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1.
Glob Chang Biol ; 28(1): 285-295, 2022 01.
Artigo em Inglês | MEDLINE | ID: mdl-34614285

RESUMO

Climate models predict that, in the coming decades, many arid regions will experience increasingly hot conditions and will be affected more frequently by drought. These regions are also experiencing rapid vegetation change, notably invasion by exotic grasses. Invasive grasses spread rapidly into native desert ecosystems due, in particular, to interannual variability in precipitation and periodic fires. The resultant destruction of non-fire-adapted native shrub and grass communities and of the inherent soil resource heterogeneity can yield invader-dominated grasslands. Moreover, recurrent droughts are expected to cause widespread physiological stress and mortality of both invasive and native plants, as well as the loss of soil resources. However, the magnitude of these effects may differ between invasive and native grasses, especially under warmer conditions, rendering the trajectory of vegetated communities uncertain. Using the Biosphere 2 facility in the Sonoran Desert, we evaluated the viability of these hypothesized relationships by simulating combinations of drought and elevated temperature (+5°C) and assessing the ecophysiological and mortality responses of both a dominant invasive grass (Pennisetum ciliare or buffelgrass) and a dominant native grass (Heteropogan contortus or tanglehead). While both grasses survived protracted drought at ambient temperatures by inducing dormancy, drought under warmed conditions exceeded the tolerance limits of the native species, resulting in greater and more rapid mortality than exhibited by the invasive. Thus, two major drivers of global environmental change, biological invasion and climate change, can be expected to synergistically accelerate ecosystem degradation unless large-scale interventions are enacted.


Assuntos
Mudança Climática , Ecossistema , Modelos Climáticos , Clima Desértico , Secas , Poaceae
2.
Chemosphere ; 350: 141023, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38141674

RESUMO

Energetics used in military exercises can potentially contaminate ground and surface waters. This study was conducted to evaluate the movement of Composition B, a formulation that includes TNT (2,4,6-trinitrotoluene), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), in runoff. Mechanisms of transport we examined include movement of energetics dissolved in runoff, as particles and adsorbed to suspended sediment, and in infiltration. Rainfall simulations were conducted under controlled conditions with two rainfall rates (approximately 30 and 50 mm h-1), two soils with different infiltration capacities, and four energetic particle sizes (4.75-9.51 mm, 2.83-4.75 mm, 2-2.83 mm, and <2 mm). Particles remaining on the soil surface after rainfall were measured as well as energetics dissolved in runoff, in suspended sediment, and in infiltration. Greater concentrations of TNT than RDX and HMX were found dissolved in runoff due to its higher solubility and dissolution rates. We also found that particle transport in runoff increased with decrease in particle size. Smaller particle sizes also led to greater transport dissolved in solution. Relationships were found relating runoff and sediment yield to the transport of RDX and TNT. The results of this study allow improved prediction of Composition B transport in runoff and therefore its contamination potential.


Assuntos
Substâncias Explosivas , Trinitrotolueno , Substâncias Explosivas/química , Azocinas/química , Trinitrotolueno/análise , Triazinas/química , Solo
3.
Chemosphere ; 310: 136866, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-36270523

RESUMO

The deposition of explosive contaminants in particulate form onto the soil surface during low-order detonations can lead to ground and surface water contamination. The vertical fate and transport of insensitive munitions formulation IMX-104 through soil has been thoroughly studied, however the lateral transport of explosive particles on the surface is less known. The objective of this research was to understand the impact of overland flow on the transport of IMX-104 constituent compounds 3-nitro-1,2,4-triazol-5-one (NTO), 2,4-dinitroanisole (DNAN), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The effect of overland flow was examined in a rill flume using several flow rates (165-, 265-, and 300-mL min-1) and IMX-104 particle sizes (4.75-9.51 mm, 2.83-4.75 mm, 2-2.83 mm, and <2 mm). We found that the smaller particles were transported more in solution and with the sediment compared to the larger particles, which had a higher percent mass remaining on the surface. As flow rate increased, there was an increase in the percent mass found in solution and sediment and a decrease in the percent mass remaining on the surface. NTO fate was dominated by transport in solution, while DNAN, RDX and HMX were predominantly transported with the sediment. This research provides evidence of the role of overland flow in the fate of energetic compounds.


Assuntos
Substâncias Explosivas , Nitrocompostos , Anisóis , Triazinas , Solo
4.
Sci Total Environ ; 866: 161434, 2023 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-36623648

RESUMO

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.

5.
Nat Commun ; 14(1): 5064, 2023 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-37604817

RESUMO

Drought can affect the capacity of soils to emit and consume biogenic volatile organic compounds (VOCs). Here we show the impact of prolonged drought followed by rewetting and recovery on soil VOC fluxes in an experimental rainforest. Under wet conditions the rainforest soil acts as a net VOC sink, in particular for isoprenoids, carbonyls and alcohols. The sink capacity progressively decreases during drought, and at soil moistures below ~19%, the soil becomes a source of several VOCs. Position specific 13C-pyruvate labeling experiments reveal that soil microbes are responsible for the emissions and that the VOC production is higher during drought. Soil rewetting induces a rapid and short abiotic emission peak of carbonyl compounds, and a slow and long biotic emission peak of sulfur-containing compounds. Results show that, the extended drought periods predicted for tropical rainforest regions will strongly affect soil VOC fluxes thereby impacting atmospheric chemistry and climate.

6.
Appl Environ Microbiol ; 78(21): 7527-37, 2012 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-22885757

RESUMO

High-throughput, culture-independent surveys of bacterial and archaeal communities in soil have illuminated the importance of both edaphic and biotic influences on microbial diversity, yet few studies compare the relative importance of these factors. Here, we employ multiplexed pyrosequencing of the 16S rRNA gene to examine soil- and cactus-associated rhizosphere microbial communities of the Sonoran Desert and the artificial desert biome of the Biosphere2 research facility. The results of our replicate sampling approach show that microbial communities are shaped primarily by soil characteristics associated with geographic locations, while rhizosphere associations are secondary factors. We found little difference between rhizosphere communities of the ecologically similar saguaro (Carnegiea gigantea) and cardón (Pachycereus pringlei) cacti. Both rhizosphere and soil communities were dominated by the disproportionately abundant Crenarchaeota class Thermoprotei, which comprised 18.7% of 183,320 total pyrosequencing reads from a comparatively small number (1,337 or 3.7%) of the 36,162 total operational taxonomic units (OTUs). OTUs common to both soil and rhizosphere samples comprised the bulk of raw sequence reads, suggesting that the shared community of soil and rhizosphere microbes constitute common and abundant taxa, particularly in the bacterial phyla Proteobacteria, Actinobacteria, Planctomycetes, Firmicutes, Bacteroidetes, Chloroflexi, and Acidobacteria. The vast majority of OTUs, however, were rare and unique to either soil or rhizosphere communities and differed among locations dozens of kilometers apart. Several soil properties, particularly soil pH and carbon content, were significantly correlated with community diversity measurements. Our results highlight the importance of culture-independent approaches in surveying microbial communities of extreme environments.


Assuntos
Archaea/classificação , Archaea/genética , Bactérias/classificação , Bactérias/genética , Cactaceae/microbiologia , Metagenoma , Microbiologia do Solo , Solo/análise , Arizona , Biodiversidade , DNA Bacteriano/genética , Clima Desértico , Geografia , Consórcios Microbianos , RNA Ribossômico 16S , Rizosfera , Análise de Sequência de DNA
7.
Sci Total Environ ; 804: 150045, 2022 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-34798718

RESUMO

Understanding the effects of elevated temperatures on soil organic matter (SOM) decomposition pathways in northern peatlands is central to predicting their fate under future warming. Peatlands role as carbon (C) sink is dependent on both anoxic conditions and low temperatures that limit SOM decomposition. Previous studies have shown that elevated temperatures due to climate change can disrupt peatland's C balance by enhancing SOM decomposition and increasing CO2 emissions. However, little is known about how SOM decomposition pathways change at higher temperatures. Here, we used an integrated research approach to investigate the mechanisms behind enhanced CO2 emissions and SOM decomposition under elevated temperatures of surface peat soil collected from a raised and Sphagnum dominated mid-continental bog (S1 bog) peatland at the Marcel Experimental Forest in Minnesota, USA, incubated under oxic conditions at three different temperatures (4, 21, and 35 °C). Our results indicated that elevated temperatures could destabilize peatland's C pool via a combination of abiotic and biotic processes. In particular, temperature-driven changes in redox conditions can lead to abiotic destabilization of Fe-organic matter (phenol) complexes, previously an underestimated decomposition pathway in peatlands, leading to increased CO2 production and accumulation of polyphenol-like compounds that could further inhibit extracellular enzyme activities and/or fuel the microbial communities with labile compounds. Further, increased temperatures can alter strategies of microbial communities for nutrient acquisition via changes in the activities of extracellular enzymes by priming SOM decomposition, leading to enhanced CO2 emission from peatlands. Therefore, coupled biotic and abiotic processes need to be incorporated into process-based climate models to predict the fate of SOM under elevated temperatures and to project the likely impacts of environmental change on northern peatlands and CO2 emissions.


Assuntos
Solo , Sphagnopsida , Mudança Climática , Temperatura , Áreas Alagadas
8.
Chemosphere ; 280: 130672, 2021 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-33964749

RESUMO

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.


Assuntos
Substâncias Explosivas , Espectrometria de Massas em Tandem , Animais , Anisóis , Nitrocompostos , Fotólise , Solubilidade , Triazinas , Triazóis
9.
FEMS Microbiol Lett ; 368(4)2021 03 03.
Artigo em Inglês | MEDLINE | ID: mdl-33547887

RESUMO

Transition from historic grasslands to woody plants in semiarid regions has led to questions about impacts on soil functioning, where microorganisms play a primary role. Understanding the relationship between microbes, plant diversity and soil functioning is relevant to assess such impacts. We evaluate the effect that plant type change in semiarid ecosystems has for microbial diversity and composition, and how this is related to carbon mineralization (CMIN) as a proxy for soil functioning. We followed a mesocosm experiment during 2 years within the Biosphere 2 facility in Oracle, AZ, USA. Two temperature regimes were established with two types of plants (grass or mesquite). Soil samples were analyzed for physicochemical and functional parameters, as well as microbial community composition using 16S rRNA amplicon metagenomics (Illumina MiSeq). Our results show the combined role of plant type and temperature regime in CMIN, where CMIN in grass has lower values at elevated temperatures compared with the opposite trend in mesquite. We also found a strong correlation of microbial composition with plant type but not with temperature regime. Overall, we provide evidence of the major effect of plant type in the specific composition of microbial communities as a potential result of the shrub encroachment.


Assuntos
Carbono/metabolismo , Ecossistema , Microbiota , Microbiologia do Solo , Carbono/análise , Plantas/classificação , Plantas/metabolismo , Plantas/microbiologia , Solo/química , Temperatura
10.
Front Microbiol ; 12: 754698, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34887842

RESUMO

Microbial communities in incipient soil systems serve as the only biotic force shaping landscape evolution. However, the underlying ecological forces shaping microbial community structure and function are inadequately understood. We used amplicon sequencing to determine microbial taxonomic assembly and metagenome sequencing to evaluate microbial functional assembly in incipient basaltic soil subjected to precipitation. Community composition was stratified with soil depth in the pre-precipitation samples, with surficial communities maintaining their distinct structure and diversity after precipitation, while the deeper soil samples appeared to become more uniform. The structural community assembly remained deterministic in pre- and post-precipitation periods, with homogenous selection being dominant. Metagenome analysis revealed that carbon and nitrogen functional potential was assembled stochastically. Sub-populations putatively involved in the nitrogen cycle and carbon fixation experienced counteracting assembly pressures at the deepest depths, suggesting the communities may functionally assemble to respond to short-term environmental fluctuations and impact the landscape-scale response to perturbations. We propose that contrasting assembly forces impact microbial structure and potential function in an incipient landscape; in situ landscape characteristics (here homogenous parent material) drive community structure assembly, while short-term environmental fluctuations (here precipitation) shape environmental variations that are random in the soil depth profile and drive stochastic sub-population functional dynamics.

12.
Sci Rep ; 10(1): 905, 2020 01 22.
Artigo em Inglês | MEDLINE | ID: mdl-31969580

RESUMO

Ecosystem carbon flux partitioning is strongly influenced by poorly constrained soil CO2 efflux (Fsoil). Simple model applications (Arrhenius and Q10) do not account for observed diel hysteresis between Fsoil and soil temperature. How this hysteresis emerges and how it will respond to variation in vegetation or soil moisture remains unknown. We used an ecosystem-level experimental system to independently control potential abiotic and biotic drivers of the Fsoil-T hysteresis. We hypothesized a principally biological cause for the hysteresis. Alternatively, Fsoil hysteresis is primarily driven by thermal convection through the soil profile. We conducted experiments under normal, fluctuating diurnal soil temperatures and under conditions where we held soil temperature near constant. We found (i) significant and nearly equal amplitudes of hysteresis regardless of soil temperature regime, and (ii) the amplitude of hysteresis was most closely tied to baseline rates of Fsoil, which were mostly driven by photosynthetic rates. Together, these findings suggest a more biologically-driven mechanism associated with photosynthate transport in yielding the observed patterns of soil CO2 efflux being out of sync with soil temperature. These findings should be considered on future partitioning models of ecosystem respiration.

13.
J Environ Qual ; 38(4): 1458-65, 2009.
Artigo em Inglês | MEDLINE | ID: mdl-19465721

RESUMO

Explosives in soils can present environmental problems for military installations. Fine, mobile particles represent the most reactive fraction of the soil and, therefore, are expected to adsorb explosives and potentially facilitate their transport. The objective of this study was to determine the relative significance of phyllosilicate clay, organic matter, and two forms of extractable iron in adsorption of 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by the colloidal water-dispersible clay (WDC) fraction of the soil. The WDC fraction of two mineral and one organic soil was separated and then treated to remove organic carbon (OC) and several forms of iron (Fe(o), oxalate extractable, and Fe(d), dithionite-citrate extractable). Adsorption coefficients were determined for whole soils, untreated, and treated WDC. For mineral soils, adsorption of TNT and RDX on the WDC was greater than on the whole soil. The presence of OC increased explosives sorption by WDC. When OC was removed, iron interfered with TNT sorption. In the presence of OC, removal of Fe(o) decreased RDX adsorption and increased TNT adsorption indicating different adsorption mechanisms. Organic carbon was a more significant indicator of explosives adsorption by WDC than clays or iron oxides and hydroxides. Therefore, OC is the most likely medium for facilitated transport of TNT and RDX.


Assuntos
Silicatos de Alumínio/química , Carbono/química , Substâncias Explosivas/química , Ferro/química , Adsorção , Argila
14.
Chemosphere ; 228: 418-426, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31051343

RESUMO

Two major components of insensitive munition formulations, nitroguanidine (NQ) and 3-nitro-1,2,4-triazol-5-one (NTO), are highly water soluble and therefore likely to photo-transform while in solution in the environment. The ecotoxicities of NQ and NTO solutions are known to increase with UV exposure, but a detailed accounting of aqueous degradation rates, products, and pathways under different exposure wavelengths is currently lacking. Here, we irradiated aqueous solutions of NQ and NTO over a 32-h period at three ultraviolet wavelengths (254 nm, 300 nm, and 350 nm) and analyzed their degradation rates and transformation products. NQ was completely degraded by 30 min at 254 nm and by 4 h at 300 nm, but it was only 10% degraded after 32 h at 350 nm. Mass recoveries of NQ and its transformation products were ≥80% for all three wavelengths, and consisted of large amounts of guanidine, nitrate, and nitrite, and smaller amounts of cyanamide, cyanoguanidine, urea, and ammonium. NTO degradation was greatest at 300 nm with 3% remaining after 32 h, followed by 254 nm (7% remaining) and 350 nm (20% remaining). Mass recoveries of NTO and its transformation products were high for the first 8 h but decreased to 22-48% by 32 h, with the major aqueous products identified as ammonium, nitrate, nitrite, and a urazole intermediate. Environmental half-lives of NQ and NTO in pure water were estimated as 4 and 6 days, respectively. We propose photo-degradation pathways for NQ and NTO supported by observed and quantified degradation products and changes in solution pH.


Assuntos
Guanidinas/química , Nitrocompostos/química , Triazóis/química , Monitoramento Ambiental , Fotólise
15.
Sci Rep ; 9(1): 15006, 2019 10 18.
Artigo em Inglês | MEDLINE | ID: mdl-31628373

RESUMO

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.

16.
Environ Toxicol Chem ; 27(9): 1932-41, 2008 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-19086318

RESUMO

Carbon nanotubes (NTs) may be among the most useful engineered nanomaterials for structural applications but could be difficult to study in ecotoxicological evaluations using existing tools relative to nanomaterials with a lower aspect ratio. Whereas the hydrophobicity and van der Waals interactions of NTs may suggest aggregation and sedimentation in aquatic systems, consideration regarding how engineered surface modifications influence their environmental fate and toxicology is needed. Surface modifications (e.g., functional groups and coatings) are intended to create conditions to make NTs dispersible in aqueous suspension, as required for some applications. In the present study, column stability and settling experiments indicated that raw, multiwalled NTs (MWNTs) settled more rapidly than carbon black and activated carbon particles, suggesting sediment as the ultimate repository. The presence of functional groups, however, slowed the settling of MWNTs (increasing order of stability: hydroxyl > carboxyl > raw), especially in combination with natural organic matter (NOM). Stabilized MWNTs in high concentrations of NOM provided relevance for water transport and toxicity studies. Aqueous exposures to raw MWNTs decreased Ceriodaphnia dubia viability, but such effects were not observed during exposure to functionalized MWNTs (> 80 mg/L). Sediment exposures of the amphipods Leptocheirus plumulosus and Hyalella azteca to different sizes of sediment-borne carbon particles at high concentration indicated mortality increased as particle size decreased, although raw MWNTs induced lower mortality (median lethal concentration [LC50], 50 to >264 g/kg) than carbon black (LC50, 18-40 g/kg) and activated carbon (LC50, 12-29 g/kg). Our findings stress that it may be inappropriate to classify all NTs into one category in terms of their environmental regulation.


Assuntos
Nanotubos/química , Nanotubos/toxicidade , Poluentes da Água/química , Poluentes da Água/toxicidade , Anfípodes , Animais , Bioensaio , Disponibilidade Biológica , Daphnia , Interpretação Estatística de Dados , Processamento de Imagem Assistida por Computador , Microscopia Eletrônica de Transmissão , Tamanho da Partícula , Propriedades de Superfície , Suspensões , Ultrassom , Água/química
17.
Sci Total Environ ; 624: 758-768, 2018 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-29272845

RESUMO

Military training exercises can result in deposition of energetic residues on range soils, which ultimately can contaminate groundwater with munitions constituents. Column experiments followed by HYDRUS-1D modeling were conducted to evaluate dissolution and transport of energetic constituents from the new insensitive munitions (IM) formulations IMX-101, a mixture of 3-nitro-1,2,4-triazol-5-one (NTO), nitroguanidine (NQ), and 2, 4-dinitroanisole (DNAN), and IMX-104, a mixture of NTO, 1,3,5-hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and DNAN. NTO and DNAN are emerging contaminants associated with the development of insensitive munitions as replacements for traditional munitions. Flow interruption experiments were performed to investigate dissolution kinetics and sorption non-equilibrium between soil and solution phases. The results indicated that insensitive munitions compounds dissolved in order of their aqueous solubility, consistent with prior dissolution studies conducted in the absence of soil. Initial elution of the high concentration pulse of highly soluble NTO and NQ was followed by lower concentrations, while DNAN had generally lower and more constant concentrations in leachate. The sorption of NTO and NQ was low, while RDX, 1,3,5,7-octahydro-1,3,5,7-tetranitrotetrazocine (HMX, an impurity in technical grade RDX), and DNAN all exhibited appreciable sorption. DNAN transformation was observed, with formation of amino-reduction products 2-ANAN (2-amino-4-nitroanisole) and 4-ANAN (4-amino-2-nitroanisole). HYDRUS-1D model, incorporating one-dimensional advective-dispersive transport with particle dissolution and first-order solute transformation was used to simulate the measured breakthrough curves. Optimized dissolution parameters varied widely but were correlated between compounds in the same formulation. Determined adsorption coefficients generally agreed with values determined from batch and column studies conducted with pure NTO and DNAN, while mass-loss rate coefficients were in better agreement with ones from batch than column studies possibly due to suppression of microbial transformation during elution of high concentrations of explosives. Even in the low organic matter soils selected in this study DNAN experienced significant retardation and transformation, indicating potential for its natural attenuation.

19.
Chemosphere ; 171: 427-434, 2017 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-28033573

RESUMO

Development of the new, insensitive, energetic compound, NTO (3-nitro-1,2,4-triazol-5-one), creates need for the data on NTO's fate and transport to predict its behavior in the environment and potential for groundwater contamination. To measure the transport of NTO in soils, we conducted miscible-displacement experiments under steady state and interrupted flow conditions using eight soils having varying physical and geochemical properties. The breakthrough curve (BTC) data were analyzed using temporal moment analysis and simulated using HYDRUS-1D to determine transport parameters and better understand the mechanisms of sorption and transformation. Parameters determined from the miscible-displacement study were compared to results obtained from batch experiments conducted for the same soils, and examined in relation to soil properties. Column NTO linear adsorption coefficients (Kd) were low and correlated well (P = 0.000049) with measurements from the batch studies. NTO transformation rate constants increased and NTO recovery decreased with increase in soil organic carbon (OC) content. Autoclaved soils had slower transformation rates and greater NTO recoveries indicating that microorganisms play a role in NTO transformation. In addition, the transformation rate increased with time in soils with higher OC. Monod-type kinetics was implemented in HYDRUS-1D to simulate the observed increase in transformation rate with time. We think this phenomenon is due to bacterial growth. Results indicate very low adsorption of NTO in a range of soils, but natural attenuation through transformation that, depending on soil OC content and hydraulic residence time, could result in complete removal of NTO.


Assuntos
Nitrocompostos/química , Poluentes do Solo/química , Solo/química , Triazóis/química , Adsorção , Água Subterrânea/química , Cinética , Nitrocompostos/análise , Poluentes do Solo/análise , Triazóis/análise
20.
J Contam Hydrol ; 199: 14-23, 2017 04.
Artigo em Inglês | MEDLINE | ID: mdl-28285171

RESUMO

The explosive 2,4,6-trinitrotoluene (TNT) is currently a main ingredient in munitions; however the compound has failed to meet the new sensitivity requirements. The replacement compound being tested is 2,4-dinitroanisole (DNAN). DNAN is less sensitive to shock, high temperatures, and has good detonation characteristics. However, DNAN is more soluble than TNT, which can influence transport and fate behavior and thus bioavailability and human exposure potential. The objective of this study was to investigate the environmental fate and transport of DNAN in soil, with specific focus on sorption processes. Batch and column experiments were conducted using soils collected from military installations located across the United States. The soils were characterized for pH, electrical conductivity, specific surface area, cation exchange capacity, and organic carbon content. In the batch rate studies, change in DNAN concentration with time was evaluated using the first order equation, while adsorption isotherms were fitted using linear and Freundlich equations. Solution mass-loss rate coefficients ranged between 0.0002h-1 and 0.0068h-1. DNAN was strongly adsorbed by soils with linear adsorption coefficients ranging between 0.6 and 6.3Lg-1, and Freundlich coefficients between 1.3 and 34mg1-nLnkg-1. Both linear and Freundlich adsorption coefficients were positively correlated with the amount of organic carbon and cation exchange capacity of the soil, indicating that similar to TNT, organic matter and clay minerals may influence adsorption of DNAN. The results of the miscible-displacement column experiments confirmed the impact of sorption on retardation of DNAN during transport. It was also shown that under flow conditions DNAN transforms readily with formation of amino transformation products, 2-ANAN and 4-ANAN. The magnitudes of retardation and transformation observed in this study result in significant attenuation potential for DNAN, which would be anticipated to contribute to a reduced risk for contamination of ground water from soil residues.


Assuntos
Silicatos de Alumínio/química , Anisóis/análise , Substâncias Explosivas/análise , Modelos Teóricos , Poluentes do Solo/análise , Solo/química , Adsorção , Argila , Condutividade Elétrica , Propriedades de Superfície
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