Effects of the ZrO2 Crystalline Phase and Morphology on the Thermocatalytic Decomposition of Dimethyl Methylphosphonate.

Thermocatalytic decomposition is an efficient purification technology that is potentially applicable to degrading chemical warfare agents and industrial toxic gases. In particular, ZrO2 has attracted attention as a catalyst for the thermocatalytic decomposition of dimethyl methylphosphonate (DMMP), which is a simulant of the nerve gas sarin. However, the influence of the crystal phase and morphology on the catalytic performance of ZrO2 requires further exploration. In this study, monoclinic- and tetragonal-phase ZrO2 (m- and t-ZrO2, respectively) with nanoparticle, flower-like shape and hollow microsphere morphologies were prepared via hydrothermal and solvothermal methods, and their thermocatalytic decomposition of DMMP was systematically investigated. For a given morphology, m-ZrO2 performed better than t-ZrO2. For a given crystalline phase, the morphology of hollow microspheres resulted in the longest protection time. The exhaust gases generated by the thermocatalytic decomposition of DMMP mainly comprised H2, CO2, H2O and CH3OH, and the by-products were phosphorus oxide species. Thus, the deactivation of ZrO2 was attributed to the deposition of these phosphorous oxide species on the catalyst surface. These results are expected to help guide the development of catalysts for the safe disposal of chemical warfare agents.

A review of organophosphonates, their natural and anthropogenic sources, environmental fate and impact on microbial greenhouse gases emissions - Identifying knowledge gaps.

Organophosphonates (OPs) are a unique group of natural and synthetic compounds, characterised by the presence of a stable, hard-to-cleave bond between the carbon and phosphorus atoms. OPs exhibit high resistance to abiotic degradation, excellent chelating properties and high biological activity. Despite the huge and increasing scale of OP production and use worldwide, little is known about their transportation and fate in the environment. Available data are dominated by information concerning the most recognised organophosphonate - the herbicide glyphosate - while other OPs have received little attention. In this paper, a comprehensive review of the current state of knowledge about natural and artificial OPs is presented (including glyphosate). Based on the available literature, a number of knowledge gaps have been identified that need to be filled in order to understand the environmental effects of these abundant compounds. Special attention has been given to GHG-related processes, with a particular focus on CH4. This stems from the recent discovery of OP-dependent CH4 production in aqueous environments under aerobic conditions. The process has changed the perception of the biogeochemical cycle of CH4, since it was previously thought that biological methane formation was only possible under anaerobic conditions. However, there is a lack of knowledge on whether OP-associated methane is also formed in soils. Moreover, it remains unclear whether anthropogenic OPs affect the CH4 cycle, a concern of significant importance in the context of the increasing rate of global warming. The literature examined in this review also calls for additional research into the date of OPs in waste and sewage and in their impact on environmental microbiomes.

A Nanoporous Polymer Modified with Hexafluoroisopropanol to Detect Dimethyl Methylphosphonate.

The increasing threat of nerve agents has prompted the need for gas sensors with fast response, high sensitivity, and good stability. In this work, the hexafluoroisopropanol functional group was modified on a porous aromatic framework material, which served as a sensitive material for detecting dimethyl methylphosphonate. A nerve agent sensor was made by coating sensitive materials on a surface acoustic wave device. Lots of pores in sensitive materials effectively increase the specific surface area and provide channels for diffusion of gas molecules. The introduction of hexafluoroisopropanols enables the sensor to specifically adsorb dimethyl methylphosphonate and improves the selectivity of the sensor. As a result, the developed gas sensor was able to detect dimethyl methylphosphonate at 0.8 ppm with response/recovery times of 29.8/43.8 s, and the detection limit of the gas sensor is about 0.11 ppm. The effects of temperature and humidity on the sensor were studied. The results show that the baseline of the sensor has a linear relationship with temperature and humidity, and the temperature and humidity have a significant effect on the response of the sensor. Furthermore, a device for real-time detection of nerve agent is reported. This work provides a new strategy for developing a gas sensor for detecting nerve agents.

Effects of dimethyl methylphosphonate (DMMP) and trimethylphosphate (TMP) on spermatogenesis of rat testis

Both dimethyl methylphosphonate (DMMP) and trimethylphosphate (TMP) are organophosphorous compounds that can evoke sterility in male rodents. The following studies examined the pathology of reproductive organ, especially on the testis, by light microscopy after treatment with both agents. Adult male rats were treated per oral with DMMP, 1,750 mg/Kg, for up to 12 weeks and per oral with TMP, 400 mg/Kg for up to 5 weeks. After 5 weeks of treatment with DMMP there were occasional multinucleated giant cells composed of late spermatids in stages X, XI, XII as well as cytoplasmic vacuolation of Sertoli cell. Anachronistic spermiations were seldom, if ever, seen throughout the experiment. After 7 weeks of DMMP those were markedly diminished. The overall changes after treatment with TMP are somewhat similar to those treated with DMMP. The major changes were composed of aggregate of multinucleated giant cells and maturation arrest at spermatid level, which appear immediately after administration of TMP. The peak frequency in the emergence of multinucleated giant cells in treatment with TMP was noted just a week after treatment, but afterwards declined. Maturation arrest was prominent after 3 weeks in the cases treated with TMP.