Transport of insensitive munitions constituents, NTO, DNAN, RDX, and HMX in runoff and sediment under simulated rainfall.

Insensitive munition constituents derived from residues of low order detonations and deposited on military training grounds present environmental risks. A series of rainfall simulation experiments on small soil plots examined the effect of precipitation, soil properties, and particle size on transport of IMX-104 munition components: NTO (3-nitro-1,2,4-triazol-5-one), DNAN (2,4-dinitroanisole), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and HMX (octahydro-1,3,5,7- tertranitro-1,3,5,7-tetrazocine). The primary pathways for rainfall driven transport were subsurface infiltration, off-site transport in solution, and transport in solid form including re-adsorption onto soil particles. The transport was solubility dependent with NTO moving mostly in solution, which was dominated by either runoff or infiltration depending on soil. DNAN, RDX, and HMX, were transported primarily in particulate form. The fine energetic fraction (<2 mm) showed the highest mobility, while the coarsest fraction (>4.75 mm) remained in-situ after rainfall. A simple linear model relating energetics transport with sediment yield and energetics particle size and was proposed. These findings provide the first comprehensive mass balance of munition constituents as affected by overland flow under rainfall. They improve our understanding of environmental fate of munitions, can further be used for predictive modelling, developing mitigation strategies, and regulatory compliance.

Outdoor dissolution and photodegradation of insensitive munitions formulations IMX-101 and IMX-104: Photolytic transformation pathway and mechanism study.

New munition compounds have been developed to replace traditional explosives to prevent unintended detonations. However, insensitive munitions (IM) can leave large proportion of unexploded charge in the field, where it is subjected to photodegradation and dissolution in precipitation. The photolytic reactions occurring on the surfaces of IMX-101 and IMX-104 formulations and the subsequent fate of photolytic products in the environment were thoroughly investigated. The constituents of IMX-101 and IMX-104 formulations dissolve sequentially under rainfall in the order of aqueous solubility: 3-nitro-1,2,4-triazol-5-one (NTO) > nitroguanidine (NQ) > 2,4-dinitroanisole (DNAN) > 1,3,5-hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). A linear relationship between DNAN dissolution and rainwater volume was observed (r2: 0.86-0.99). It was estimated that it would take 16-228 years to completely dissolve these formulation particles under natural environmental conditions in Oracle, AZ. We used LC/MS/MS and GC/MS to examine the dissolution samples from IMX-101 and 104 particles exposed to rainfall and sunlight and found six DNAN photo-transformation products including 2-methoxy-5-nitrophenol, 4-methoxy-3-nitrophenol, 4-methoxy-3-nitroaniline, 2-methoxy-5-nitroaniline, 2,4-dinitrophenol, and methoxy-dinitrophenol, which are in good agreement with computational modeling results of bond strengths. The main DNAN photodegradation pathways are therefore proposed. Predicted eco-toxicity values suggested that the parent compound DNAN, methoxy-nitrophenols, methoxy-nitroanilines and the other two products (2,4-dinitrophenol and methoxy-dinitrophenol) would be harmful to fish and daphnid. Our study provides improved insight about the rain dissolution and photochemical behavior of IM formulations under natural conditions, which helps to form target-oriented strategies to mitigate explosive contamination in military training sites.

Ecosystem-bedrock interaction changes nutrient compartmentalization during early oxidative weathering.

Ecosystem-bedrock interactions power the biogeochemical cycles of Earth's shallow crust, supporting life, stimulating substrate transformation, and spurring evolutionary innovation. While oxidative processes have dominated half of terrestrial history, the relative contribution of the biosphere and its chemical fingerprints on Earth's developing regolith are still poorly constrained. Here, we report results from a two-year incipient weathering experiment. We found that the mass release and compartmentalization of major elements during weathering of granite, rhyolite, schist and basalt was rock-specific and regulated by ecosystem components. A tight interplay between physiological needs of different biota, mineral dissolution rates, and substrate nutrient availability resulted in intricate elemental distribution patterns. Biota accelerated CO2 mineralization over abiotic controls as ecosystem complexity increased, and significantly modified the stoichiometry of mobilized elements. Microbial and fungal components inhibited element leaching (23.4% and 7%), while plants increased leaching and biomass retention by 63.4%. All biota left comparable biosignatures in the dissolved weathering products. Nevertheless, the magnitude and allocation of weathered fractions under abiotic and biotic treatments provide quantitative evidence for the role of major biosphere components in the evolution of upper continental crust, presenting critical information for large-scale biogeochemical models and for the search for stable in situ biosignatures beyond Earth.

Ecosystem Composition Controls the Fate of Rare Earth Elements during Incipient Soil Genesis.

The rare earth elements (REE) are increasingly important in a variety of science and economic fields, including (bio)geosciences, paleoecology, astrobiology, and mining. However, REE distribution in early rock-microbe-plant systems has remained elusive. We tested the hypothesis that REE mass-partitioning during incipient weathering of basalt, rhyolite, granite and schist depends on the activity of microbes, vascular plants (Buffalo grass), and arbuscular mycorrhiza. Pore-water element abundances revealed a rapid transition from abiotic to biotic signatures of weathering, the latter associated with smaller aqueous loss and larger plant uptake. Abiotic dissolution was 39% of total denudation in plant-microbes-mycorrhiza treatment. Microbes incremented denudation, particularly in rhyolite, and this resulted in decreased bioavailable solid pools in this rock. Total mobilization (aqueous + uptake) was ten times greater in planted compared to abiotic treatments, REE masses in plant generally exceeding those in water. Larger plants increased bioavailable solid pools, consistent with enhanced soil genesis. Mycorrhiza generally had a positive effect on total mobilization. The main mechanism behind incipient REE weathering was carbonation enhanced by biotic respiration, the denudation patterns being largely dictated by mineralogy. A consistent biotic signature was observed in La:phosphate and mobilization: solid pool ratios, and in the pattern of denudation and uptake.

Vegetation and arthropod responses to wastewater enrichment of a pine forset.

The effects of spraying secondary-treated wastewater on a young pine forest were studied in South Carolina, U.S.A. Soil, herb-shrub layer vegetation and arthropods were analyzed in control, low-spray and high-spray areas to determine the overall impact of four years of chronic nutrient and water enrichment. Spraying had no significant effect on soil organic matter and cation exchange capacity. Soil cation buildups did not occur and cation leaching was evident.Wastewater application produced a more mesic environment and the herb-shrub layer vegetation shifted to an earlier stage in succession. Plant diversity decreased significantly as a few rapidly-growing opportunistic species (e.g., Erechtites hieracifolia, Polygonum pensylvanicum) replaced the more diverse perennial herbshrub layer vegetation of the pine forest. Peak vegetation biomass levels doubled and net primary production rates were 10 times greater in high spray areas. Litter biomass levels, however, did not change significantly. Litter decomposition rates were significantly greater in treated areas which apparently offset the added litter resulting from increased plant production.Arthropod production increased 3-fold in treated areas. All herbivore guilds had higher biomasses that reflected seasonal changes in producer phenology. Total arthropod diversity increased despite the lower vegetation diversity in spray areas. Arthropod diversity apparently increased because of greater resource availability in treated areas.

The old and the new physical anthropology in the careers of E. A. Hooton and W. M. Krogman.

Physical anthropology changed many of its theoretical premises after World War II under the influence of the synthetic theory of evolution. Earnest Albert Hooton (1887-1954) and Wilton Marion Krogman (1903-1987) were excellent examples of leading workers whose research orientations differed, but whose students were important parts of the new consensus. These theoretical innovations undermined the racial morphological typology which underlay much of Hooton's work on racial history, and radiographs of the sizes of bone, marrow, muscle, and fat in the human brachium undermined his work and researches of other constitutionalists and increased the prestige of alternative work on body composition. Krogman, however, initially worked on the growth of the skull and dentition of the great apes and was a leader in human growth studies all his life. He was the most important writer in the United States on forensic applications of human skeletal biology. Since neither growth studies nor forensic applications depended much on typology, Krogman's publications were generally more modern than Hooton's. In terms of parsimony, Hooton's works can be criticized in terms of his cumbersome typology, but not his ideas on arborealism and the adaptive radiation of the primates. Krogman's interest in roentgenographic cephalometry may have been motivated by a concern for parsimonious explanations of craniofacial growth. Indeed, research in the new physical anthropology can truly be said to stand on the shoulders of these two giants.