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This report details a study investigating the environmental impacts associated with the development and manufacturing of carbon nanotube (CNT)–based ink (called CNTRENE 1030 material) and novel CNT temperature, flex, and moisture sensors. Undertaken by a private-public partnership involving Brewer Science (Rolla, Missouri), Jordan Valley Innovation Center of Missouri State University (Springfield, Missouri), and the US Army Engineer Research and Development Center (Vicksburg, Mississippi), this work demonstrates the environmental life cycle assessment (ELCA) methodology as a diagnostic tool to pinpoint the particular processes and materials posing the greatest environmental impact associated with the manufacture of the CNTRENE material and CNT-based sensor devices. Additionally, ELCA tracked the degree to which optimizing the device manufacturing process for full production also changed its predicted marginal environmental impacts.

Modeling contaminant sorption data using a linear model is very common; however, the rationale for whether the y-intercept should be constrained or not remains a subject of debate. This article justifies constraining the y-intercept in the linear model to zero. By doing so, one imposes consistency on the system of linear equations, allowing for direct comparison of the sorption coefficients., Organic contaminants; Linear sorption modeling; Distribution coefficient; System of consistent linear equations; Homogeneous system of linear equations; Surface chemistry; Soil chemistry; Soil pollution; Environmental pollution; Contaminant transport; Environmental science

After nearly a century of use in numerous munition platforms, TNT and RDX contamination has turned up largely in the environment due to ammunition manufacturing or as part of releases from low-order detonations during training activities. Although the basic knowledge governing the environmental fate of TNT and RDX are known, accurate predictions of TNT and RDX persistence in soil remain elusive, particularly given the universal heterogeneity of pedomorphic soil types. In this work, we proposed overcoming this problem by considering the environmental persistence of these munition constituents (MC) as multivariate mathematical functions over a variety of taxonomically distinct soil types, instead of a single constant or parameter of a specific absolute value. To test this idea, we conducted experiments where the disappearance kinetics of TNT and RDX were measured over a >300 h period in taxonomically distinct soils. Classical fertility-based soil measurements were log-transformed, statistically decomposed, and correlated to TNT and RDX disappearance rates ( k -TNT and k -RDX ) using multivariate dimension-reduction and correlation techniques. From these efforts, we generated multivariate linear functions for k parameters across different soil types based on a statistically reduced set of their chemical and physical properties: Calculations showed that the soil properties exhibited strong covariance, with a prominent latent structure emerging as the basis for relative comparisons of the samples in reduced space. Loadings describing TNT degradation were largely driven by properties associated with alkaline/calcareous soil characteristics, while the degradation of RDX was attributed to the soil organic matter content – reflective of an important soil fertility characteristic. In spite of the differing responses to the munitions, batch data suggested that the overall nutrient dynamics were consistent for each soil type, as well as readily distinguishable from the other soil types used in this study. Thus, we hypothesized that the latent structure arising from the strong covariance of full multivariate geochemical matrix describing taxonomically distinguished “soil types” may provide the means for potentially predicting complex phenomena in soils.

After nearly a century of use in numerous munition platforms, TNT and RDX contamination has turned up largely in the environment due to ammunition manufacturing or as part of releases from low-order detonations during training activities. Although the basic knowledge governing the environmental fate of TNT and RDX are known, accurate predictions of TNT and RDX persistence in soil remain elusive, particularly given the universal heterogeneity of pedomorphic soil types. In this work, we proposed a new solution for modeling the sorption and persistence of these munition constituents as multivariate mathematical functions correlating soil attribute data over a variety of taxonomically distinct soil types to contaminant behavior, instead of a single constant or parameter of a specific absolute value. To test this idea, we conducted experiments measuring the sorption of TNT and RDX on taxonomically different soil types that were extensively physical and chemically characterized. Statistical decomposition of the log-transformed, and auto-scaled soil characterization data using the dimension-reduction technique PCA (principal component analysis) revealed a strong latent structure based in the multiple pairwise correlations among the soil properties. TNT and RDX sorption partitioning coefficients (KD-TNT and KD-RDX) were regressed against this latent structure using partial least squares regression (PLSR), generating a 3-factor, multivariate linear functions. Here, PLSR models predicted KD-TNT and KD-RDX values based on attributes contributing to endogenous alkaline/calcareous and soil fertility criteria, respectively, exhibited among the different soil types: We hypothesized that the latent structure arising from the strong covariance of full multivariate geochemical matrix describing taxonomically distinguished soil types may provide the means for potentially predicting complex phenomena in soils. The development of predictive multivariate models tuned to a local soil's taxonomic designation would have direct benefit to military range managers seeking to anticipate the environmental risks of training activities on impact sites.

Soil heterogeneity is a major contributor to the uncertainty in predicting the environmental fate of data-scare contaminants. For this paper, we focused on research designed to predict the soil environmental fate of the new munition compound, called 2,4-dinitroanisole (DNAN) -a compound increasingly employed by the U.S. and international militaries in the next-generation, insensitive explosive formulations. Here, we employed multivariate statistical correlation models to predict DNAN sorption among different soil “types” seeking to reduce the uncertainty common in all contaminant sorption models by using soil taxonomic designation as a calibrant. We collected composite soils classified under the Ultisols taxonomic Order in the U.S. National Resource Conservation Service soil classification system and quantified their properties via physical and chemical characterizations. Using multivariate statistical modeling modified for compositional data analysis (CoDa), we developed quantitative analogies of the Ultisols by partitioning the characterization data up into four different compositions: Water-extracted, Mehlich-III (referring to the weak acid) extracted, particle-size distribution, and solid-phase carbon‑nitrogen‑sulfur compositions. DNAN sorption was measured in batch soil suspensions and distribution coefficients (KD) were calculated using linear regression modeling. Prediction models testing the correlation of the DNAN KD values to the centered logratio -transformed compositions were calculated using CoDa-modified multilinear regression. Results showed that DNAN sorption was only predictable by dissolved organic carbon, pH, and the exchangeable cations Ca and K within the water-extracted composition. Analogies for DNAN sorption were the most discriminating at the Suborder level because of the inherent ambiguity in the Hapludults class at the Great Group level.

Underwater military munitions (UWMM) may pose a risk to aquatic environments because they typically contain munitions constituents (MC) such as 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). If UWMM become corroded or breaches, the fill material may leak or dissolve into the surrounding environment, which could potentially adversely affecting affect the exposed biota. In large part, because of the high cost and complexity associated with sampling MC at UWMM sites, detailed and reliable information about MC in water, sediment, and biota is available for only a few sites, and therefore temporal and spatial uncertainties persist. Examination of available data indicates that concentrations of MC in water and sediment were largely below detection or were relatively low (e.g., parts per billion), with higher concentrations being highly localized and typically near a point source. These findings were in accordance with predictive modeling and with fate studies. Available toxicity data derived for a variety of freshwater and marine species were compiled and used to derive interim water quality criteria and protective values derived from species sensitivity distributions. Toxicity varied widely across a diversity of MC and species. For most aquatic sites, MC contamination in sediment and in the water-column presents low risk to the resident biota.

Soil heterogeneity is a major contributor to the uncertainty in near-surface biogeochemical modeling. We sought to overcome this limitation by exploring the development of a new classification analogy concept for transcribing the largely qualitative criteria in the pedomorphologically based, soil taxonomic classification systems to quantitative physicochemical descriptions. We collected soil horizons classified under the Alfisols taxonomic Order in the U.S. National Resource Conservation Service (NRCS) soil classification system and quantified their properties via physical and chemical characterizations. Using multivariate statistical modeling modified for compositional data analysis (CoDA), we developed quantitative analogies by partitioning the characterization data up into three different compositions: Water-extracted (WE), Mehlich-III extracted (ME), and particle-size distribution (PSD) compositions. Afterwards, statistical tests were performed to determine the level of discrimination at different taxonomic and location-specific designations. The analogies showed different abilities to discriminate among the samples. Overall, analogies made up from the WE composition more accurately classified the samples than the other compositions, particularly at the Great Group and thermal regime designations. This work points to the potential to quantitatively discriminate taxonomically different soil types characterized by varying compositional datasets.

This work seeks to understand how the balance of abiotic and biotic kinetic processes in sediments control the residual concentration of TNT in marine systems after release from ocean-dumped source. Kinetics of TNT disappearance were followed using marine sediments at different temperatures and under both biotic and presumably abiotic conditions (through sodium azide addition). Sediments exhibiting the highest rate of TNT disappearance under biotic conditions also exhibited the highest sorption affinity for TNT under abiotic conditions. Significant temperature dependence in the abiotic processes was observed in the diffusion coefficient of TNT and not sediment sorption affinity. At higher temperature, kinetics of biotic processes outpaced abiotic processes, but at low temperature, kinetics of abiotic processes were much more significant. We concluded that the differential influence of temperature on the kinetics of abiotic and biotic processes could provide distinguishing predictions for the potential residual concentration of TNT contamination in marine-sediment systems.

This paper focuses on the chemistry of DoD-relevant organic contaminants in soil. Most of the work presented here is based on the author’s experience with the environmental fate of the munition constituents, TNT and RDX, for DoD related issues. The principles and challenges of understanding the transport of nitrobenzene and triazine compounds in the environment are captured. In this work, disparities in the current scientific literature with respect to the construction of sorption experiments are discussed, in terms of soil sample handling, dispersion state of the soil, and sorption hysteresis/equilibrium. Here is discussed the concept of environmentally formulated compounds and its implications toward reduced accuracy of predicting the environmental fate of munition constituents. Also, further research linking simple but oft-forgotten basic concepts of soil fertility to the transport and environmental fate of munition constituents are discussed.

BACKGROUND: Blood transfusion therapy is an established treatment for primary and secondary prevention of strokes in children with sickle cell disease (SCD), a disease that predominantly affects African Americans. African American blood donors are more likely to have compatible minor red blood cell antigens for children with SCD who routinely receive transfusions. This study tested the hypothesis that when informed at church about the importance of blood donation, African Americans will have a higher than expected rate of first-time blood donation compared to the general population. STUDY DESIGN AND METHODS: The Sickle Cell Sabbath Program was developed to increase awareness about SCD and the importance of blood donations within the African American faith community. Church involvement in the program included a 5-minute scripted educational session about SCD that included the importance of blood donations followed by a blood donor drive that was hosted by the church. RESULTS: Thirteen African American churches sponsored 34 blood drives from 2003 through 2006. Each church sponsored at least two blood drives. Approximately 1200 donors participated in the sickle cell blood drives. The majority of the donors were first-time donors and represented a greater than expected first-time donor rate when compared to first-time donors in the metropolitan St Louis area, 60 percent (422 of 699) and 12.2 percent (21,516 of 175,818), respectively (p = 0.001). CONCLUSION: An educational program that engages the African American faith community more than quadruples the rate of expected first-time blood donors when compared to the general community over this 4-year period.

Objective: To test the hypothesis that children with sickle cell disease (SCD) who have an initial stroke temporally unrelated to another medical event are at higher risk for recurrent stroke than are children who had strokes temporally related to medical events. Methods: A retrospective cohort study of children with SCD and stroke who received regularly scheduled blood transfusions for a minimum of 5 years was conducted. Medical records were examined for the documentation of antecedent or concurrent medical events (hypertension, acute chest syndrome, aplastic crisis, fever associated with infection, exchange transfusion) associated with physician contact within 14 days before the initial stroke. Results: A total of 137 pediatric patients from 14 centers were studied. Mean age at first stroke was 6.3 years (1.4 to 14.0 years) with mean follow-up of 10.1 years (5 to 24 years). Thirty-one (22%) patients had a second stroke (2.2 per 100 patient years); 26 patients had an identified medical or concurrent event associated with their initial stroke. None of these patients had recurrent stroke 2 or more years after the initial event. The remaining 111 patients had an ongoing risk of recurrent stroke (1.9 per 100 patient-years) despite long-term transfusions ( P = .038). Conclusions: The absence of an antecedent or concurrent medical event associated with an initial stroke is a major risk factor for subsequent stroke while receiving regular transfusions. (J Pediatr 2002;140:348-54)

Selenium (Se) chemistry can be very complex in the natural environment, exhibiting different valence states (−2, 0, +4, +6) representing multiple inorganic, methylated, or complexed forms. Since redox associated shifts among most of known Se species can occur at environmentally relevant conditions, it is important to identify these species in order to assess their potential toxicity to organisms. In June of 2009, researchers from the US Army Engineer Research & Development Center (ERDC) conducted investigations of the fly ash spilled 6 months previously into the Emory River at the TVA Kingston Fossil Plant, TN. Ash samples were collected on site from both the original ash pile (that did not move during the levee failure), from the spill zone (including the Emory River), and from the ash recovery ditch (ARD) containing ash removed during dredging cleanup operations. The purpose of this work was to determine the state of Se in the spilled fly ash and to assess its potential for transformation and resultant chemical stability from its prolonged submersion in the river and subsequent dredging. Sequential chemical extractions suggested that the river environment shifted Se distribution toward organic/sulfide species. Speciation studies by bulk XANES analysis on fly ash samples showed that a substantial portion of the Se in the original ash pile had transformed from inorganic selenite to a mixture of Se sulfide and reduced (organo)selenium (Se(-II)) species over the 6-month period. μ-XRF mapping data showed that significant trends in the co-location of Se domains with sulfur and ash heavy metals. Ten-d extended elutriate tests (EETs) that were bubbled continuously with atmospheric air to simulate worst-case oxidizing conditions during dredging showed no discernible change in the speciation of fly ash selenium. The enhanced stability of the organo- and sulfide-selenium species coincided with the mixture of the ash material with humic materials in the river, corresponding with notable shifts in the ash carbon- and nitrogen-functionality.

Preface 1. Solid-Phase Considerations for the Environmental Fate of TNT and RDX in Soil Mark A. Chappell Environmental Assesments 2. Environmental Assessment of Small Arms Live Firing: Study of Gaseous and Particulate Residues S. Brochu, I. Poulin, D. Faucher, E. Diaz, and M. R. Walsh 3. Canadian Approach to the Environmental Characterization and Risk Assessment of Military Training S. Brochu, S. Thiboutot, G. Ampleman, E. Diaz, I. Poulin, and R. Martel 4. The Use of Conventional and Surface Enhanced Raman Spectroscopy to Evaluate Chemistries for the Detection and/or Remediation of Pechlorate in Aqueous Systems P. A. Mosier-Boss 5. Assessing Sample Processing and Sampling Uncertainty for Energetic Residues on Military Training Ranges: Method 8330B Marianne E. Walsh, Alan D. Hewitt, Thomas F. Jenkins, Charles A. Ramsey, Michael R. Walsh, Susan R. Bigl, Charles M. Collins, and Mark A. Chappell 6. Energetic Residue Observations for Operational Ranges J. L. Clausen Properties, Reactions, and Environmental Fate 7. Dissolution of High Explosives on Range Soils Susan Taylor, James H. Lever, Jennifer Fadden, Susan R. Bigl, Nancy M. Perron, Kathleen F. Jones, and Bonnie Packer 8. Photolysis of 2,4,6-Trinitrotoluene in Seawater: Effect of Salinity and Nitrate Concentration Daniel W. O'Sullivan, Jeffrey R. Denzel, and Dianne J. Luning Prak 9. 2,4,6-Trinitrotoluene Mineralization and Incorporation by Natural Bacterial Assemblages in Coastal Ecosystems Michael T. Montgomery, Thomas J. Boyd, Joseph P. Smith, Shelby E. Walker, and Christopher L. Osburn 10. TNT, RDX, and HMX Association with Organic Fractions of Marine Sediments and Bioavailability Implications Judith C. Pennington, Guilherme Lotufo, Charolett A. Hayes, Beth Porter, and Robert D. George 11. The Fate of Nitroaromatic (TNT) and Nitramine (RDX and HMX) Explosive Residues in the Presence of Pure Metal Oxides Thomas A. Douglas, Marianne E. Walsh, Christian J. McGrath, Charles A. Weiss, Jr., Ashley Marie Jaramillo, and Thomas P. Trainor 12. Soil Vadose Zone Chemistry of TNT and RDX Under Water-Saturated Conditions Mark A. Chappell, Cynthia L. Price, Gerald G. Bourne, Brad A. Pettway, and Beth E. Porter 13. Transport of RDX and TNT from Composition-B Explosive During Simulated Rainfall Richard A. Price, Michelle Bourne, Cynthia L. Price, Jay Lindsay, and Jim Cole 14. The Contaminant Transport, Transformation, and Fate Sub-Model for Predicting the Site-Specific Behavior of Distributed Sources (Munitions Constituents) on U.S. Army Training and Testing Ranges Zhonglong Zhang and Billy E. Johnson 15. Fate and Transport of Energetics from Surface Soils to Groundwater J. L. Clausen and Nic Korte 16. Release Rate and Transport of Munitions Constituents from Breached Shells in Marine Environment Pei-Fang Wang, Qian Liao, Robert George, and William Wild Remediation Options and Technologies 17. Degradation Products of TNT after Fenton Oxidation in the Presence of Cyclodextrins Curt W. Jarand, Kan Chen, Boguslaw Pozniak, Richard B. Cole, Duc-Truc Pham, Stephen F. Lincoln, and Matthew A. Tarr 18. Potential Anaerobic Bioremediation of Perchlorate-Contaminated Soils through Biosolids Applications Cynthia L. Price, Mark A. Chappell, Brad A. Pettway, and Beth E. Porter 19. Effects of Wildfire and Prescribed Burning on Distributed Particles of Composition-B Explosive on Training Ranges Richard A. Price and Michelle Bourne 20. Remediation of Surface Soils Contaminated with Energetic Materials by Thermal Processes Isabelle Poulin 21. Residual Dinitrotoluenes from Open Burning of Gun Propellant Emmanuela Diaz, Sylvie Brochu, Isabelle Poulin, Dominic Faucher, Andre Marois, and Annie Gagnon Editors' Biographies Indexes Author Index Subject Index

The premise of the nanotechnology revolution is based on the increased surface reactivity of nanometer-sized particles. Thus, these newly realized applications of noble metal nanoparticles introduce new concerns about the environmental fate of these materials if released during use or product disposal. In this paper, the focus is on silver nanoparticles, a known biocidal agent. In particular, this work explores the effect of model solutes chosen for their simple chemical structure yet their ability to simulate chemical attributes common to soil humic material: a chelating molecule, EDTA; a nonionic surfactant, Brij 35; and a large polysaccharide, alginic acid. Batch systems containing concentrated (1600 mg L −1 ) silver nanoparticle (nAg) suspensions were equilibrated with varying additions of EDTA, Brij 35, or alginic acid to solutions containing 1 or 100 mM NaNO 3 background electrolyte. In general, both EDTA and alginate were shown to exhibit poor control over nAg dispersion stability, while Brij 35 served as a good dispersant of nAg particles, showing little difference in particle size with respect to electrolyte concentration. The data also show that loading of the model organic compounds resulted in the supersaturation of dissolved Ag for most of the systems. Mechanisms by which these occurred are discussed in more detail. The evidence suggests that regardless of the effect of humics on the stability of nAg dispersions in aqueous systems, polymer loading may enhance the dissolution and release of dissolved Ag into the environment.

Environmental context Nanometre-sized silver particles promote unique chemical reactions on their surface. This work examines the ability of silver nanoparticles to collect and store unpaired electrons, called radicals, on their surface. This capability by silver nanoparticles could potentially serve to drive degradation reactions in the environment. Abstract Radicals drive important chemical reactions in the environment. These unpaired electron species can be generated by energetic inputs, such as electromagnetic radiation, or from ultrasonication processes, whereby oxygen radicals are generated in aqueous solution through a cavitation mechanism. Previous evidence has demonstrated the potential for radicals to be stored on the surface of metallic gold nanoparticles, thus suggesting a potential transference of radical species from the nanoparticle surface for catalytic reactions, particularly during preparations of nanoparticle suspensions through ultrasonication. This work investigates the potential for the nanosilver (nAg) particles to similarly scavenge radicals from solution. nAg suspensions were reacted with 0.3-mM solutions containing the stable nitroxy radicals 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPONE) and 4-amino-2,2,6,6-tetramethylpiperidino-1-oxyl (TEMPAMINE) analysed by quantitative electron spin resonance (ESR) spectroscopy. In ambient air, the addition of a nAg suspension to the 0.3-mM solutions reduced the integrated ESR intensity of the stable radicals by 50–93% depending on radical species and nAg concentration, which we attributed to the sorption of the radicals onto the nAg surface. In separate experiments, the ESR intensities were further decreased under an Ar atmosphere, suggesting potential competition from ambient OH• to the sorption of the stable radicals. To verify this, we observed substantial increases in the integrated ESR intensity when the systems previously equilibrated under Ar atmosphere were exposed to ambient air. These results demonstrated that nAg scavenged the stable radicals from solution and were exchangeable from the metallic conduction band with OH•. Our work represents the first evidence for this mechanism to be demonstrated for nAg.

This report documents Phases I and II to evaluate the testing and analysis of upland disposal of dredged material from the Appomattox River, Petersburg, VA. Phase I of this study evaluated the environmental and engineering effect of dredging and placing the Appomattox River sediment in the proposed Puddledock site. Phase II of this study evaluated screening of potential contaminate release to atmosphere and evaluated environmental dredging case studies conducted by the U.S. Army Corps of Engineers. The Phase I testing included physical and chemical characterization of the sediment to support design/management operations decision making and contaminant pathway analysis. Additional analyses using characterization data were performed to predict the behavior of the contaminants in various pathways. Phase 11 testing included tests that predict the potential emission release of volatiles during and after dredging. Physical characterization included a number of geotechnical tests including grain-size analyses, Atterberg limits, soil classification, specific gravity, moisture content, self-weight and standard odometer consolidation, and sedimentation testing. Chemical characterization included bulk sediment chemical analysis, toxicity characteristics leaching procedure (TCLP), and ambient water chemical analysis.