Uptake Of RDX Research Articles

Multiple stressors in multiple species: Effects of different RDX soil concentrations and differential water-resourcing on RDX fate, plant health, and plant survival.

Response to simultaneous stressors is an important facet of plant ecology and land management. In a greenhouse trial, we studied how eight plant species responded to single and combined effects of three soil concentrations of the phytotoxic munitions constituent RDX and two levels of water-resourcing. In an outdoor trial, we studied the effects of high RDX soil concentration and two levels of water-resourcing in three plant species. Multiple endpoints related to RDX fate, plant health, and plant survival were evaluated in both trials. Starting RDX concentration was the most frequent factor influencing all endpoints. Water-resourcing also had significant impacts, but in fewer cases. For most endpoints, significant interaction effects between RDX concentration and water-resourcing were observed for some species and treatments. Main and interaction effects were typically variable (significant in one treatment, but not in another; associated with increasing endpoint values for one treatment and/or with decreasing endpoint values in another). This complexity has implications for understanding how RDX and water-availability combine to impact plants, as well as for applications like phytoremediation. As an additional product of these greenhouse and outdoor trials, three plants native or naturalized within the southeastern United States were identified as promising species for further study as in situ phytoremediation resources. Plumbago auriculata exhibited relatively strong and markedly consistent among-treatment mean proportional reductions in soil RDX concentrations (112% and 2.5% of the means of corresponding values observed within other species). Likewise, across all treatments, Salvia coccinea exhibited distinctively low variance in mean leaf chlorophyll content index levels (6.5% of the means of corresponding values observed within other species). Both species also exhibited mean wilting and chlorosis levels that were 66% and 35%, and 67% and 84%, of corresponding values observed in all other plants, respectively. Ruellia caroliniensis exhibited at least 43% higher mean survival across all treatments than any other test species in outdoor trials, despite exhibiting similar RDX uptake and bioconcentration levels.

Synthesis of highly-energetic nanoparticles based on monodisperse hollow mesoporous nanospheres

Abstract Highly-energetic monodisperse nanospheres were prepared based on surface-modified, hollow mesoporous silica nanospheres. The monodisperse, cationic polymer nanospheres were prepared by the emulsifier-free emulsion copolymerization and used as a template to obtain copolymer/silica core-shell nanospheres and monodisperse, hollow mesoporous silica (HMS) nanospheres. The surface of the HMS nanospheres was treated with (3-aminopropyl) trimethoxysilane to obtain (3-aminopropyl)trimethoxysilane-grafted HMS nanospheres, which facilitated the adsorption of cyclomethylene trinitramine within the inorganic framework. The uptake of RDX within the dried, final nanospheres was measured by thermogravimetric analysis.

Uptake and fate of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in coastal marine biota determined using a stable isotopic tracer, 15N – [RDX

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is globally one of the most commonly used military explosives and environmental contaminant. 15N labeled RDX was added into a mesocosm containing 9 different coastal marine species in a time series experiment to quantify the uptake of RDX and assess the RDX derived 15N retention into biota tissue. The 15N attributed to munitions compounds reached steady state concentrations ranging from 0.04 to 0.67 μg 15N g dw−1, the bulk 15N tissue concentration for all species was 1–2 orders of magnitude higher suggesting a common mechanism or pathway of RDX biotransformation and retention of 15N. A toxicokinetic model was created that described the 15N uptake, elimination, and transformation rates. While modeled uptake rates were within previous published values, elimination rates were several orders of magnitude smaller than previous studies ranging from 0.05 to 0.7 days−1. These small elimination rates were offset by high rates of retention of 15N previously not measured. Bioconcentration factors and related aqueous:organism ratios of compounds and tracer calculated using different tracer and non-tracer methods yielded a broad range of values (0.35–101.6 mL g−1) that were largely method dependent. Despite the method-derived variability, all values were generally low and consistent with little bioaccumulation potential. The use of 15N labeled RDX in this study indicates four possible explanations for the observed distribution of compounds and tracer; each with unique potential implications for possible toxicological impacts in the coastal marine environment.

Elevated root retention of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in coniferous trees

For decades, the explosive RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) has been used for military and industrial applications. Residues of RDX pollute soils in large areas globally and the persistence and high soil mobility of these residues can lead to leaching into groundwater. Dendroremediation, i.e. the long-term use of trees to clean up polluted soils, is gaining acceptance as a green and sustainable strategy. Although the coniferous tree species Norway spruce and Scots pine cover large areas of military land in Central Europe, the potential of any coniferous tree for dendroremediation of RDX is still unknown. In this study, uptake experiments with a (14)C-labelled RDX solution (30 mg L(-1)) revealed that RDX was predominantly retained in the roots of 6-year-old coniferous trees. Only 23 % (pine) to 34 % (spruce) of RDX equivalents (RDXeq) taken up by the roots were translocated to aboveground tree compartments. This finding contrasts with the high aerial accumulation of RDXeq (up to 95 %) in the mass balances of all other plant species. Belowground retention of RDXeq is relatively stable in fine root fractions, since water leaching from tissue homogenates was less than 5 %. However, remobilisation from milled coarse roots and tree stubs reached up to 53 %. Leaching from homogenised aerial tree material was found to reach 64 % for needles, 58 % for stems and twigs and 40 % for spring sprouts. Leaching of RDX by precipitation increases the risk for undesired re-entry into the soil. However, it also opens the opportunity for microbial mineralisation in the litter layer or in the rhizosphere of coniferous forests and offers a chance for repeated uptake of RDX by the tree roots.

Concentration-dependent RDX uptake and remediation by crop plants

The potential RDX contamination of food chain from polluted soil is a significant concern in regards to both human health and environment. Using a hydroponic system and selected soils spiked with RDX, this study disclosed that four crop plant species maize (Zea mays), sorghum (Sorghum sudanese), wheat (Triticum aestivum), and soybean (Glycine max) were capable of RDX uptake with more in aerial parts than roots. The accumulation of RDX in the plant tissue is concentration-dependent up to 21mg RDX/L solution or 100mg RDX/kg soil but not proportionally at higher RDX levels from 220 to 903mg/kg soil. While wheat plant tissue harbored the highest RDX concentration of 2,800μg per gram dry biomass, maize was able to remove a maximum of 3,267μg RDX from soil per pot by five 4-week plants at 100mg/kg of soil. Although RDX is toxic to plants, maize, sorghum, and wheat showed reasonable growth in the presence of the chemical, whereas soybeans were more sensitive to RDX. Results of this study facilitate assessment of the potential invasion of food chain by RDX-contaminated soils.

Functional Characterization of pGKT2, a 182-Kilobase Plasmid Containing the xplAB Genes, Which Are Involved in the Degradation of Hexahydro-1,3,5-Trinitro-1,3,5-Triazine by Gordonia sp. Strain KTR9

Several microorganisms have been isolated that can transform hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), a cyclic nitramine explosive. To better characterize the microbial genes that facilitate this transformation, we sequenced and annotated a 182-kb plasmid, pGKT2, from the RDX-degrading strain Gordonia sp. KTR9. This plasmid carries xplA, encoding a protein sharing up to 99% amino acid sequence identity with characterized RDX-degrading cytochromes P450. Other genes that cluster with xplA are predicted to encode a glutamine synthase-XplB fusion protein, a second cytochrome P450, Cyp151C, and XplR, a GntR-type regulator. Rhodococcus jostii RHA1 expressing xplA from KTR9 degraded RDX but did not utilize RDX as a nitrogen source. Moreover, an Escherichia coli strain producing XplA degraded RDX but a strain producing Cyp151C did not. KTR9 strains cured of pGKT2 did not transform RDX. Physiological studies examining the effects of exogenous nitrogen sources on RDX degradation in strain KTR9 revealed that ammonium, nitrite, and nitrate each inhibited RDX degradation by up to 79%. Quantitative real-time PCR analysis of glnA-xplB, xplA, and xplR showed that transcript levels were 3.7-fold higher during growth on RDX than during growth on ammonium and that this upregulation was repressed in the presence of various inorganic nitrogen sources. Overall, the results indicate that RDX degradation by KTR9 is integrated with central nitrogen metabolism and that the uptake of RDX by bacterial cells does not require a dedicated transporter.

Role of soil interstitial water in the accumulation of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine in the earthworm Eisenia andrei

The uptake of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) from soil by the earthworm Eisenia andrei was examined by using the equilibrium partitioning (EqP) theory and a three-compartment model including soil (S), interstitial water (IW), and earthworms (E). The RDX concentrations were measured using U.S. Environmental Protection Agency (U.S. EPA) Method 8330A and high-performance liquid chromatography (HPLC). The S-IW studies were conducted using four natural soils with contrasting physicochemical properties that were hypothesized to affect the bioavailability of RDX. Each soil was amended with nominal RDX concentrations ranging from 1 to 10,000 mg/kg. The HPLC analysis showed that the IW extracted from soil was saturated with RDX at 80 mg/kg or greater soil concentrations. The calculated S-IW coefficient (K(p)) values for RDX ranged from 0.4 to 1.8 ml/g soil, depending on the soil type, and were influenced by the organic matter content. In the IW-E studies, earthworms were exposed to nonlethal RDX concentrations in aqueous media. The uptake of RDX by the earthworms correlated well (r(2) = 0.99) with the dissolved RDX concentrations. For the E-S studies, earthworms were exposed to RDX-amended soils used in the S-IW studies. The bioconcentration factors (BCF; ratios of E-to-IW RDX concentrations) were relatively constant ( approximately 5) up to 80 mg/kg soil RDX concentrations, which encompass the RDX saturation limit in the interstitial water of the tested soils. At this concentration range, the RDX uptake from interstitial water was likely dominated by passive diffusion and could be used as an indicator of bioavailability. Other mechanisms may be involved at greater RDX soil concentrations.

Selective sampling with direct ion mobility spectrometric detection for explosives analysis

This study investigates the potential and limitations of a field-deployable analytical approach that involves selective capture of explosive materials with direct analysis by ion mobility spectrometry (IMS). Selective capture of explosives was performed on deactivated quartz fiber filters impregnated with metal β-diketonate polymers. These Lewis acidic polymers selectively interact with Lewis base analytes such as explosives. The filters were directly inserted into an IMS instrument for analysis. The uptake kinetics of 2,4,6-trinitrotoluene (TNT) from a saturated atmosphere were characterized, and based on these studies, passive equilibrium sampling was applied to estimate the TNT concentration within an ammunition magazine that contained bulk TNT. Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) uptake from a saturated environment also was examined over a one-month period. Each incremental sampling period showed increasing quantities of RDX culminating with collection of approximately 5 ng of RDX on the filter at the end of one month. This is the first time that gas-phase uptake of RDX has been demonstrated.

Accumulation of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine by the earthworm Eisenia andrei in a sandy loam soil

The heterocyclic polynitramine hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a highly energetic compound found as a soil contaminant at some defense installations. Although RDX is not lethal to soil invertebrates at concentrations up to 10,000 mg/kg, it decreases earthworm cocoon formation and juvenile production at environmentally relevant concentrations found at contaminated sites. Very little is known about the uptake of RDX in earthworms and the potential risks for food-chain transfer of RDX in the environment. Toxicokinetic studies were conducted to quantify the bioaccumulation factors (BAFs) using adult earthworms (Eisenia andrei) exposed for up to 14 d to sublethal concentrations of nonlabeled RDX or [14C]RDX in a Sassafras sandy loam soil. High-performance liquid chromatography of acetonitrile extracts of tissue and soil samples indicated that nonlabeled RDX can be accumulated by the earthworm in a concentration- and time-dependent manner. The BAF, expressed as the earthworm tissue to soil concentration ratio, decreased from 6.7 to 0.1 when the nominal soil RDX concentrations were increased from 1 to 10,000 mg/kg. Tissue concentrations were comparable in earthworms exposed to nonlabeled RDX or [14C]RDX. The RDX bioaccumulation also was estimated using the kinetically derived model (BAFK), based on the ratio of the uptake to elimination rate constants. The established BAFK of 3.6 for [14C]RDX uptake was consistent with the results for nonlabeled RDX. Radioactivity also was present in the tissue residues of [14C]RDX-exposed earthworms following acetonitrile extraction, suggesting the formation of nonextractable [14C]RDX metabolites associated with tissue macromolecules. These findings demonstrated a net accumulation of RDX in the earthworm and the potential for food-chain transfer of RDX to higher-trophic-level receptors.

Physiologically based pharmacokinetic modeling of cyclotrimethylenetrinitramine in male rats

A physiologically based pharmacokinetic (PBPK) model for simulating the kinetics of cyclotrimethylene trinitramine (RDX) in male rats was developed. The model consisted of five compartments interconnected by systemic circulation. The tissue uptake of RDX was described as a perfusion-limited process whereas hepatic clearance and gastrointestinal absorption were described as first-order processes. The physiological parameters for the rat were obtained from the literature whereas the tissue : blood partition coefficients were estimated on the basis of the tissue and blood composition as well as the lipophilicity characteristics of RDX (logP = 0.87). The tissue : blood partition coefficients (brain, 1.4; muscle, 1; fat, 7.55; liver, 1.2) obtained with this algorithmic approach were used without any adjustment, since a focused in vitro study indicated that the relative concentration of RDX in whole blood and plasma is about 1 : 1. An initial estimate of metabolic clearance of RDX (2.2 h(-1) kg(-1)) was obtained by fitting PBPK model simulations to the data on plasma kinetics in rats administered 5.5 mg kg(-1) i.v. The rat PBPK model without any further change in parameter values adequately simulated the blood kinetic data for RDX at much lower doses (0.77 and 1.04 mg (-1) i.v.), collected in this study. The same model, with the incorporation of a first order oral absorption rate constant (K(a) 0.75 h(-1)), reproduced the blood kinetics of RDX in rats receiving a single gavage dose of 1.53 or 2.02 mg kg(-1). Additionally, the model simulated the plasma and blood kinetics of orally administered RDX at a higher dose (100 mg kg(-1)) or lower doses (0.2 or 1.24 mg kg(-1)) in male rats. Overall, the rat PBPK model for RDX with its parameters adequately simulates the blood and plasma kinetic data, obtained following i.v. doses ranging from 0.77 to 5.5 mg kg(-1) as well as oral doses ranging from 0.2 to 100 mg kg(-1).

Lateral Transfer of Genes for Hexahydro-1,3,5-Trinitro-1,3,5-Triazine (RDX) Degradation

Recent studies demonstrated that degradation of the military explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by species of Rhodococcus, Gordonia, and Williamsia is mediated by a novel cytochrome P450 with a fused flavodoxin reductase domain (XplA) in conjunction with a flavodoxin reductase (XplB). Pulse field gel analysis was used to localize xplA to extrachromosomal elements in a Rhodococcus sp. and distantly related Microbacterium sp. strain MA1. Comparison of Rhodococcus rhodochrous 11Y and Microbacterium plasmid sequences in the vicinity of xplB and xplA showed near identity (6,710 of 6,721 bp). Sequencing of the associated 52.2-kb region of the Microbacterium plasmid pMA1 revealed flanking insertion sequence elements and additional genes implicated in RDX uptake and degradation.

Phytotoxicity to and uptake of RDX by rice

Phytoremediation is an emerging strategy to remediate soils contaminated with pollutants like explosives in which plants will uptake, degrade and/or accumulate pollutants. To implement this technology on a site contaminated with RDX, we chose rice, which is able to grow in lagoons, and we tested its ability to grow in soils with high levels of RDX and to decrease RDX concentrations in soil. Rice was grown for 40 days in soil contaminated with increasing [ 14C]RDX concentrations. Emergence and growth were not affected by RDX. Total chlorophyll content decreased with RDX concentrations of over 500 mg kg −1. Amounts of chlorophyll were correlated with the appearance of necrosis in leaf extremities. After 40 days, rice translocated 89% of uptaken radioactivity to leaves with 90% in leaf extremities. Analyzes of leaf extracts showed that 95% of radioactivity was RDX in its parent form. Necrosis appears to be a phytotoxic symptom of RDX accumulation.

Accumulation of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine in channel catfish (ictalurus punctatus) and aquatic oligochaetes (lumbriculus variegatus)

The extensively used military explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) has been widely released to the environment during production, usage, and disposal operations. Toxic effects of RDX have been reported in terrestrial and aquatic receptors, but investigations regarding the bioaccumulation potential of RDX in aquatic systems are scarce. The objective of the present study was to describe the toxicokinetics of RDX during aqueous exposure for the channel catfish (Ictalurus punctatus) and aquatic oligochaetes (Lumbriculus variegatus) and to compare the amount of RDX accumulation in juvenile catfish following aqueous exposure only, dietary exposure only, and a combination of dietary and aqueous exposure. The toxicokinetics measurements included bioconcentration factors (BCFs), uptake rates, elimination rates, and biological half-lives. First-order, single-compartment models described the toxicokinetics for both species. Uptake of RDX into oligochaetes was relatively rapid (uptake clearance constant [k(u)] of 5.17 ml/g/h) compared to that in catfish (k(u) = 1.28 ml/g/h). However, elimination also was more rapid in oligochaetes, with biological half-lives of 0.28 and 1.09 h for oligochaetes and catfish, respectively. Thus, both species had very similar estimated BCFs of 2.1 ml/g for oligochaetes and 2.0 ml/g for catfish. Accumulation of RDX in fish that were fed oligochaetes exposed to an exceedingly high water concentration of RDX was minimal. The present investigation indicates that RDX uptake via the aqueous route is the expected dominant uptake pathway, with dietary uptake contributing minimally to the overall body burden in fish inhabiting RDX-contaminated sites. Because of the exceedingly low bioaccumulative potential and low reported toxicity of RDX, the presence of this explosive in aquatic systems is unlikely to pose unacceptable risks to invertebrates and fish.

Uptake of RDX and TNT by Agronomic Plants

(2002). Uptake of RDX and TNT by Agronomic Plants. Soil and Sediment Contamination: An International Journal: Vol. 11, No. 3, pp. 307-326.