Chemical Warfare Surrogates Research Articles

(Invited) Atmospheric Pressure Plasma Treatment and Decontamination of Water Samples

As water scarcity becomes widespread concern in many countries, new approaches for water processing are being considered. In order to have the potential to be applied in the industry, these new methods should be primarily environmentally friendly and with low-energy consumption. Employment of non-equilibrium plasma for water treatment entirely satisfies these two points and therefore makes plasma a good candidate. Non-equilibrium (or cold) plasma at atmospheric pressure has so far been successfully used in various applications related to biology and medicine. Plasma rich-chemistry environment produced at room atmosphere with ambient temperature enabled treatment of cells, plants, bacteria, tissues etc. with aims ranging from destruction of pathogens to healing or enhancing the growth in biological systems. Therefore, these applications clearly point out that plasma sources can deliver broad spectrum of treatment conditions.The latest research direction related to plasma and liquid treatment is plasma agriculture where different approaches for application of plasma in agricultural processes are investigated. Within these novel research area we investigate two possible applications: for the treatment of clean water samples for the production of plasma activated water (PAW); and for decontamination of polluted water containing organic micro pollutants (OMPs). PAW in comparison to clean water is rich in reactive oxygen and nitrogen species (RONS) and this proves to be an important asset when applied to seeds and plants. We showed that germination and plant growth can be enhanced when PAW is applied for seed imbibition and plant watering. On the other hand, the presence of reactive oxygen species in plasma and inside the treated water samples (especially droplets or aerosols) induces the decomposition of different molecules of OMPs. We demonstrated ability of plasma decontamination for several different organic molecules, such as decomposition of Malathion in atmospheric pressure plasma jet with high efficiency, and also for some chemicals used as chemical warfare surrogates. Apart from direct treatment of polluted samples by plasma, we have investigated a possibility of using PAW as a decontamination chemical to decompose organic dye Acid Blue 25 dissolved in water. Along the line of plasma agriculture research we combined the effects of two plasma applications in the plasma processing of agricultural waste water for reuse in irrigation. The experimental results showed that pesticide-containing polluted water can be decontaminated and at the same time enriched with RONS that positively influence germination of maize and radish.These successful applications unfold many questions related to the plasma properties, plasma gas and liquid phase chemical reactions, an entangled connection between plasma produced reactive species and their chemical interactions with organic molecules in water. In order to make a detailed insight into the treatment process, we performed comprehensive diagnostics of the plasma and of the liquid samples. Our results provide information about electrical and optical plasma properties and make connection with physical parameters of the liquid sample (pH, electrical conductivity). We used colorimetric methods to determine RONS in the treated liquids. To acquire information about plasma-induced decomposition and obtain by-products in the treated samples we performed liquid chromatography coupled with mass spectrometry. All these results provide important knowledge on plasma water treatments and represent another step towards understanding which are the best parameters for treatment monitoring and techniques for up-scaling plasma devices to treat large amounts of water.Acknowledgement: This study was partially supported by NATO SPS 984555, projects ON141037 and III 41011 of MESTD Republic of Serbia and H2020-MSCA-ITN 812880 Nowelties.

Kinetic study of the combustion of organophosphorus compounds

The thermochemistry and kinetics of organophosphorus compounds were studied, with BAC-MP4 method estimations as a basis and PM3 semi-empirical estimations for many new compounds. New group additivity values were proposed for enthalpies of formation at 298 K, and entropies and heat capacities of species involving pentavalent phosphorus bonded to carbon, hydrogen, oxygen, fluorine, nitrogen, and sulfur atoms. The kinetic features of unimolecular elimination were investigated by modeling pyrolysis experiments of dimethyl ethyl phosphonate (DEMP), triethyl phosphate (TEP), and di-isopropyl methyl phosphonate (DIMP). Rate constants were proposed for four- and six-center eliminations. A new combustion mechanism was developed in a systematic and comprehensive way and involved 41 phosphorus compounds in 202 reactions. All possible intermediates were taken into account. This reaction mechanism was applied to the modeling of H2/O2 flames doped with dimethyl methyl phosphonate (DMMP) and trimethyl phosphate (TMP), which are chemical warfare surrogates. The promoting effect of the agent and the species profiles were correctly reproduced. The decomposition reaction channels were studied: they included radical reactions and molecular eliminations. The cause of the increase of the reactivity of the flame was attributed to some radical combination cycles leading to an increase of heat release, which enhances the global reaction rate in spite of the radical concentration drop.

The destruction of chemical warfare surrogates and subsequent phosphorus distribution during gasification

The ChemChar process enables gasification of a wide variety of liquid and sludge wastes on a readily handled macroporous granular char. The process produces combustible gas products, largely retains metals and halides on the char matrix, and effectively destroys organohalides without producing SOX, NOX, chlorinated dibenzodioxins or chlorinated dibenzoflirans (which can occur with incineration). To study chemical warfare agent wastes under gasification conditions, the destruction removal efficiencies (DRE) of the chemical warfare surrogates parathion and diethylchlorothiophosphate were determined. DREs of > 99.9996 % and > 99.99998 % were found for parathion and diethylchlorothiophosphate, respectively. Additionally, a study of the distribution of radiolabeled phosphorus (P‐32) after gasification of parathion and tributylphosphate showed essentially complete retention of the phosphorus within the gasification system. This study illustrates that the ChemChar gasification process holds significant promise as an alternative to incineration for the safe and complete destruction of chemical warfare agent wastes.