Determining degradation kinetics, byproducts and toxicity for the reductive treatment of Nitroguanidine (NQ) by magnesium-based bimetal Mg/Cu.

Energetic-laden process water from industrial munition facilities can be treated by zero-valent metals (ZVMs) or zero-valent iron (ZVI) to remove residual energetics. This reduction-based treatment is significantly enhanced with the addition of a secondary catalytic metal (i.e. forming a bimetal reagent). The reagent is further enhanced by using a more reductive base metal, such as Mg. In this work, the reductive degradation of nitroguanidine (NQ) in aqueous solutions by Mg/Cu bimetal is investigated. Two initial pH conditions (unadjusted and pH 2.7) were studied. Under unadjusted initial pH conditions, 90% of NQ degraded within 30 min reaction time. After 150 min, NQ degradation generated a suite of products including guanidine (44%), cyanamide (31%), formamide (15%), aminoguanidine (AQ) (6%), urea (2%) and cyanoguanidine (0.03%), leading to 100.0% carbon closure when accounting for residual NQ. The experimentally-derived degradation reaction pathway consisted of two parallel reactions: nitroreduction led to formation of AQ with further degradation to urea, cyanamide and formamide, or reductive cleavage of the N-N bond led to guanidine formation. Toxicological assessments indicated only cyanamide and AQ were toxic to S. obliquus at certain concentrations. A lowered initial pH promoted AQ transformation to benign formamide, thus reducing toxicity and complexity of products.

Characteristics and products of the reductive degradation of 3-nitro-1,2,4-triazol-5-one (NTO) and 2,4-dinitroanisole (DNAN) in a Fe-Cu bimetal system.

It has been shown previously that, under acidic conditions, 3-nitro-1,2,4-triazol-5-one (NTO) and 2,4-dinitroanisole (DNAN) degrade in the presence of iron/copper bimetal particles; the reactions can be modeled by pseudo-first-order kinetics. This study investigates the reaction mechanisms of the degradation processes under different conditions. Batch studies were conducted using laboratory-prepared solutions and an industrial insensitive munition-laden (IMX) wastewater. The influence of parameters such as initial pH of the solution, copper/iron (Fe-Cu) contact, and solid/liquid ratio were systematically investigated to assess their impact on the reaction kinetics. These parameters were subsequently incorporated into pseudo-first-order decomposition models for NTO and DNAN. The activation energies for the degradation reactions were 27.40 and 30.57 kJ mol-1, respectively. Degradation intermediates and products were identified. A nitro-to-amino pathway, which ultimately may lead to partial mineralization, is postulated. The amino intermediate, aminonitroanisole, was detected during DNAN degradation, but for NTO, aminotiazolone is suggested. Additionally, urea was identified as a degradation product of NTO.

A review of tungsten: from environmental obscurity to scrutiny.

Since its discovery, tungsten, a transition element of Group VIb of the Periodic Table of Elements, and its compounds have been considered environmentally benign. Its presence in biological and drinking water samples in Fallon, Nevada, an acute lymphocytic leukemia cluster struck community has alarmed public health, environmental and regulatory agencies. Tungsten, a metal of extraordinary properties that make it hardly substitutable, is considered an essential commodity with a wide variety of uses stretching from household necessities to highly specialized applications. This work is undertaken in order to explore aspects of environmental behavior of tungsten and its compounds. Occurrence data in terrestrial, atmospheric, aquatic and biotic systems are presented. Various aspects of environmental chemistry, fate transport across environmental interfaces and toxicology are discussed with the objective of identifying knowledge gaps and outlining directions for future research.

Kinetics of the alkaline hydrolysis of nitrocellulose.

Cellulose nitrate (nitrocellulose) is an explosive solid substance used in large quantities in various formulations of rocket and gun propellants. Safe destruction of nitrocellulose can be achieved by alkaline hydrolysis, which converts it to biodegradable products that can then be treated by conventional biological processes. The kinetics of the alkaline hydrolysis of munitions-grade nitrocellulose in sodium hydroxide solutions were investigated in completely mixed batch reactors. Experiments were conducted using solutions of alkaline strength ranging from 0.1 to 15% by mass and temperatures in the range of 30 to 90 degrees C. Regression analysis of the kinetic data revealed that alkaline hydrolysis of nitrocellulose is of the order 1.0 and 1.5 with respect to nitrocellulose and hydroxide concentration, respectively. The activation energy of the hydrolysis reaction was found to be 100.9 kJ/mol with a preexponential Arrhenius constant of 4.73 x 10(13). Nitrite and nitrate, in a 3:1 ratio, were the primary nitrogen species present in the posthydrolysis solution. The kinetic information is pertinent to the development and optimization of nitrocellulose chemical-biological treatment systems.