detection sensitivity of 2 x 10(-6) cm(-1) Hz(-(1/2)) (for signal-to-noise ratio SNR=1) is achieved, corresponding to detection limits of 900 ppb (parts in 10(9)) for MMA, 450 ppb for DMA, and 120 ppb for TMA in mixtures containing H2O and CO2 with concentrations of up to those present in human breath (2% and 5%, respectively). Future developments are discussed to further improve these detection limits that are currently still about 2 orders of magnitude higher than required for direct methylamine monitoring in human breath.     

Spectroscopic investigation of methylated amines by a cavity-ringdown-based spectrometer

High-resolution absorption spectra of gas-phase monomethylamine (MMA, CH(3)NH(2)) and dimethylamine [DMA, (CH(3))(2)NH] in the region of the first overtone of the NH stretch vibration are reported. Measurements were performed with a near-infrared laser spectrometer based on the cavity-ringdown (CRD) detection technique. The minimum detectable absorption coefficient for the CRD detection setup is alpha(min)=1.55 x 10(-8) cm(-1) (for SNR = 1). This corresponds to detection limits of 350 parts in 10(9) (ppb) for MMA and 1.6 parts in 10(6) (ppm) for DMA in synthetic gas mixtures under interference-free conditions, or 10 ppm and 60 ppm for MMA and DMA, respectively, in the case of gas mixtures such as exhaled human breath containing H(2)O, CO(2), and other absorbing gases in this range.     

Wavelength-modulation laser hygrometer for ultrasensitive detection of water vapor in semiconductor gases

Water vapor is measured by use of a near-infrared diode laser and wavelength-modulation absorption spectroscopy. Humidity levels as low as 5 nmol/mol [1 nmol/mol = 1 ppb (1 ppb equals 1 part in 10(9))] of water vapor in air are measured with a sensitivity of better than 0.2 nmol/mol (3varsigma). The sensitivity, linearity, and stability of the technique are determined in experiments conducted at the National Institute of Standards and Technology, Gaithersburg, Maryland, by use of the low frost-point humidity generator over the range from 5 nmol/mol to 2.5 mumol/mol of water vapor in air. The pressure-broadening coefficients for water broadened by helium [0.0199(6) cm(-1) atm(-1) HWHM] and by hydrogen chloride [0.268(6) cm(-1) atm(-1) HWHM] are reported for the water line at 1392.5 nm.     

Real-time, ultralow concentration detection of analytes in solution by infrared intracavity laser absorption

Two intracavity laser absorption techniques for ultralow concentration detection of chemicals in solution are compared. The first consists of a laser diode in a grating extended cavity, which produces a linear calibration curve for parts in 10(9) (ppb) concentrations corresponding to 17 nM. By replacing the grating with a highly reflective mirror, parts in 10(12) (ppt) concentration detection is achieved, which corresponds to 340 pM. We report, to our knowledge for the first time, ppt detection of analyte concentration in liquid solution demonstrating good agreement between theory and experiment.     

Detection and false-alarm probabilities for laser radars that use Geiger-mode detectors

For a direct-detection laser radar that uses a Geiger-mode detector, theory shows that the single-pulse detection probability is reduced by a factor exp(-K), where K is the mean number of primary electrons created by noise in the interval t between detector turn-on and arrival of laser photons reflected from the target. The corresponding false-alarm probability is at least 1 - exp(-K). For fixed-rate noise, one can improve the detection and false-alarm probabilities by reducing t. Moreover, when background-light noise is significant and dominates dark-current noise and when the laser signal is of the order of ten photoelectrons or more, the probabilities can be improved by reducing the amount of light falling on the detector, even if the laser signal is reduced by the same factor as the background light is. Additional analytical calculations show that identifying coincidences in data from as few as three pulses canreduce the false-alarm probability by orders of magnitude and, for some conditions, can also improve the detection probability.     

Comments on 'constant false-alarm rate algorithm based on test cell information'

In a recent paper, Cao proposed and analysed a new switching constant false-alarm rate (CFAR) detection algorithm (S-CFAR), which exploits the magnitude of the test cell for the selection of the reference samples. Here we use the order statistic theory to obtain alternative expressions for the detection probability and the false-alarm rate of the S-CFAR in homogeneous background. They are not bulky and thus are easy to calculate for the thresholding parameters.     

Threshold detection in the presence of atmospheric turbulence

Recently there has been increased interest in threats to spacecraft from ground-based lasers. It has been suggested that some spacecraft should use laser-threat-warning receivers. We consider the effects of atmospheric turbulence on threshold detection of optical signals by an exoatmospheric receiver. The results are applicable to both cw and pulsed optical illumination that results from ground-based lasers. In particular we obtain accurate analytical expressions, over a wide range of conditions of practical interest, that yield the required signal-to-noise ratio for a given (single-event) probability of detection, false-alarm rate, and turbulence-induced log-intensity variance. The degrading effects of atmospheric turbulence on threshold detection are most important for large zenith angles in the blue-green region of the visible. As an illustrative example, a false-alarm rate of 1 in 3 years is assumed, and specific numerical results are presented for the required signal-to-noise ratio necessary to obtain a detection probability of at least 95% over a range of optical wavelengths and propagation conditions of interest.     

Detection probabilities for photon-counting avalanche photodiodes applied to a laser radar system

Arrays of photon-counting avalanche photodiodes with time-resolved readout can improve the performance of three-dimensional laser radars. A comparison of the detection and false-alarm probabilities for detectors in linear mode and in Geiger mode is shown. With low background radiation their performance is comparable. It is shown that in both cases it will be necessary to process several laser shots of the same scene to improve detection and reduce the false-alarm rate. Additional calculations show that the linear mode detector is much better at detecting targets behind semitransparent obscurations such as vegetation and camouflage nets.