Environmental context: There is a growing need to understand how insensitive munitions compounds behave in natural environments, particularly in soils, where non-combusted residues accumulate. Here, we tested the ability of sulfate green rust, a naturally occurring mineral, to transform munitions compounds by reacting with the mineral surface. Our results show that both the munitions compounds and the mineral structures are transformed in an oxidation–reduction reaction that alters the compounds’ environmental fates. Abiotic transformation of contaminants by redox-active mineral surfaces plays an important role in the fate and behaviour of pollutants in soils and sediments. However, there is very little information on such transformations for the insensitive munitions compounds (IMCs), 3-nitro-1,2,4-triazol-5-one (NTO) and 2,4-dinitroanisole (DNAN), developed in recent years to replace the traditional munition compounds in explosive mixtures. We tested the ability of sulfate green rust to transform NTO and DNAN (0.5 mM) under anoxic conditions at pH 8.4 in laboratory experiments, by using green rust supplied at 10 g kg-1 (w/w) solid concentration. Results indicate that NTO and DNAN underwent rapid abiotic reduction to their organic amine daughter products. NTO was completely transformed to 5-amino-1,2 4-triazol-3-one (ATO) within 20 min of reaction. This is the first report of NTO reduction by a naturally occurring mineral. Similarly, DNAN was rapidly transformed to 2-methoxy-5-nitroaniline (MENA) and 4-methoxy-5-nitroaniline (iMENA). The reduction occurred with an intriguing staggered regioselectivity. Over the first 10 min, the para-nitro group of DNAN was selectively reduced to generate iMENA. Thereafter, the ortho-nitro group was preferentially reduced, generating MENA. Both iMENA and MENA were subsequently transformed to the final reduction product 2,4-diaminoanisol (DAAN) within 1 day. Iron Ka X-ray absorption near-edge spectroscopy (XANES) studies of reacted solids indicated oxidative transformation of the green rust to lepidocrocite-like mineral forms. These results indicate that the IMCs can be rapidly transformed in soil, sediment or aquatic environments containing green rust.

This research focuses on the efficiency of recommended heavy use area protection (HUAP) pads installed in poultry houses utilizing the Choptank River, a tributary of the Chesapeake Bay. The Chesapeake Bay watershed is severely affected by crop agriculture and poultry feeding operations. Water quality degradation along with scarcity of water is a significant concern in this area, suggesting a need for changes in both environmental and groundwater management practices. Our objective in this study was to compare the efficiency of HUAP in reducing litter spillage and nutrient runoff between two poultry houses, one of which was constructed in 2005 and the other in 2009. The poultry house constructed in 2005 did not have HUAP pads initially; they were built in 2006. The poultry house built in 2009 had the pads from the starting point. We collected soil and water samples each month and analyzed them for pH, electrical conductivity (EC), nitrate, nitrite, total nitrogen, phosphate, and other soil properties throughout the year. The pH of soil and water samples was in the range of 6.8–8.0 and 6.5–7.2, respectively. We collected six water samples in total in the ditch, from points at retention ponds near the farm ditch to sites in wooded areas on the farm. Water sample B (where ditch water meets retention pond water from the poultry farm) had the highest EC value and nitrate, nitrite, and total nitrogen concentrations compared with other water samples. The subsequent water samples downstream had reduced loads of nutrients. The study results suggest that there was a minimum carryover of nutrients from soil into the runoff water, storm ditches, and adjacent stream. There was also a minimal effect of house cleaning and storm events in raising the concentration of nutrients in soil and water samples at our study sites. The older poultry site had higher total nitrogen and phosphorous surrounding the pads, whereas no elevated levels of nutrients were identified at the newer site. The ability of HUAP pads to hold onto contaminates decreases with age and use. This study also shows that the impacts from poultry activities on surface and groundwater can be minimized by using management practices such as HUAP pads. These practices can reduce pollution in the farm, increase productivity, and save farmers and ranchers time and money in the long run.

The application of agrichar derived from organic feedstocks has the potential to improve soil fertility and crop production by providing major nutrients like phosphorus (P) to the crop, and in some cases also reducing P leaching. The effect of agrichar on the leaching of P in soils is not uniform and can vary depending on the type of agrichar and amount applied. The objective of this study was to (i) evaluate the behavior of four agrichars (rice hulls RH, palm fronds PF, horse bedding HB, and bagasse BG) for their ability to retain/release P and (ii) determine the effect of wet sonication on P sorption behavior. The feedstocks were torrefied at 500 °C using a top-lit updraft gasifier and used in multiple batch incubation experiments to evaluate equilibrium phosphorus concentration, maximum P sorption capacity (Smax), and adsorption/desorption potential. Both, RH (12.6 g kg-1) and HB (11.5 g kg-1) contained 10-15 times higher total P concentration than PF and BG, rendering RH and HB as potentially suitable products to be used as soil amendments. However, this initial P content of the agrichar seemed to have an overriding effect on the P sorption behavior of the agrichar. PF had Smax of 676 (±127) mg kg-1 for the non-sonicated agrichar, and 237 (±91) mg kg-1 following sonication. There was significant increase in CEC for PF and BG agrichar upon sonication. PF agrichar increased from 27 (±3) cmolc kg-1 to 41 (±4) cmolc kg-1 with sonication. Similarly, BG agrichar CEC increased from 21 (±2) cmolc kg-1 to 45 (±5) cmolc kg-1 with sonication. Initial total P and Ca concentration and their ratios was found to play significant roles on P adsorption and desorption. Major cations like Ca, Fe, Al and Mn are found to act as active sorption site for phosphorus controlling its fate and mobility along with compounding effects of other physicochemical parameters.