Stability of nitroaromatic specialty explosives in reversed-phase liquid chromatographic systems.

In this study, the stability of 2,4-dinitroanisole, 2,2',4,4',6,6'-hexanitrodiphenylsulfide, 2,3,4,6-tetranitroaniline, 2,4,6-trinitroaniline, 2,4,6-trinitroanisole, and 2,4,6-trinitrochlorobenzene in liquid chromatographic systems was studied under different solvent/eluent conditions. Stock solutions of the explosives were prepared in acetonitrile and diluted with acetone/water, acetonitrile/water, or methanol/water mixtures. Within 48h, these working solutions were repeatedly injected onto a silica column and eluted with acetonitrile/water or methanol/water mobile phases. Under all conditions, 2,4-dinitroanisole was stable, whereas 2,4,6-trinitroaniline was stable only in the methanol/water system. Regarding the other compounds, a more or less pronounced decomposition occurred making the reversed-phase high-performance liquid chromatography analysis difficult or even impossible. The stock standards of 2,4-dinitroanisole and 2,4,6-trinitroaniline were stable for at least 12 months. In addition, some leachate samples were collected from a former explosive factory in Germany and analyzed for nitroaromatic compounds. 2,4,6-Trinitroaniline was detected at concentrations of 60.7-245.5 microg/l.

Exposure assessment of a burning ground for chemical ammunition on the Great War battlefields of Verdun.

The destruction of arsenical shells from the 1914/18 war in the vicinity of Verdun (France) during the 1920s resulted in a locally limited but severe soil contamination by arsenic and heavy metals. At the study site, the main part of the contaminant inventory occurs in the upper 20 cm of the topsoil which is essentially composed of combustion residues. Besides, some Cu (cmax.=16,877 mg/kg) and Pb (cmax.=26,398 mg/kg) in this layer, As (cmax.=175,907 mg/kg) and Zn (cmax.=133,237 mg/kg) were detected in very high concentrations. The mobilities of Cu, Mn, Pb and Zn in the soil system were derived from ammonium nitrate eluates. They are strongly influenced by the soil pH and can be described by quadratic regression curves from which threshold pH values were calculated. Below these values more than 10% of the element content was available as mobile species. Within the examined pH range, this method could not be adopted for arsenic, because the mobility of As was only slightly controlled by the soil pH. In the heavily contaminated topsoil, Cu and Pb were fixed by the moderately acidic soil pH which varied from 4.8 to 5.8. No migration to the underlying horizons occurred. A different behavior was observed for As and Zn. The calculated threshold pH of Zn was 5.5, so certain amount of this element was transferred to the subsoil and the leachate (cmax.=350 microg/l). However, a major dispersion of Zn was prevented by a rise of the soil pH in the carbonate-containing subsoil. Elevated concentrations of As were found in all soil horizons up to a depth of 2 m and also in the leachate (cmax.=2377 microg/l). Contrary to Cu, Pb and Zn the mobility of As evidently was less affected by the subsoil. Regarding organic contaminants, nitroaromatic explosives were detected only in minor concentrations in the soil (cmax.=14.7 mg/kg) and the leachate (cmax.=13.5 microg/l). No aromatic organoarsenicals were detected in the soil and the leachate samples. The main hazard of the site is the severe arsenic contamination and the transfer of this carcinogen by leachate, surface runoff and probably by wind. Nevertheless, some studies on the effects of the contaminant inventory on the local vegetation revealed that ammonium nitrate elutable zinc is responsible for the spatial distribution of some tolerant plant species and not arsenic. Previously undetected buried munitions from the former delaboration facility can be an other source of environmental contaminants. This is supported by elevated concentrations of chlorate (cmax.=71 mg/l) and perchlorate (cmax.=0.8 mg/l) detected in the leachate samples. This is the second report about environmental contamination related to post-war ammunition destruction activities along the 1914/18 Western Front.

TNT transformation products are affected by the growth conditions of Raoultella terrigena.

High concentrations of 2,4,6-trinitrotoluene (TNT) and related nitroaromatic compounds are commonly found in soil and groundwater at former explosive plants. The bacterium, Raoultella terrigena strain HB, isolated from a contaminated site, converts TNT into the corresponding amino products. Radio-HPLC analysis with [(14)C]TNT identified aminodinitrotoluene, diaminonitrotoluene and azoxy-dimers as the main metabolites. Transformation rate and the type of metabolites that predominated in the culture medium and within the cells were significantly influenced by the culture conditions. The NAD(P)H-dependent enzymatic reduction of nitro-substituted compounds by cell-free extracts of R. terrigena was evaluated in vitro.

Determination of mono-, di- and trinitronaphthalenes in soil samples contaminated by explosives.

We investigated the extraction of eight mono-, di- and trinitronaphthalenes from soil samples by ultrasonic, respectively, soxhlet extraction. Sonication was the more convenient procedure with a usually higher repeatability than the soxhlet method. All extracts were analysed by high-performance liquid chromatography with diode array detection. These methods were used to determine the concentration of nitronaphthalenes in five soil samples polluted by explosives. The most abundant contaminants were 1,5- and 1,8-dinitronaphthalene as well as 1,3,5-, 1,3,8- and 1,4,5-trinitronaphthalene. In all samples the sum of trinitronaphthalenes exceeded the sum of mono- and dinitronaphthalenes. It is recommendable to include these eight compounds in the analytical exploration of sites contaminated by explosives.