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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.

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-O x 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-O x 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.

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.

Detection of explosive residues in soil and postblast debris is an important issue in sensor design for environmental and criminological purposes. An easy-to-use and low-cost gold nanoparticle (AuNP)-based colorimetric sensor was developed for the determination of nitroaromatic explosives, i.e., trinitrotoluene (TNT) and tetryl, capable of analyte detection at picomolar (pM) levels. The sensor nanoparticles were synthesized by functionalizing the negatively charged thioglycolic acid (TGA)-modified AuNPs with positively charged (±)- trans-1,2-diaminocyclohexane (DACH) at a carefully calculated pH. The working principle of the sensor is charge-transfer (CT) interaction between the electron-rich free amino (-NH 2 ) group of DACH and the electron-deficient -NO 2 groups of TNT/tetryl, added to possible nanoparticle agglomerization via electrostatic interaction of TNT-Meisenheimer anions with more than one cationic DACH-modified AuNP. The limit of detection (LOD) and limit of quantification (LOQ) of the sensor were 1.76 pM and 5.87 pM for TNT and 1.74 pM and 5.80 pM for tetryl, respectively. TNT, tetryl, and tetrytol, extracted from a nitroaromatic explosive-contaminated soil sample, were determined with the proposed sensor, yielding good recoveries. The sensor could be selectively applied to various mixtures of TNT with common energetic materials such as RDX, HMX, and PETN. Additionally, common soil ions (Cl - , NO 3 - , SO 4 2- , K + , Mg 2+ , Ca 2+ , Cu 2+ , Fe 2+ , Fe 3+ , and Al 3+ ) as well as detergents, sugar, sweeteners, acetylsalicylic acid (aspirin), caffeine, and paracetamol-based painkiller drugs, which may be used as camouflage materials for explosives, either had no adverse effects or removable interferences on the detection method. The developed method was statistically validated against a GC-MS literature method.

Since nitroaromatic- and nitramine-type energetic materials, mostly arising from military activities, are persistent pollutants in soil and groundwater, on-site sensing of these hazardous chemicals has gained importance. A novel electrochemical sensor was designed for detecting nitroaromatic- and nitramine-type energetic materials, relying on gold nanoparticles (Au nano ), modified glassy carbon (GC) electrode coated with nitro-energetic memory-poly(carbazole-aniline) copolymer (Cz- co-ANI) film (e.g., TNT memory-GC/P(Cz- co-ANI)-Au nano modified electrode). Current was recorded against concentration to build the calibration curves that were found to be linear within the range of 100-1000 μg L -1 for 2,4,6-trinitrotoluene (TNT) and 2,4-dinitrotoluene (DNT): 50-1000 μg L -1 for 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The corresponding limits of detection were 25 μg L -1 for TNT, 30 μg L -1 for DNT, and 10 μg L -1 for both RDX and HMX, using nitro-energetic memory-GC/P(Cz- co-ANI)-Au nano electrodes. These electrodes were used separately, and specific determinations were made in various mixtures of nitro-energetic materials. The developed method could be efficiently used in electroanalyzing nitroaromatics and nitramines in military explosives (i.e., comp B, octol, and comp A5). The sensor electrodes were specific for the tested nitro-energetic compounds and did not respond to paracetamol-caffeine-based analgesic drug, acetylsalicylic acid (aspirin), sweetener, and sugar that can be used as camouflage materials in passenger belongings. The developed method was statistically validated against the standard LC-MS reference method in contaminated clay soil samples containing TNT and RDX explosives.

Synchronized discharge ionization (SDI) was previously developed for hand-held mass spectrometers with discontinuous atmospheric pressure interfaces. The function of SDI has been demonstrated for analysis of volatile organic compounds in air at high sensitivity, which is attributed to the fact that ions were produced next to the ion trap mass analyzer inside the vacuum manifold. In this study, a simple sampling device was designed and fitted to a hand-held mass spectrometer to characterize its potential in direct analysis of low-volatility chemicals on surfaces. Nine chemicals of vapor pressures ranging from 10(-4) to 10(-8) Torr (at room temperature), including pesticides, illicit drugs, and explosives, were selected to evaluate and demonstrate the analytical capability of the designed system. Compounds of vapor pressures below 10(-7) Torr, such as tetryl, cocaine, and tetrahydrocannabinol (THC), have been successfully detected. Direct analysis of pesticides from fruit and explosives from a large surface area has also been demonstrated. Tandem mass analysis was performed, which helped to confirm the analyte identity as well as to improve the signal-to-noise ratio (S/N).

A series of uranyl-organic frameworks (UOFs), {[(UO2)2(H2TTHA)(H2O)]·4,4'-bipy·2H2O}n (1), {[(UO2)3(TTHA)(H2O)3]}n (2), and {[(UO2)5(TTHA) (HTTHA)(H2O)3]·H3O}n (3), have been obtained by the hydrothermal reaction of uranyl acetate with a flexible hexapodal ligand (1,3,5-triazine-2,4,6-triamine hexaacetic acid, H6TTHA). These compounds exhibited three distinct 3D self-assembly architectures as a function of pH by single-crystal structural analysis, although the used ligand was the same in each reaction. Surprisingly, all of the coordination modes of the H6TTHA ligand in this work are first discovered. Furthermore, the photoluminescent results showed that these compounds displayed high-sensitivity luminescent sensing functions for nitrobenzene. Additionally, the surface photovoltage spectroscopy and electric-field-induced surface photovoltage spectroscopy showed that compounds 1-3 could behave as p-type semiconductors.

Formation of nitrosamines and nitramines from reactions between flue gas NOx and the amines used in CO2 capture units has arisen as a significant concern. Washwater scrubbers can capture nitrosamines and nitramines. They can also capture amines, preventing formation of nitrosamines and nitramines downwind by amine reactions with ambient NOx. The continuous application of UV alone, or a combination of UV and ozone to the return line of a washwater treatment unit was evaluated to control the accumulation of nitrosamines, nitramines and amines in a laboratory-scale washwater unit. With model secondary amine solvents ranging from nonvolatile diethanolamine to volatile morpholine, application of 272-537 mJ/cm(2) UV incident fluence alone reduced the accumulation of nitrosamines and nitramines by approximately an order of magnitude. Modeling indicated that the gains achieved by UV treatment should increase over time, because UV treatment converts the time dependence of nitrosamine accumulation from a quadratic to a linear function. Ozone (21 mg/L) maintained low steady-state concentrations of amines in the washwater. While modeling indicated that more than 80% of nitrosamine accumulation in the washwater was associated with reaction of washwater amines with residual NOx, a reduction in nitrosamine accumulation rates due to ozone oxidation of amines was not fully realized because the ozonation products of amines reduced nitrosamine photolysis rates by competing for photons.

We developed an efficient one-pot strategy for the preparation of hydrophilic amine-functionalized nanocomposites by using hydrophobic fluorescence quantum dots ZnS:Mn(2+)@allyl mercaptan (QDs@AM) as building blocks through novel light-induced in situ polymerization. The average size of as-prepared hydrophilic nanocomposites was ∼50 nm, which could be further tuned by varying the concentrations of the monomers. Importantly, these nanocomposites were further utilized for the facile, highly sensitive, and selective detection of nitroaromatics. The linear ranges for 2,4,6-trinitrotoluene (TNT) and 2,4,6-trinitrophenol (TNP) lie in 0.01-0.5 μg/mL and 0.05-8.0 μg/mL, respectively, barely interfered with by other nitroaromatics such as 2,4-dinitrotoluene (DNT) and nitrobenzene (NB). Moreover, the novel surface modification method developed here offered a general strategy for fabricating hydrophobic nanocomposites with hydrophilic properties and indicated various potential applications including sensing and imaging.

In this work, five novel 2D isostructural Cd(II)-lanthanide(III) heterometallic-organic frameworks [CdCl(L)Eu(x)Tb(y)(H2O)(DMA)](NO3)·3DMA (IFMC-36-Eu(x)Tb(y): x = 1, y = 0, IFMC-36-Eu; x = 0.6, y = 0.4, IFMC-36-Eu(0.6)Tb(0.4); x = 0.5, y = 0.5, IFMC-36-Eu(0.5)Tb(0.5); x = 0.4, y = 0.6, IFMC-36-Eu(0.4)Tb(0.6); x = 0, y = 1, IFMC-36-Tb; H3L is 4,4',4″-((2,2',2″-(nitrilotris(methylene))tris(1H-benzo[d]imidazole-2,1-diyl))tris(methylene))tribenzoic acid; IFMC = Institute of Functional Material Chemistry) have been successfully synthesized by taking advantage of different molar ratios of lanthanide(III) (Ln(III)) and metalloligands under solvothermal conditions. Further luminescent measurements indicate that IFMC-36-Eu(x)Tb(y) exhibits characteristic sharp emission bands of Eu(III) and Tb(III), and the intensities of red and green can be modulated correspondingly by tuning the ratios of Eu(III) and Tb(III). Particularly, the solvent-dependent luminescent behavior of IFMC-36-Eu shows a potential application in detection of small-molecule pollutant nitrobenzene by significant fluorescence quenching. Furthermore, IFMC-36-Eu displays preeminent anti-interference ability and could be used for sensing in the systems with complicated components. This is the first time that a d-f heterometallic-organic framework can be investigated as a chemical sensor for selective, sensitive, and recyclable detection of nitrobenzene.

Amine-based technologies are emerging as the prime contender for postcombustion CO2 capture. However, concerns have arisen over the health impacts of amine-based CO2 capture associated with the release of nitrosamines and nitramines, which are byproducts from the reactions between flue gas NOx and solvent amines. In this study, flue gas compositions were systematically varied to evaluate their effects on the formation of nitrosamines and nitramines in a lab-scale CO2 capture reactor with morpholine as a model solvent amine. The accumulation of N-nitrosomorpholine in both the absorber and washwater increased linearly with both NO and NO2 for concentrations up to ∼20 ppmv. These correlations could be extrapolated to estimate N-nitrosomorpholine accumulation at extremely low NOx levels (0.3 ppmv NO2 and 1.5 ppmv NO). NO played a particularly important role in driving N-nitrosomorpholine formation in the washwater, likely following partial oxidation to NO2 by O2. The accumulation of N-nitromorpholine in both the absorber and washwater positively correlated with flue gas NO2 concentration, but not with NO concentration. Both N-nitrosomorpholine and N-nitromorpholine accumulated fastest in the absence of CO2. Flue gas humidity did not affect nitrosamine accumulation in either the absorber or the washwater unit. These results provide a basis for estimating the effects of flue gas composition on nitrosamine and nitramine accumulation in postcombustion CO2 capture systems.

Oxidation of aromatic rings and its alkyl substituents are often competing initial steps of organic pollutant transformation. The use of compound-specific isotope analysis (CSIA) to distinguish between these two pathways quantitatively, however, can be hampered by large H isotope fractionation that precludes calculation of apparent (2)H-kinetic isotope effects (KIE) as well as the process identification in multi-element isotope fractionation analysis. Here, we investigated the C and H isotope fractionation associated with the transformation of toluene, nitrobenzene, and four substituted nitrotoluenes by permanganate, MnO4(-), to propose a refined evaluation procedure for the quantitative distinction of CH3-group oxidation and dioxygenation. On the basis of batch experiments, an isotopomer-specific kinetic model, and density functional theory (DFT) calculations, we successfully derived the large apparent (2)H-KIE of 4.033 ± 0.20 for the CH3-group oxidation of toluene from H isotope fractionation exceeding >1300‰ as well as the corresponding (13)C-KIE (1.0324 ± 0.0011). Experiment and theory also agreed well for the dioxygenation of nitrobenzene, which was associated with (2)H- and (13)C-KIEs of 0.9410 ± 0.0030 (0.9228 obtained by DFT) and 1.0289 ± 0.0003 (1.025). Consistent branching ratios for the competing CH3-group oxidation and dioxygenation of nitrotoluenes by MnO4(-) were obtained from the combined modeling of concentration as well as C and H isotope signature trends. Our approach offers improved estimates for the identification of contaminant microbial and abiotic oxidation pathways by CSIA.

The determination of nitroaromatic compounds in aqueous solution was investigated at β-cyclodextrin (β-CD)/silver nanoparticle (AgNPs) composite modified ITO electrodes. This method relies on the different reduction potentials for the various nitroaromatic isomers, the different binding strengths of the nitroaromatic isomer guests to the β-CD host, and excellent electron transfer ability of AgNPs. After incubation in a solution with different single nitroaromatic compounds, reduction peaks in the range from -550 to -913 mV were observed at the modified electrode, depending on the nitroaromatic compound present. The sensor exhibited selectivity for some isomers in a solution containing a mixture of nitroaromatic compounds. In particular, the sensor shows specificity for 4-nitroaniline and 1-chloro-2-nitrobenzene over other nitroaniline isomers and nitrochlorobenzene isomers, respectively. The results show that all the nitroaromatic compounds, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 1-chloro-2-nitrobenzene, 1-chloro-3-nitrobenzene, and 1-chloro-4-nitrobenzene, could not only be detected but the electrode demonstrated a preference for the more strongly complexing species.

Rapid, sensitive, and selective detection of explosives such as 2,4,6-trinitrotoluene (TNT) and 2,4,6-trinitrophenol (TNP), especially using a facile paper sensor, is in high demand for homeland security and public safety. Although many strategies have been successfully developed for the detection of TNT, it is not easy to differentiate the influence from TNP. Also, few methods were demonstrated for the selective detection of TNP. In this work, via a facile and versatile method, 8-hydroxyquinoline aluminum (Alq(3))-based bluish green fluorescent composite nanospheres were successfully synthesized through self-assembly under vigorous stirring and ultrasonic treatment. These polymer-coated nanocomposites are not only water-stable but also highly luminescent. Based on the dramatic and selective fluorescence quenching of the nanocomposites via adding TNP into the aqueous solution, a sensitive and robust platform was developed for visual detection of TNP in the mixture of nitroaromatics including TNT, 2,4-dinitrotoluene (DNT), and nitrobenzene (NB). Meanwhile, the fluorescence intensity is proportional to the concentration of TNP in the range of 0.05-7.0 μg/mL with the 3σ limit of detection of 32.3 ng/mL. By handwriting or finger printing with TNP solution as ink on the filter paper soaked with the fluorescent nanocomposites, the bluish green fluorescence was instantly and dramatically quenched and the dark patterns were left on the paper. Therefore, a convenient and rapid paper sensor for TNP-selective detection was fabricated.

With years of full-scale experience for precombustion CO(2) capture, amine-based technologies are emerging as the prime contender for postcombustion CO(2) capture. However, concerns for postcombustion applications have focused on the possible contamination of air or drinking water supplies downwind by potentially carcinogenic N-nitrosamines and N-nitramines released following their formation by NO(x) reactions with amines within the capture unit. Analytical methods for N-nitrosamines in drinking waters were adapted to measure specific N-nitrosamines and N-nitramines and total N-nitrosamines in solvent and washwater samples. The high levels of amines, aldehydes, and nitrite in these samples presented a risk for the artifactual formation of N-nitrosamines during sample storage or analysis. Application of a 30-fold molar excess of sulfamic acid to nitrite at pH 2 destroyed nitrite with no significant risk of artifactual nitrosation of amines. Analysis of aqueous morpholine solutions purged with different gas-phase NO and NO(2) concentrations indicated that N-nitrosamine formation generally exceeds N-nitramine formation. The total N-nitrosamine formation rate was at least an order of magnitude higher for the secondary amine piperazine (PZ) than for the primary amines 2-amino-2-methyl-1-propanol (AMP) and monoethanolamine (MEA) and the tertiary amine methyldiethanolamine (MDEA). Analysis of pilot washwater samples indicated a 59 μM total N-nitrosamine concentration for a system operated with a 25% AMP/15% PZ solvent, but only 0.73 μM for a 35% MEA solvent. Unfortunately, a greater fraction of the total N-nitrosamine signal was uncharacterized for the MEA-associated washwater. At a 0.73 μM total N-nitrosamine concentration, a ~25000-fold reduction in concentration is needed between washwater units and downwind drinking water supplies to meet proposed permit limits.

Significant security threats posed by highly energetic nitroaromatic compounds in aquatic environments and the demilitarization and pending cleanup of areas previously used for munitions manufacture and storage represent a challenge for less expensive, faster, and more sensitive systems capable of analyzing groundwater and seawater samples for trace levels of explosive materials. Presented here is an inexpensive high throughput microfluidic immunosensor (HTMI) platform intended for the rapid, highly selective quantitation of nitroaromatic compounds in the field. Immunoaffinity and fluorescence detection schemes were implemented in tandem on a novel microfluidic device containing 39 parallel microchannels that were 500 μm tall, 250 μm wide, and 2.54 cm long with covalently tethered antibodies that was engineered for high-throughput high-volume sample processing. The devices were produced via a combination of high precision micromilling and hot embossing. Mass transfer limitations were found in conventional microsystems and were minimized due to higher surface area to volume ratios that exceeded those possessed by conventional microdevices and capillaries. Until now, these assays were limited to maximum total volume flow rates of ~1 mL/min due in part to kinetics and high head pressures of single microchannels. In the design demonstrated here, highly parallelized microchannels afforded up to a 100-fold increase in total volume flow rate while maintaining favorable kinetic constraints for efficient antigen-antibody interaction. The assay employed total volume throughput of up to 6 mL/min while yielding signal-to-noise ratios of >15 in all cases. In addition to samples being processed up to 60 times faster than in conventional displacement-based immunoassays, the current system was capable of quantitating 0.01 ng/mL TNT samples without implementing offline preconcentration, thereby, demonstrating the ability to improve sensitivity by as much as 2 orders of magnitude while decreasing total analysis times up to 60-fold.

Oxidation of the Ag nanoparticle surface has a dramatic effect on the adsorption, orientation, and SERS detection limit of nitroaromatic molecules in aqueous solutions. Ultrasensitive SERS detection of p-nitrophenol can be achieved when oxidation of surface-immobilized Ag nanoparticles is inhibited by replacing the oxygen dissolved in water with argon gas. The presence of silver oxide at the nanoparticle surface hinders charge transfer between the aromatic ring and the underlying Ag metal surface and drastically decreases the overall detection sensitivity.

The effect of nitrate reduction onthe reductive biotransformation of pentachloronitrobenzene (PCNB), an organochlorine fungicide, was assessed with a mixed fermentative/methanogenic culture enriched from a contaminated estuarine sediment. Glucose and methanol served asthe electron and carbon source. PCNB at an initial concentration of 3 microM was transformed to pentachloroaniline (PCA) simultaneously with nitrate reduction in cultures amended with 10 to 200 mg N/L nitrate. PCA sequentially dechlorinated to dichlorinated anilines (mainly 2,5-DCA) in the nitrate-free control culture, and the culture which was amended with 10 mg N/L nitrate. PCA partially dechlorinated to tetrachloroanilines (TeCAs), and methanogenesis was completely inhibited in the cultures amended with 50-200 mg N/L nitrate, whereas fermentation was only inhibited in the cultures amended with 200 mg N/L nitrate. The impact of nitrate reduction on the sequential dechlorination of PCA was attributed to the production of nitric oxide (NO) and nitrous oxide (N2O). Partial nitrate reduction to ammonia was observed in the cultures amended with 50, 100, or 200 mg N/L nitrate and PCNB (3 microM). Therefore, nitrate concentrations at or above 50 mg N/L lead to accumulation of toxic compounds such as highly chlorinated anilines (i.e., PCA, TeCAs) and denitrification intermediates (i.e., NO, N2O). These findings have significant environmental implications in terms of the fate and transformation of PCNB in subsurface environments where nitrate is present.

The distribution of organochlorine pesticides (OCP; in past and current use) in the mountains of western Canada was determined by sampling air, soil, and lichen along three elevational transects in 2003-2004. Two transects west of the Continental Divide were located in Mount Revelstoke and Yoho National Park, while the Observation Peak transect in Banff National Park is east of the divide. XAD-based passive air samplers, yielding annually averaged air concentrations, were deployed, and soils were collected at all 22 sampling sites, whereas lichen were only sampled in Revelstoke. Back trajectory analysis showed limited air mass transport from the Prairies to the east, but a high frequency of air arriving from the southwest, which includes agricultural regions in British Columbia and Washington State. Endosulfan, dieldrin, and a-hexachlorocyclohexane were the most prevalent OCPs in air and soil; hexachlorobenzene was only abundant in air; chlorothalonil, dacthal, and pentachloronitrobenzene were also consistently present. OCP air concentrations were similar across the three transects, suggesting efficient atmospheric mixing on a local and regional scale. Soil concentrations and soil/air concentration ratios of many OCPs were significantly higher west of the Continental Divide. The soil and lichen concentrations of most OCPs increased with altitude in Revelstoke, and displayed maxima at intermediate elevations at Yoho and Observation Peak. These distribution patterns can be understood as being determined by the balance between atmospheric deposition to, and retention within, the soils. Higher deposition, due to more precipitation falling at lower temperatures, likely occurs west of the divide and at higher elevations. Higher retention, due to higher soil organic matter content, is believed to occur in soils below the tree line. Highest pesticide concentrations are thus found intemperate mountain soils that are rich in organic matter and receive large amounts of cold precipitation.

A competitive enzyme-linked immunosorbent assay (ELISA) for pentachloronitrobenzene (PCNB), a fungicide and chemical intermediate, was developed using a polyclonal antiserum produced against a hapten-protein conjugate of pentachlorophenoxypropionic acid-bovine serum albumin (BSA). An indirect competitive ELISA of PCNB showed an IC50 of 37 ng/mL and a limit of detection (LOD) of 7 ng/mL. The ELISA can tolerate up to 10% (v/v) methanol, 5% (v/v) acetonitrile, or 5% (v/v) acetone without significant fluctuation of Amax and IC50. The assay sensitivity showed little change in a range of pH from 6 to 8 and concentrations of 0.05-0.2 M NaCl in the assay buffer. Very low cross-reactivities were observed for some structurally related compounds except for hexachlorobenzene (12%). The average recoveries of PCNB from fortified well water, river water, and soil samples were in ranges of 88-94, 80-91, and 70-81%, respectively. The correlations between the gas chromatographic and ELISA results were excellent (r 2 >or= 0.97, slopes from 0.86 to 1.10) for those fortified samples. The ELISA is a good alternative tool for monitoring PCNB residues in environmental samples.

The development of predictive models for the reductive transformation of nitroaromatics requires further clarification of the effect of environmentally relevant variables on reaction kinetics and the identification of readily available molecular descriptors for calculating reactivity. Toward these goals, studies were performed on the reduction of a series of monosubstituted nitrobenzenes in Fe(II)-treated goethite suspensions. The energy of the lowest unoccupied molecular orbital, ELUMO (B3LYP/6-31G*,water), of the nitrobenzenes was capable of explaining 99% of the variability in the rates. Results of experiments in which the surface area loading of ferric oxides was systematically varied indicate that (i) the reactivity of mineral-surface-associated Fe(II), Fe(II)surf, toward the reduction of p-cyanonitrobenzene (CNNB) decreased in the order hematite > goethite > lepidocrocite > ferrihydrite and (ii) the surface density of Fe(II)surf did not play a crucial role in determining the observed reactivity trend. CNNB was reduced in Fe(II)-only control experiments in a pH range of 7.28-7.97 with a pH dependency consistent with the transformation of Fe(II) to Fe(OH)3 or related oxides. The pH dependency of the reduction of CNNB in Fe(II)-treated ferric oxide suspensions (pH 6.1-7.97) could be accounted for by the oxidation of Fe(II)surf, forming an Fe(III) oxide.

Metal nanoparticles (Pt, Au, or Cu) together with multiwalled and single-walled carbon nanotubes (MWCNT and SWCNT) solubilized in Nafion have been used to form nanocomposites for electrochemical detection of trinitrotoluene (TNT) and several other nitroaromatics. Electrochemical and surface characterization by cyclic voltammetry, AFM, TEM, SEM, and Raman spectroscopy confirmed the presence of metal nanoparticles on CNTs. Among various combinations tested, the most synergistic signal effect was observed for the nanocomposite modified glassy carbon electrode (GC) containing Cu nanoparticles and SWCNT solubilized in Nafion. This combination provided the best sensitivity for detecting TNT and other nitroaromatic compounds. Adsorptive stripping voltammetry for TNT resulted in a detection limit of 1 ppb, with linearity up to 3 orders of magnitude. Selectivity toward the number and position of the nitro groups in different nitroaromatics was very reproducible and distinct. Reproducibility of the TNT signal was within 7% (n = 8) from one electrode preparation to another, and the response signal was stable (+/-3.8% at 95% confidence interval) for 40 repeated analyses with 10 min of preconditioning. The Cu-SWCNT-modified GC electrode was demonstrated for analysis of TNT in tap water, river water, and contaminated soil.

Reactions mediated by iron mineral surfaces play an important role in the fate of organic contaminants in both natural and engineered systems. As such reactions proceed, the size, morphology, and even the phase of iron oxide minerals can change, leading to altered reactivity. The reductive degradation of 4-chloronitrobenzene and trichloronitromethane by Fe(II) associated with goethite (alpha-FeOOH) was examined by performing sequential-spike batch experiments. The particle size and size distribution of the pre- and postreaction particles were quantified using transmission electron microscopy (TEM). Results demonstrate that the degradation reactions result in goethite growth in the c-direction. Furthermore, pseudo-first-order reaction rate constants for the degradation of 4-chloronitrobenzene and trichloronitromethane and for the loss of aqueous Fe(II) decrease dramatically with each subsequent injection of organic compound and Fe(II). This result indicates that the newly formed material, which TEM and X-ray diffraction results confirm is goethite, is progressively less reactive than the original goethite. These results represent an important step toward elucidating the link between mineral surface changes and the evolving kinetics of contaminant degradation at the mineral-water interface.

An electrochemical sensor for ultratrace nitroaromatic compounds (NACs) using mesoporous SiO2 of MCM-41 as sensitive materials is reported. MCM-41 was synthesized and characterized by scanning electron microscope, transmission electron microscopy, and small-angle X-ray diffraction. Glassy carbon electrodes modified with MCM-41 show high sensitivity for cathodic voltammetric detection of NACs (including 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitrobenzene (TNB), 2,4-dinitrotoluene, and 1,3-dinitrobenzene) down to the nanomolar level. The high sensitivity is attributed to the strong adsorption of NACs by MCM-41 and large surface area of the working electrode resulting from MCM-41 modification. The voltammetric response is fast, and the detection of NACs can be finished within 14 s. SiO2 nanospheres were similarly used to modify glassy carbon electrodes for electrochemical detection of TNT and TNB. The detection limit of SiO2 nanosphere-modified electrodes is lower than that of MCM-41-modified electrodes, possibly due to the smaller surface area of SiO2 nanospheres than mesoporous MCM-41. The results show mesoporous SiO2-modified glassy carbon electrodes, particularly MCM-41-modified electrodes, open new opportunities for fast, simple, and sensitive field analysis of NACs.

Environmental black carbon (BC) is believed to be an important adsorbent of organic pollutants. In this study, we examined the effects of changes in surface properties and adsorbate structure. A series of apolar compounds (cyclohexane, 1,2-dichlorobenzene, 1,4-xylene, 1,2,3,5-tetramethylbenzene, 1,3,5-triethylbenzene) and a series of polar compounds (o-cresol, 4-nitrotoluene, 2,4-dinitrotoluene, and 2,4,6-trinitrotoluene) were sorbed from aqueous solution to maple wood char prepared under five thermochemical conditions. Two chars were prepared in air at 340 degrees C (C340) and 400 degrees C (C400). A subsample of C400 was treated with H2 in the presence of a supported Pt catalyst at 500 degrees C (C400-H) to remove surface O. Another was treated under N2 at 500 degrees C (C400-N) to serve as a control for C400-H. The reduced C400-H was further oxidized in air at 340 degrees C to reintroduce O (C400-H-A). The five chars vary in O content (26.1, 22.3, 4.2, 20.8, and 18.6 wt %, respectively) but show only minor differences in surface area and pore size distribution on the basis of N2 and CO2 adsorption analysis. These chars provide a basis for rationalizing sorption intensity as a function of sorbate molecular structure and surface chemistry. The following conclusions were drawn. (1) Polar interactions with surface O functional groups are not a significant driving force for adsorption. (2) When isotherms are adjusted for solute hydrophobicity (n-hexdecane-water partition coefficient), sorption intensity of the polar compounds is greater than that of the apolar compounds, possibly because of pi-pi EDA interactions of the polar compounds with the basal plane of the graphene sheets. (3) The largest test compounds show steric exclusion from a portion of the adsorption space available to the other compounds. (4) Removal of O functionality by hydrogenation enhances sorption intensity of polar and apolar compounds, alike by reducing competitive adsorption by water molecules.

A prototype electron monochromator (EM) reflectron time-of-flight (TOF) mass spectrometer has been constructed and demonstrated to record resonant electron capture (REC) mass spectra of electron-capturing compounds. The electron energy is ramped from -1.7 to +25 eV at a preset frequency, and the energy spread of the electron beam at 15 nA is 100 meV or better. Ions are orthogonally extracted into the analyzer at a frequency of up to 80 kHz while maintaining an upper m/z-limit of at least 300 and a mass resolving power of approximately 1000. A complete REC mass spectrum, which includes an effective yield versus electron energy curve for each negative ion formed from the compound being analyzed, typically takes several days to produce with a quadrupole or magnetic sector mass spectrometer. With the EM TOF described in this work, three-dimensional negative ion electron capture spectra are recorded in an interval on the order of only 1 s and displayed in real time. This new analytical capability could make it possible to perform GC REC mass spectrometry as well as easier (a) to measure the temperature dependence of REC cross sections, (b) to determine enthalpies of negative ion formation (accurate determination of the enthalpy of ion formation requires knowledge of the translational energy released during a dissociative capture event), and (c) to provide complete thermochemical descriptions of dissociative electron attachment by measuring ion lifetimes.

We present here the synthesis and characterization of four photolabile derivatives of urea in which alpha-substituted 2-nitrobenzyl groups are covalently attached to the urea nitrogen. These derivatives photolyze readily in aqueous solution to release free urea. The alpha-substituents of the 2-nitrobenzyl group strongly influence the rate of the photolysis reaction measured with transient absorption spectroscopy. Rates of photolysis at pH 7.5 and room temperature (approximately 22 degrees C) for N-(2-nitrobenzyl)urea, N-(alpha-methyl-2-nitrobenzyl)urea, N-(alpha-carboxymethyl-2-nitrobenzyl)urea, and N-(alpha-carboxy-2-nitrobenzyl)urea are, respectively, 1.7 x 10(4), 8.5 x 10(4), 4.0 x 10(4), and 1.1 x 10(5) s(-)(1). The quantum yields determined by measurement of free urea following irradiation by a single laser pulse at 308 nm were 0.81 for N-(2-nitrobenzyl)urea, 0.64 for N-(alpha-methyl-2-nitrobenzyl)urea, and 0.56 for N-(alpha-carboxy-2-nitrobenzyl)urea. The caged N-(alpha-carboxy-2-nitrobenzyl)urea is not a substrate of the enzyme urease, while the photolytically released urea is. Also, neither this caged urea nor its photolytic side products inhibit hydrolysis of free urea by urease. Thus, the alpha-carboxy-2-nitrobenzyl derivative of urea is suitable for mechanistic investigations of the enzyme urease.

To more fully understand the potential for transport of nitroaromatic compounds in soils and subsoils,the adsorption of a series of para- and meta-substituted nitrobenzenes (SNBs) by K-smectite clay was measured. Adsorption isotherms were fit to the Freundlich equation, and the resultant Freundlich adsorption coefficients (log(Kf) were positively correlated with the Hammett substituent constant (r2 = 0.80). This relationship and a positive reaction constant (p = 1.15) indicate that the adsorption reaction is favored by electron-withdrawing substituents. These results are consistent with an electron donor (smectite)-acceptor (substituted nitrobenzene) mechanism offered previously. However, quantum calculations did not reveal any systematic relationship between the Hammett constant and the electron density on the aromatic ring, which would explain a donor-acceptor relationship. Rather, electron density donated by a second substituent on nitrobenzene appears to be appropriated by the nitro group leaving ring electron density unchanged. Fourier transform infrared spectroscopy revealed shifts in the -NO2 vibrational modes of 1,3,5-trinitrobenzene (TNB) upon adsorption to K+-smectite that were consistent with the complexation of K+ by -NO2 groups. Such TNB vibrational shifts were not observed for SWy-1 saturated with more strongly hydrated cations (i.e., Na+, Mg2+, Ca2+, and Ba2+). The simultaneous interaction of multiple -NO2 groups with exchangeable K+ was indicated by molecular dynamic simulations. Adsorption of SNBs by smectite clays appears to result from the additive interactions of -NO2 groups and secondary substituents with interlayer K+ ions. Adsorption occurs to a greater or lesser extent depending on the abilities of substituents to complex additional interlayer cations and the water solubilities of SNBs. We conclude that the adsorption trends of SNBs on K-SAz-1 can be explained without recourse to hypothetical electron donor-acceptor complexes.

Ion chromatographic (IC) methods using sodium hydroxide and methanol gradients were used for the determination of small inorganic and organic anions as decomposition products of a tecnazene solution in water irradiated by UV light. After 60 min of UV irradiation, >99% of the tecnazene was decomposed, and 11 organic and 3 inorganic anions were identified and quantified. A fourth inorganic anion, carbonate, was not quantified due to likely losses as carbon dioxide. The final content of chloride, total nitrogen, and total carbon released from the saturated tecnazene solution after 60 min of UV irradiation were 108, 85, and 38%, respectively. These results suggest that other products rich in carbon and/or nitrogen (such as phenolic compounds and nitrobenzenes) were formed during the UV irradiation of the tecnazene solution. The results obtained indicate several decomposition pathways of tecnazene in water solutions, for example, ring opening reactions, dechlorination, and replacement of the ring nitro group. The determination of nonionic decomposition products from the latter two possibilities is the subject of further study.

The oxidizing agent tris(bipyridyl)ruthenium(III), or Ru-(bpy)(3)3+, is used as a postcolumn reagent for the detection of nitroaromatic and nitramine explosive compounds. After separation, the explosives are reduced electrochemically to oxidizable products such as hydroxlamines and nitrosamines, and these products react readily with Ru-(bpy)(3)3+ and Ru(bpy)(3)2+. The photoluminescence from the latter is used for detection. A porous carbon electrode was used for on-line analyte reduction following chromatography. Another porous carbon electrode was used to generate the nonluminescent Ru(bpy)(3)3+ from Ru(bpy)(3)3+ on-line at high efficiency. The two streams were combined, and the Ru(bpy)(3)2+ produced by oxidation of the reduced analytes was detected by laser illumination and light detection. Reductive hydrodynamic voltammograms of nitrobenzene, 2,4,6-trinitrotoluene, and hexahydro-1,3,5-trinitro-1,3,5-triazine indicated that a potential of - 1500 mV vs Ag/AgCl was sufficient to achieve a maximum signal from the reduced analytes. HPLC with a water/acetonitrile gradient on a C-18 reversed-phase column was then used to determine these three compounds plus the four additional examples, 1,3,5,7-tetrazocine, 2,4-dinitrotoluene; 2,6-dinitrotoluene, and 4-nitrotoluene. For both hydrodynamic voltammetry and HPLC detection, the photoluminescence following electron-transfer signal was calibrated using the one-electron standards ferrocene and ferrocenecarboxylic acid. Detection limits were in the low-nanomolar range for 20-microL injections of nonpreconcentrated nitro compounds.