Long-term TNT and DNT contamination: 1-D modeling of natural attenuation in the vadose zone: case study, Portugal

The vadose zone of a trinitrotoluene (TNT) and dinitrotoluene (DNT) contaminated site was investigated to assess the mobility of those explosives under natural conditions. Located in the left margin of the River Tejo Basin, Portugal, the site is located on unconsolidated sediments. Wastewaters associated with the 50-year explosives production were disposed in excavated ponds, from where water would infiltrate and pollute the unsaturated and saturated parts of the local aquifers. Two boreholes were drilled to 9 m depth in such a former waste pond to investigate the contaminant's fate in the vadose zone. Sediment samples were taken every 1-2 m for analysis of the polynitroaromatics (p-NACs) and organic volatile compounds, pH, organic carbon content, cation exchange capacity and grain size analysis. The main contaminant was TNT representing >70 % of the total p-NACs concentration that peaked approximately 7 mg/kg in one borehole, even if the median in both boreholes was of similar to 1 mg/kg. DNT was 4-30 % of the total p-NACs and nitrotoluene (NT), up to 5 %. No other (volatile) organic compound was detected. The predominance of TNT as the main contaminant implies that any natural mass reduction has been inefficient to clean the site. Several 1-D model simulations of p-NACs cleaning of the vadose zone under natural conditions indicated that the most probable scenario of combined advection and partitioning will only remove TNT after 10's of years, whereas DNT and NT will hardly be removed. Such low concentrations and long times for the p-NACs removal, suggest that by now those compounds have been washed-out to a level below standard limits

Sewage pollution in the coastal waters of Madras, east coast of India

259-262The extent of pollution over the coastal waters of Madras due to sewage inflow through the river Cooum was studied. Analyses were carried out at both low and high tides. Monitoring of estuarine and seawater opposite the mouth of the river at short intervals indicated a recovery in water quality with time from low to high tide and the effect appeared to be localized. Laboratory studies revealed that drastic reduction in faecal coliforms was aided by the native flora

Molecular simulation study of the adsorption of naphthalene and ozone on atmospheric air/ice interfaces

The adsorption of gas-phase naphthalene and ozone on atmospheric air/ice interfaces was investigated using classical molecular dynamics (MD) simulations and potential of mean force (PMF) calculations. Naphthalene and ozone exhibit a strong preference to be adsorbed at the air/ice interface, rather than being dissolved into the bulk of the quasi-liquid layer (QLL) or incorporated into the ice crystals. When the air/ice interface is coated with increasing concentrations of naphthalene molecules, the QLL becomes thinner and surface adsorption of ozone is enhanced. Furthermore, ozone tends to adsorb on top of the naphthalene film, although significant penetration of ozone into this film is also observed. Naphthalene molecules tend to adopt a flat orientation on the air/ice interface. Less variation in the orientation was observed for lower concentrations of naphthalene, whereas variations in the ozone concentration do not affect the orientation of naphthalene molecules. However, as the concentration of ozone increases, most of the naphthalene molecules still prefer to stay close to the mobile water molecules in the QLL, but a significant fraction of the naphthalene molecules spends a considerable amount of time inside the thicker layer of ozone. We also monitored the number of contacts between naphthalene and ozone at the air/ice interface upon variations in the concentrations of these two species. These contacts were assumed to be proportional to the reaction rate between these two species. When the number of ozone molecules was held constant, the number of contacts showed a linear relationship to the number of naphthalene molecules. However, when the naphthalene concentration was held constant, for all systems we observed a linear relationship at low ozone concentrations and a plateau at high ozone concentrations

Adsorption of naphthalene and ozone on atmospheric air/ice interfaces coated with surfactants: a molecular simulation study

The adsorption of gas-phase naphthalene and ozone molecules onto air/ice interfaces coated with different surfactant species (1-octanol, 1-hexadecanol, or 1-octanal) was investigated using classical molecular dynamics (MD) simulations. Naphthalene and ozone exhibit a strong preference to be adsorbed at the surfactant-coated air/ice interfaces, as opposed to either being dissolved into the bulk of the quasi-liquid layer (QLL) or being incorporated into the ice crystals. The QLL becomes thinner when the air/ice interface is coated with surfactant molecules. The adsorption of both naphthalene and ozone onto surfactant-coated air/ice interfaces is enhanced when compared to bare air/ice interface. Both naphthalene and ozone tend to stay dissolved in the surfactant layer and close to the QLL, rather than adsorbing on top of the surfactant molecules and close to the air region of our systems. Surfactants prefer to orient at a tilted angle with respect to the air/ice interface; the angular distribution and the most preferred angle vary depending on the hydrophilic end group, the length of the hydrophobic tail, and the surfactant concentration at the air/ice interface. Naphthalene prefers to have a flat orientation on the surfactant coated air/ice interface, except at high concentrations of 1-hexadecanol at the air/ice interface; the angular distribution of naphthalene depends on the specific surfactant and its concentration at the air/ice interface. The dynamics of naphthalene molecules at the surfactant-coated air/ice interface slow down as compared to those observed at bare air/ice interfaces. The presence of surfactants does not seem to affect the self-association of naphthalene molecules at the air/ice interface, at least for the specific surfactants and the range of concentrations considered in this study

Immobilization of aqueous Hg(II) by mackinawite (FeS)

As one of the major constituents of acid volatile sulfide (AVS) in anoxic sediments, mackinawite (FeS) is known for its ability to scavenge trace metals. The interaction between aqueous Hg(II) (added as HgCl(2)) and synthetic FeS was studied via batch sorption experiments conducted under anaerobic conditions. Due to the release of H(+) during formation of hydrolyzed Hg(II) species which is more reactive than Hg(2+) in surface adsorption, the equilibrium pH decreased with the increase in Hg(II)/FeS molar ratio. Counteracting the loss of FeS solids at lower pH, the maximum capacity for FeS to remove aqueous Hg(II) was approximately 0.75 mol Hg(II) (mol FeS)(-1). The comparison of X-ray power diffraction (XRPD) patterns of synthetic FeS sorbent before and after sorption showed that the major products formed from the interaction between FeS and the aqueous Hg(II) were metacinnabar, cinnabar, and mercury iron sulfides. With the addition of FeS at 0.4 g L(-1) to a 1 mM Hg(II) solution with an initial pH of 5.6, Fe(2+) release was approximately 0.77 mol Fe(2+) per mol Hg(II) removed, suggesting that 77% of Hg(II) was removed via precipitation reaction under these conditions, with 23% of Hg(II) removed by adsorption. Aeration does not cause significant release of Hg(II) into the water phase

Ice Growth from Supercooled Aqueous Solutions of Benzene, Naphthalene, and Phenanthrene

Classical molecular dynamics (MD) were performed to investigate the growth of ice from supercooled aqueous solutions of benzene, naphthalene, or phenanthrene. The main objective of this study is to explore the fate of those aromatic molecules after freezing of the supercooled aqueous solutions, i.e., if these molecules become trapped inside the ice lattice or if they are displaced to the QLL or to the interface with air. Ice growth from supercooled aqueous solutions of benzene, naphthalene, or phenanthrene result in the formation of quasi-liquid layers (QLLs) at the air/ice interface that are thicker than those observed when pure supercooled water freezes. Naphthalene and phenanthrene molecules in the supercooled aqueous solutions are displaced to the air/ice interface during the freezing process at both 270 and 260 K; no incorporation of these aromatics into the ice lattice is observed throughout the freezing process. Similar trends were observed during freezing of supercooled aqueous solutions of benzene at 270 K. In contrast, a fraction of the benzene molecules become trapped inside the ice lattice during the freezing process at 260 K, with the rest of the benzene molecules being displaced to the air/ice interface. These results suggest that the size of the aromatic molecule in the supercooled aqueous solution is an important parameter in determining whether these molecules become trapped inside the ice crystals. Finally, we also report potential of mean force (PMF) calculations aimed at studying the adsorption of gas-phase benzene and phenanthrene on atmospheric air/ice interfaces. Our PMF calculations indicate the presence of deep free energy minima for both benzene and phenanthrene at the air/ice interface, with these molecules adopting a flat orientation at the air/ice interface