Modulating covalent organic frameworks with accessible carboxyl to boost superior extraction of polar nitrobenzene compounds from matrix-complicated beverages.

The wide use and high polarity of nitrobenzene compounds (NBCs) have caused a concern for their residues in daily beverages. Herein, the covalent organic frameworks (COFs) with abundant carboxyl were ingeniously designed by introducing a novel modulator, and further developed as solid phase microextraction (SPME) coatings. Due to the enhanced polar interaction, the extraction efficiencies of modified COF for NBCs were sharply increased. After coupling the high-performance SPME fiber with gas chromatograph-mass spectrometry (GC-MS), an ultrasensitive analytical method was developed, with a wide linear range (0.50-5000 ng/L), and low limits of detection (0.15-3.0 ng/L). More importantly, the method was highly feasible and practical, leading to the precise determinations of trace NBCs from variously matrix-complicated samples. This work provides a viable and efficacious approach for the extraction and analysis of polar pollutants form complicated matrices, and is of great significance for mild COF modification and its extended applications in analytical chemistry.

Random Copolymers of Styrene with Pendant Fluorophore Moieties: Synthesis and Applications as Fluorescence Sensors for Nitroaromatics.

Five random copolymers comprising styrene and styrene with pendant fluorophore moieties, namely pyrene, naphthalene, phenanthrene, and triphenylamine, in molar ratios of 10:1, were synthesized and employed as fluorescent sensors. Their photophysical properties were investigated using absorption and emission spectral analyses in dichloromethane solution and in solid state. All copolymers possessed relative quantum yields up to 0.3 in solution and absolute quantum yields up to 0.93 in solid state, depending on their fluorophore components. Fluorescence studies showed that the emission of these copolymers is highly sensitive towards various nitroaromatic compounds, both in solution and in the vapor phase. The detection limits of these fluorophores for nitroaromatic compounds in dichloromethane solution proved to be in the range of 10-6 to 10-7 mol/L. The sensor materials for new hand-made sniffers based on these fluorophores were prepared by electrospinning and applied for the reliable detection of nitrobenzene vapors at 1 ppm in less than 5 min.

Abiotic Transformation of Nitrobenzene by Zero Valent Iron under Aerobic Conditions: Relative Contributions of Reduction and Oxidation in the Presence of Ethylene Diamine Tetraacetic Acid.

Zero valent iron (ZVI) applications to remediation of shallow groundwaters can be affected by dissolved oxygen (DO) and organic ligands. To explore the intersection between these complicating factors, this study thoroughly characterized the reactions of nitrobenzene (NB) with ZVI in the presence DO and the model ligand ethylene diamine tetraacetic acid (EDTA). The results showed that NB is degraded by both ZVI reduction and ZVI-induced advanced oxidation under oxygen-limited conditions. The contribution of ·OH to the degradation of NB increased with time so that nearly 39% of NB was oxidized by ·OH at 15 min (pH = 3), but reduction was still the main pathway of NB transformation throughout. NB reduction products, such as aniline (AN), were also oxidized by ·OH. The lower the pH, the greater the contribution of advanced oxidation, but DO was the limiting factor for ·OH generation. Only 4.7% NB was fully degraded by ring opening and/or mineralization because the production of •OH was limited by low DO. After the transformation of NB and AN, other benzene ring and nitrogen-containing intermediates were identified (e.g., p-nitrophenol, p-aminophenol, hydroquinone, and p-benzoquinone). The removal of total organic carbon and total organic nitrogen was minimal. The results suggested that the relative doses of ZVI, DO, and iron-complexing ligands can be balanced for the optimal (rapid and deep) removal of organic contaminants.

DNA-templated silver nanoclusters as an efficient catalyst for reduction of nitrobenzene derivatives: a systematic study.

Nitrobenzene compounds are highly toxic pollutants with good stability, and they have a major negative impact on both human health and the ecological environment. Herein, it was found for the first time that fluorescent DNA-silver nanoclusters (DNA-AgNCs) can catalyze the reduction of toxic and harmful nitro compounds into less toxic amino compounds with excellent tolerance to high temperature and organic solvents. In this study, the reduction of p-nitrophenol (4-NP) as a model was systematically investigated, followed by expending the substrate to disclose the versatility of this reaction. This report not only expanded the conditions for utilizing catalytic reduction conditions of DNA-AgNCs as an efficient catalyst in the control of hazardous chemicals but also widened the substrate range of DNA-AgNCs reduction, providing a new angle for the application of noble metal nanoclusters.

Biogenesis of Prism-Like Silver Oxide Nanoparticles Using Nappa Cabbage Extract and Their p-Nitrophenol Sensing Activity.

The present study aimed to explore the eco-friendly synthesis of prism-like silver oxide nanoparticles (Ag2ONPs) from nappa cabbage extract and its p-nitrophenol sensing activity. The prepared Ag2ONPs were characterized by X-ray diffraction (XRD), field-emission scanning spectroscopy (FESEM), energy-dispersive spectroscopy (EDS), transmission electron microscopy (TEM), and ultraviolet (UV)-visible light spectral analysis (UV-Vis). p-Nitrophenol sensing properties of the prepared nanoparticles were also determined using a simple I-V method. The results showed that the as-prepared Ag2ONPs have a face-centered cubic (fcc) crystalline nature and a prism-like morphology with particle size in the range 21.61-92.26 nm. The result also showed a high intensity of the (111) facet, making the Ag2ONP-carbon black/nickel foam electrode (Ag2ONP-C/NFE) exhibit a high-performance response to p-nitrophenol spanning a wide range of concentrations from 1.0 mM to 0.1 pM and a response time of around 5 s, indicating a high potential for water treatment applications.

Simulated kinetics of the atmospheric removal of aniline during daytime.

Oxidations of aniline (AN) initiated by OH-radicals are simulated in the temperature range 200-400 K using DFT/M06-2X/6-311++G(2df,2p) and ab initio ROCBS-QB3 levels. Chemical kinetics of such reactions were investigated based on several approaches including classical transition state theory (TST), conical variational transition state theory (CVT), and Rice-Ramsperger-Kassel-Marcus master equation (RRKM-ME) theories. Under atmospheric conditions, the reaction of OH radical with AN and the subsequent reactions with O2 molecules are investigated. The results indicate that the majority of O2 addition goes to the anti-directions with a branching ratio of 97.7% and produces the bicyclic peroxy radicals (BPRs) that can react with NO radical to form bicyclic alkoxy radicals (BARs). The latter compounds can be stabilized either by cyclization or via ring cleavage.

Facilitated bioreduction of nitrobenzene by lignite acting as low-cost and efficient electron shuttle.

The searching for efficient and economical redox mediators to promote the treatment of wastewater containing recalcitrant organic compounds is greatly needed. In this study, the redox mediator activities of four different lignite samples to facilitate the bioreduction of nitrobenzene by Shewanella oneidensis MR-1 were tested for the first time. The initial nitrobenzene reduction rate was increased by 40.4%-90.3% in the presence of 50 mg/L of different lignite samples. Lignite collected from Xinjiang (XJL) having more oxygenated groups performed better in enhancing nitrobenzene bioreduction. The stimulating effects increased with the increase of lignite dosage (0-200 mg/L) and the decrease of lignite particle size (150-0.1 µm). However, the pristine XJL samples with assorted sizes of particles exhibited better stimulating effects than size-fractionated ones, implying that different-sized XJL particles might have synergetic effects on the bioreduction process. When humic acid or iron was removed from XJL, its promoting effects were decreased, demonstrating the crucial roles of both components in lignite-enhanced nitrobenzene bioreduction. Nitric acid treatment could form more oxygenated moieties on lignite surface, which played vital roles in promoting nitrobenzene bioreduction. The initial nitrobenzene bioreduction rate in the presence of HNO3-treated XJL was 80.8% higher than that obtained with pristine XJL. This study proposed an effective and readily available redox mediator that could be applied to promote the bioreduction of recalcitrant electrophilic pollutants.

A dual mode photoelectrochemical sensor for nitrobenzene and L-cysteine based on 3D flower-like Cu2SnS3@SnS2 double interfacial heterojunction photoelectrode.

In this work, 3D hierarchical Cu2SnS3@SnS2 flower assembled from nanopetals with sandwich-like Cu2SnS3-SnS2-Cu2SnS3 double interfacial heterojunction was successfully designed and synthesized on fluoride doped tin oxide (FTO) for photoelectrochemical (PEC) sensor by in situ electrodeposition p-type Cu2SnS3 nanoparticles on both inner and outer surfaces of n-type SnS2 nanopetals. The unique double interfacial heterojunction simultaneously combines 3D flower-like architectures to drastically increase the light trapping and absorption in visible-near infrared range (Vis-NIR), and dramatically inhibites the charge carrier recombination, which is crucial for boosting the PEC activity. Benefitting from the shape and compositional merits, the Cu2SnS3@SnS2 heterojunction possess dual-mode signal by controlling the electrodeposition time to manipulate the composition ratio of Cu2SnS3 and SnS2. The Cu2SnS3@SnS2/FTO electrode not only exhibits excellent photoeletro-reduction capacity for ultra-sensitive sensing trace persistent organic pollutant (nitrobenzene, NB), but also presents photoeletro-oxidization activity for high selective detection of L-cysteine (L-Cys) without any auxiliary enzyme under the light illumination. Dual mode sensor displayed superb performance for the detection of NB/L-Cys, showing a wide linear range from 100 pM to 300 µM/10 nM to 100 µM and a low detection limit (3S/N) of 68 pM/8.5 nM, respectively. Such a tunable double interfacial heterojunction design opened up new avenue for constructing multifunction PEC sensing platform.

Synthesis of metallic copper modified g-C3N4 by molecular self-assembly structure and its combined catalytic performance with activated sludge.

Copper modified carbon nitride (CuCN) was prepared by a hydrothermal self-assembly reaction and following high temperature thermal polymerization process. Finally, the sample exhibits uniform one-dimensional tubular structure. Interestingly, the separation efficiency of electron-hole pair is improved, and more catalytic active sites are exposed due to the special hollow structure. Meanwhile, the presence of copper element narrows its band gap, leading to the enhancement of photocatalytic degradation performance under simulated sunlight. In addition, the effect of CuCN on dehydrogenase activity of activated sludge was determined by TTC reduction method. After adding CuCN-2, the activity of activated sludge reached 0.134 µmol g-1 min-1, which indicated that the prepared CuCN-2 had good biocompatibility. It is suitable for both photocatalytic process and activated sludge treatment process. Therefore, the combination of photocatalytic technology and activated sludge process can further completely degrade organic pollutants. We found that CuCN could protect the survival and growth of microorganisms in activated sludge, so that the degradation efficiency of CuCN to nitrobenzene could reach 94.4 %. Therefore, CuCN has broad application prospects in photocatalytic-activated sludge combined treatment.

Nature of the Synergistic Effect of N and S Co-Doped Graphene for the Enhanced Simultaneous Determination of Toxic Pollutants.

N-doped graphene (NG), S-doped graphene (SG), and N and S co-doped graphene nanocatalysts with different doping sequences (N-SG and S-NG) are successfully synthesized by a facile low-temperature hydrothermal method. By changing the synthetic sequence, S-NG significantly increases the electron transport rate of the sensor and the electrocatalytic ability compared to NG, SG, and N-SG due to the optimal proportion of doping element content and suitable N- and S-bonding configurations. The origin of the synergistic effect of N and S co-doped graphene is confirmed. Traces of S doping greatly enhance the electrochemical performance. The large volume of S-Ox groups may prevent the analytes from approaching the catalytic sites of the sensing materials due to a steric hindrance effect. S-NG, which possesses less S-Ox groups, exhibits better performance than N-SG. Pyridinic N plays an important role in enhancing the electrochemical activity and conductivity. The simultaneous determination of aniline (AN), p-phenylenediamine (PPD), and nitrobenzene (NB) as typical toxic pollutants is performed by employing the S-NG nanoarchitecture. The detection limits (S/N = 3) for AN, PPD, and NB are 0.023, 0.051, and 0.216 µM, respectively. In addition, the S-NG sensors also have excellent anti-interference, stability, and reproducibility. The precise control and synthesis of multiheteroatoms into graphene represent a promising strategy to enhance the electrocatalytic performance in energy and environmental fields.

Ultratrace Nitroaromatic Vapor Detection via Surface-Enhanced Fluorescence on Carbazole-Terminated Black Silicon.

Detection of nitroaromatic compounds (NACs) is an important applied task for environmental monitoring, medical diagnostics, and forensic analysis. However, detection of NAC vapors is challenging owing to their low vapor pressure and relatively weak sensitivity of the existing detection techniques. Here, we propose a novel concept to design fluorescence (FL) detection platforms based on chemical functionalization of nanotextured dielectric surfaces exhibiting resonant light absorption, trapping, and localization effects. We demonstrate highly-efficient NAC vapor sensor with selective FL-quenching response from monolayers of carbazole moieties covalently bonded to a spiky silicon surface, "black" silicon, produced over the centimeter-scale area using simple reactive ion etching. The sensor is shown to provide unprecedented ppt (10-12) range limits of detection for several NAC vapors. Easy-to-implement scalable fabrication procedure combined with simple and versatile functionalization techniques applicable to all-dielectric surfaces make the suggested concept promising for realization of various gas sensing systems for social and environmental safety applications.

Enhanced nitrobenzene reduction by modified biochar supported sulfidated nano zerovalent iron: Comparison of surface modification methods.

In our previous study, biochar (BC) supported sulfidated nano zerovalent iron (S-nZVI@BC) was prepared for nitrobenzene (NB) reduction. In this study, in order to further improve the reduction performance of S-nZVI@BC, BC was modified before the loading of S-nZVI through three methods: oxidant (H2O2) pretreatment, alkali (NaOH) pretreatment and acid (HCl) pretreatment. The results indicated that S-nZVI could be evenly distributed onto HCl-BC due to increased surface area, negative surface charge and increased acidic functional groups on HCl-BC. At an initial concentration of 200 mg L-1, NB could be completely removed by S-nZVI@HCl-BC within a reaction time as short as 60 min, indicating rather excellent performance of S-nZVI@HCl-BC. NB reduction performance followed the order: S-nZVI@HCl-BC > S-nZVI@NaOH-BC > S-nZVI@BC > S-nZVI@H2O2-BC. The mass ratio of S-nZVI and HCl-BC was optimized in terms of NB removal efficiency, with 3:1 being identified as the best mass ratio. Furthermore, the mechanism involved in the enhanced NB reduction by S-nZVI@HCl-BC was proposed. This study demonstrated that S-nZVI@HCl-BC is a promising alternative for efficient NB removal from wastewater.

Effective biodegradation of pentachloronitrobenzene by a novel strain Peudomonas putida QTH3 isolated from contaminated soil.

To eliminate pentachloronitrobenzene (PCNB) residue in PCNB-contaminated environment, the degradation potential of Pseudomonas putida QTH3 to PCNB was evaluated in this study. Peudomonas putida QTH3 could grow well in mineral salt medium (MSM) containing PCNB as sole carbon and was able to degrade PCNB efficiently, whereas the degradation rate of P. putida QTH3 to PCNB increased gradually, and reached 49.84% in 35 days. The degradation rates of P. putida QTH3 to 13 tested organochlorine compounds found to be 10.85%-42.51% after 14 days. The metabolites during PCNB biodegradation by P. putida QTH3 were identified as catechol, 2, 3, 5, 6-tetrachloroaniline (TCA), 2, 3, 4, 5- TCA, 2, 3, 4, 5, 6-pentachloroaniline (PCA) and pentachlorothioanisole (PCTAs). Furthermore, possible degradation pathway of PCNB by P. putida QTH3 was proposed. The degradation rates of intracellular enzyme and extracellular enzyme were 44.73% and 8.93% after incubation with 100 mg L-1 PCNB for 30 min, respectively. Thus, intracellular enzyme is a major enzyme responsible for PCNB degradation. The results indicate that P. putida QTH3 can be a suitable organism for the degradation of PCNB, and facilitate its potential for the bioremediation of the environments contaminated with major organochlorine compounds used during this study.

4-Mercaptobenzoic acid capped terbium(III)-doped CaF2 nanocrystals: a fluorescent probe for nitroaromatic pollutants.

The authors report on an energy transfer based fluorometric approach for the detection of nitroaromatic pollutants. This is achieved using 4-mercaptobenzoic acid (4-MBA)-capped CaF2:Tb3+ nanocrystals that were synthesized by a microwave procedure. 4-MBA acts as both a capping agent and a sensitizer for the Tb3+ ions in CaF2 host matrix. This approach is different from the earlier studies where Ce3+ is generally used as the sensitizer for the Ln3+ ions. The use of capping ligand as sensitizer has the feature that binding of nitroaromatics directly to the sensitizer can alter the energy transfer efficiency between the sensitizer and the Tb3+ ions. The fluorescent nanocrystal probe doped with 2% of Tb3+ displays green emission with a peak at 542 nm if photoexcited at 311 nm. The emission is quenched if the nanocrystals are exposed to nitroaromatic compounds such as 4-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol (picric acid), 4-nitrotoluene, 2,4-dinitrotoluene and 2,4,6-trinitrotoluene. These analytes also cause a (longwave/shortwave) shift in the excitation maxima which helps in identifying the individual nitroaromatic compound using single nanoprobe. The respective detection limits (by applying the 3σ/K criterion) are 0.86 µM, 0.83 µM, 0.78 µM, 0.36 µM, 1.5 µM, and 1.96 µM. Graphical abstract Schematic illustration of the use of 4-mercaptobenzoic acid (MBA)-capped CaF2:Tb3+ nanocrystals as a fluorescent nanoprobe for the detection of nitroaromatic analytes. The Tb3+ ions show strong green fluorescence via 4-MBA-induced ligand sensitization. The specific π interaction between 4-MBA capped CaF2 nanocrystals and nitroaromatics leads to reduction in the fluorescence intensity by inhibiting the energy transfer from 4-MBA to Tb3+ ion in CaF2 nanocrystals.

Performance of a novel magnetic solid-phase-extraction microsphere and its application in the detection of organic micropollutants in the Huai River, China.

Solid phase extraction has been increasingly applied for the detection of organic micropollutants (OMPs). However, time-consuming and high-cost disadvantages also limit the widespread use of this method, especially for the extraction of large-volume field water samples. In this study, a gas chromatography-mass spectrometry (GC-MS) method based on the magnetic microsphere (M150) solid-phase-extraction (MSPE) was established to investigate the OMPs in source water throughout the whole Huai River. In brief, the results demonstrated that the extraction efficiency of the M150 was superior to that of C18 and HLB for the selected OMPs, including species of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), phthalate esters (PAEs) and nitrobenzenes (NBs), and the method detection limits of M150 for these OMPs were comparable to those of C18 and HLB. The optimized conditions of extraction and elution were the 100 mg/L dosages of microspheres, extraction time of 60 min and pH of 2, and the eluent with a similar polarity, hydrophobicity and molecular structure to the OMPs rendered higher elution efficiencies. A total of 21 types of OMPs affiliating to PAHs, OCPs, PAEs and NBs were detected by the established method, with the total concentrations of 505-2310 ng/L in source water of the Huai River. Spatial differences of the OMPs were also observed, demonstrating the link between pollutant profiles and geographical locations. This study provides an alternative to enrich OMPs in filed water samples, and it reveals pollutant profiles of source water throughout the whole Huai River.

Efficient reduction of nitrobenzene by sulfate-reducer enriched biocathode in microbial electrolysis cell.

This study aimed to enhance treatment of wastewater containing nitrobenzene (NB) and sulfate using biocathode enriched with sulfate-reducing bacteria in microbial electrolysis cell (MEC). Artificial wastewater with 50 mg L-1 NB and 200 mg L-1 sulfate was used as the catholyte. With 0.8 V applied voltage, removal efficiencies of NB and sulfate reached 98% and 34%, respectively, within 36 h. Aniline and sulfide were the main reductive products in the catholyte with concentrations increased to 0.32 and 0.51 mM, which accounted for 97% and 78% of the removed NB and sulfate, respectively. Sulfate-reducer Desulfovibrio sp. and Wolinella sp. played the dominant role in the biocathode for the reductions of sulfate and NB. Analyses of scanning electron microscope and X-ray photoelectron spectroscopy showed the formation of elemental S on the biocathode surface. The relative abundance of sulfur-oxidizing bacterium Thioclava sp. reached 24% on the biocathode. The results indicated that the oxidation process from S2- to S0 occurred on the biocathode, which provided electrons to biofilm for NB reduction. The MEC with sulfate-reducer enriched biocathode can be used as an alternative to treat complex wastewater containing NB and sulfate.

Method development and laboratory intercomparison of an RP-HPLC-UV method for energetic chemicals in marine tissues.

Experiments were conducted to develop a method for the determination of a set of 17 military-relevant energetic compounds (including nitroaromatics, nitramines, and nitrate esters) in 5 types of marine tissues (Dungeness crab, Manila clam, starry flounder, sea cucumber, and geoduck) using reversed-phase high performance liquid chromatography with a UV detector (RP-HPLC-UV). Dry-ice grinding was evaluated and found to be an excellent method of sample homogenization prior to sample extraction and determination. An extract cleanup procedure based on solid-phase extraction was assessed. A cleanup procedure using solid phase extraction was adequate for the removal of interferences prior to HPLC analysis for the five marine tissue matrices tested. Mean method detection limits (MDLs) were estimated using two columns at two wavelengths (254 and 210 nm) and ranged from 17 to 293 µg/kg for the five tissue matrices tested. A six-laboratory intercomparison test was conducted to evaluate the performance of the method, each analyzing five marine tissue matrices fortified at three levels. The same marine tissues were used in the laboratory intercomparison study except Pacific halibut was substituted for starry flounder. Overall, USEPA Method 8330B modified for tissue analysis showed suitable detection capability, analytical accuracy, precision, sensitivity, linear range, and robustness for sixteen (16) of the seventeen (17) analytes, for all five (5) of the marine tissue matrices studied. The exception was tetryl that proved to be unstable for all matrices as has been found for soils and sediments.

Sorption behaviors of phenanthrene, nitrobenzene, and naphthalene on mesoplastics and microplastics.

The occurrence of plastic particles in aquatic environment has led to enormous concern in the past few years. The sorption behaviors of harmful organic compounds by plastic particles can increase their concentrations by several orders of magnitude influencing their global transport in the marine environment. Five types of mesoplastics (5-20 mm) and five types of microplastics (< 5 mm) were selected to investigate the sorption behaviors of three typical organic compounds (phenanthrene, nitrobenzene, and naphthalene). For phenanthrene, most microplastics have stronger sorption ability than that of mesoplastics due to the higher specific surface area (SSA). However, the sorption ability of nitrobenzene on low-density polyethylene (LDPE) mesoplastics was higher than that on LDPE microplastics, and the sorption ability of naphthalene on polyvinyl chloride (PVC) mesoplastics was higher than that on PVC microplastics, which were attributed to the presence of functional groups on the surface of mesoplastics, induced by adding slip agents, lubricant, plasticizer, stabilizer, etc. during film production. Talcum-filled polypropylene (PP) microplastics had strongest sorption ability to nitrobenzene and naphthalene due to the presence of talcum and high SSA. For unmodified microplastics, the sorption abilities of phenanthrene, nitrobenzene, and naphthalene were all followed the order of high-density polyethylene (HDPE) > polystyrene (PS) > LDPE > PVC after SSA normalization. Thus, SSA and the functional groups on the surface of plastic particles should be considered when the sorption behaviors of harmful organic compounds on plastic particles are studied.

Tetrathiafulvalene-calix[4]pyrrole: a versatile synthetic receptor for electron-deficient planar and spherical guests.

The first tetrakis-tetrathiafulvalene-calix[4]pyrrole (TTF-C[4]P) was reported in 2004. Early on it and related π-extended TTF-C[4]Ps were found to function as both anion receptors and as hosts for planar electron deficient neutral guests, including nitroaromatic explosives. Anion binding was found to occur with a 1 : 1 binding stoichiometry and to stabilise the cone C[4]P conformation, whereas planar electron deficient guests were bound in a cooperative 1 : 2 fashion to the 1,3-alternate conformer. Addition of strongly complexing anions was found to trigger release of the electron deficient guests concurrent with a conformational change to the cone form. Subsequent studies led to the discovery of anion-induced complexation with C60, and the finding that the resulting complexes would support fast photoinduced electron transfer events. Synthetic advances then led to the preparation of nonsymmetric TTF-C[4]Ps where a single moiety organises the receptor in either the 1,3-alternate conformation or the partial cone conformation, thus modifying both selectivity and sensitivity. TTF-C[4]P-based stimulus responsive systems, that rely on anions and cations as controlling inputs, have also been developed and studied in recent years. This review provides a summary of TTF-C[4]P-related chemistry.

Passive in situ biobarrier for treatment of comingled nitramine explosives and perchlorate in groundwater on an active range.

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and perchlorate (ClO4-) are common, and often co-mingled, contaminants at military ranges worldwide. This project investigated the feasibility of using a passive emulsified oil biobarrier plus a slow release pH buffering reagent to remediate RDX, HMX, and ClO4- in a low pH aquifer at an active range. A 33 m biobarrier was emplaced perpendicular to the contaminant plumes, and dissolved explosives, perchlorate, and other relevant parameters were monitored. The pH increased and the DO and ORP decreased after emulsified oil injection, leading to >90% reductions in perchlorate, RDX, and HMX compared to upgradient groundwater. Some nitroso breakdown products were observed immediately downstream of the barrier, but generally decreased to below detection limits farther downgradient. First-order rate constants of approximately 0.1/d were obtained for all three contaminants. Dissolved metals (including As) also increased in the wells immediately adjacent to the barrier, but attenuated as the plume re-aerated in downgradient areas. Biobarrier installation and sampling were performed during scheduled range downtime and had no impacts to ongoing range activities. The field trial suggests that an emulsified oil biobarrier with pH buffering can be a viable alternative to remove explosives and perchlorate from shallow groundwater on active ranges.