Experimental and Computational Study of Pyrogenic Carbonaceous Matter Facilitated Hydrolysis of 2,4-Dinitroanisole (DNAN).

This study investigated the reaction pathway of 2,4-dinitroanisole (DNAN) on the pyrogenic carbonaceous matter (PCM) to assess the scope and mechanism of PCM-facilitated surface hydrolysis. DNAN degradation was observed at pH 11.5 and 25 °C with a model PCM, graphite, whereas no significant decay occurred without graphite. Experiments were performed at pH 11.5 due to the lack of DNAN decay at pH below 11.0, which was consistent with previous studies. Graphite exhibited a 1.78-fold enhancement toward DNAN decay at 65 °C and pH 11.5 relative to homogeneous solution by lowering the activation energy for DNAN hydrolysis by 54.3 ± 3.9%. This is supported by our results from the computational modeling using Car-Parrinello simulations by ab initio molecular dynamics/molecular mechanics (AIMD/MM) and DFT free energy simulations, which suggest that PCM effectively lowered the reaction barriers by approximately 8 kcal mol-1 compared to a homogeneous solution. Quaternary ammonium (QA)-modified activated carbon performed the best among several PCMs by reducing DNAN half-life from 185 to 2.5 days at pH 11.5 and 25 °C while maintaining its reactivity over 10 consecutive additions of DNAN. We propose that PCM can affect the thermodynamics and kinetics of hydrolysis reactions by confining the reaction species near PCM surfaces, thus making them less accessible to solvent molecules and creating an environment with a weaker dielectric constant that favors nucleophilic substitution reactions. Nitrite formation during DNAN decay confirmed a denitration pathway, whereas demethylation, the preferred pathway in homogeneous solution, produces 2,4-dinitrophenol (DNP). Denitration catalyzed by PCM is advantageous to demethylation because nitrite is less toxic than DNAN and DNP. These findings provide critical insights for reactive adsorbent design that has broad implications for catalyst design and pollutant abatement.

Detection Limits of Trinitrotoluene and Ammonium Nitrate in Soil by Raman Spectroscopy.

The detection limit of 2,4,6-trinitrotoluene (TNT) and ammonium nitrate (AN) in mixtures of Ottawa sand (OS) was studied using a Raman microscope applying conventional calibration curves, Pearson correlation coefficients, and two-sample t-tests. By constructing calibration curves, the conventionally defined detection limits were estimated to be 1.9 ± 0.4% by mass in OS and 1.9 ± 0.3% by mass in OS for TNT and AN. Both TNT and AN were detectable in concentrations as low as 1% by mass when Pearson correlation coefficients were used to compare averaged spectra to a library containing spectra from a range of soil types. AN was detectable in concentrations as low as 1% by mass when a test sample of spectra was compared to the same library using two-sample t-tests. TNT was not detectable at a concentration of 1% by mass when using two-sample t-tests.

Photo-transformation of aqueous nitroguanidine and 3-nitro-1,2,4-triazol-5-one: Emerging munitions compounds.

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

Ice Core Perspective on Mercury Pollution during the Past 600 Years.

Past emissions of the toxic metal mercury (Hg) persist in the global environment, yet these emissions remain poorly constrained by existing data. Ice cores are high-resolution archives of atmospheric deposition that may provide crucial insight into past atmospheric Hg levels during recent and historical time. Here we present a record of total Hg (HgT) in an ice core from the pristine summit plateau (5340 m asl) of Mount Logan, Yukon, Canada, representing atmospheric deposition from AD 1410 to 1998. The Colonial Period (∼1603-1850) and North American "Gold Rush" (1850-1900) represent minor fractions (8% and 14%, respectively) of total anthropogenic Hg deposition in the record, with the majority (78%) occurring during the 20th Century. A period of maximum HgT fluxes from 1940 to 1975 coincides with estimates of enhanced anthropogenic Hg emissions from commercial sources, as well as with industrial emissions of other toxic metals. Rapid declines in HgT fluxes following peaks during the Gold Rush and the mid-20th Century indicate that atmospheric Hg deposition responds quickly to reductions in emissions. Increasing HgT fluxes from 1993 until the youngest samples in 1998 may reflect the resurgence of Hg emissions from unregulated coal burning and small-scale gold mining.

Natural and anthropogenic variations in atmospheric mercury deposition during the Holocene near Quelccaya Ice Cap, Peru.

Mercury (Hg) is a toxic metal that is transported globally through the atmosphere. The emission of Hg from mineral reservoirs and subsequent recycling in surface reservoirs (i.e., soil/biomass, ocean, and atmosphere) are fundamental to the modern global Hg cycle, yet past emissions from anthropogenic and natural sources are not fully constrained. We use a sediment core from Yanacocha, a headwater lake in southeastern Peru, to study the anthropogenic and natural controls on atmospheric Hg deposition during the Holocene. From 12.3 to 3.5 ka, Hg fluxes in the record are relatively constant (mean ± 1σ: 1.4 ± 0.6 µg m-2 a-1, n = 189). Past Hg deposition does not correlate with changes in regional temperature and precipitation, inferred from nearby paleoclimate records, or with most large volcanic events that occurred regionally, in the Andean Central Volcanic Zone (~300-400 km from Yanacocha), and globally. In B.C. 1450 (3.4 ka), Hg fluxes abruptly increased and reached the Holocene-maximum flux (6.7 µg m-2 a-1) in B.C. 1200, concurrent with a ~100-year peak in Fe and chalcophile metals (As, Ag, Tl) and the presence of framboidal pyrite. Continuously elevated Hg fluxes from B.C. 1200-500 suggest a protracted mining-dust source near Yanacocha that is identical in timing to documented pre-Incan cinnabar mining in central Peru. During Incan and Colonial time (A.D. 1450-1650), Hg deposition remains elevated relative to background levels but lower relative to other Hg records from sediment cores in central Peru, indicating a limited spatial extent of preindustrial Hg emissions. Hg fluxes from A.D. 1980 to 2011 (4.0 ± 1.0 µg m-2 a-1, n = 5) are 3.0 ± 1.5 times greater than pre-anthropogenic fluxes and are similar to modern fluxes documented in remote lakes around the world.

Effects of historical and modern mining on mercury deposition in southeastern Peru.

Both modern anthropogenic emissions of mercury (Hg), primarily from artisanal and small-scale gold mining (ASGM), and preindustrial anthropogenic emissions from mining are thought to have a large impact on present-day atmospheric Hg deposition. We study the spatial distribution of Hg and its depositional history over the past ∼400 years in sediment cores from lakes located regionally proximal (∼90-150 km) to the largest ASGM in Peru and distal (>400 km) to major preindustrial mining centers. Total Hg concentrations in surface sediments from fourteen lakes are typical of remote regions (10-115 ng g(-1)). Hg fluxes in cores from four lakes demonstrate preindustrial Hg deposition in southeastern Peru was spatially variable and at least an order of magnitude lower than previously reported fluxes in lakes located closer to mining centers. Average modern (A.D. 2000-2011) Hg fluxes in these cores are 3.4-6.9 µg m(-2) a(-1), compared to average preindustrial (A.D. 1800-1850) fluxes of 0.8-2.5 µg m(-2) a(-1). Modern Hg fluxes determined from the four lakes are on average 3.3 (±1.5) times greater than their preindustrial fluxes, similar to those determined in other remote lakes around the world. This agreement suggests that Hg emissions from ASGM are likely not significantly deposited in nearby down-wind regions.

Effect of bioirrigation on sediment-water exchange of methylmercury in Boston Harbor, Massachusetts.

Coastal marine sediments are important sites of methylmercury (MMHg) production, and dissolved efflux provides an important source of MMHg to near-shore, and possibly offshore, water columns and food webs. We measured the flux of MMHg across the sediment-water interface at four stations in Boston Harbor that span a range of infaunal population densities and bioirrigation intensities. At each station we carried out total MMHg flux measurements using core incubations and collected near-surface pore waters to establish MMHg gradients for diffusive flux calculations. The flux cores were also imaged by CT scanning to determine the distribution of infaunal burrows, and pore-water sulfide and 222Rn profiles were measured. Total MMHg fluxes, measured using core incubations, ranged from -4 to 191 pmol m(-2) d(-1), and total MMHg fluxes were strongly correlated with burrow densities at the stations. Estimated diffusive fluxes, calculated based on MMHg concentration gradients below the sediment-water interface, were much lower than total fluxes at three of the stations, ranging from 2-19 pmol m(-2) d(-1). These results indicate that MMHg exchange may be significantly enhanced over molecular diffusion in bioturbated sediments. Furthermore, burrow density provides a strong predictor of total MMHg flux. Pore-water exchange of both dissolved MMHg and 222Rn, a naturally occurring pore-watertracer, increased across the range of observed burrow densities, suggesting that the presence of burrows enhances both MMHg production and flux.