Photochemistry of 1-nitro-2-phenylnaphthalene available to the environment

Photolysis (254 nm, 72h) of 1-nitro-2-phenylnaphthalene $\text{1}$ in methanol gave 2-phenyl-1,4-naphthoquinone-4-monoxime $\text{2}$, 2,2′-diphenyl-4,4′-binaphth-1,1′-diol $\text{3}$ and 2,2′-diphenyl-4,4′-binaphth-1,1′-dione $\text{4}$. Straightforward reactions available to the environment account for the formation of the products: (a) isomerisation of the nitro compound into a nitrite ester followed by either (a) migration of the nitroso group and isomerisation into the oxime $\text{2}$ or (b) oxidative coupling and solvolysis into the binaphthol $\text{3}$ and followed by oxidation into the binaphthone $\text{4}$.     

Molarity provides better clarity – using molar-based data when evaluating chlorinated volatile organic compound impacted sites

Abstract

Chlorinated volatile organic compounds are common constituents observed at many contaminated groundwater sites. Common industry practice has been to measure these constituents in groundwater on a weight concentration basis (e.g. µg/l, mg/l). This paper highlights the use of molar-based concentrations, especially in the case of parent-daughter degradation sequences commonly observed with the chloroethene, chloroethane, and chloromethane families of compounds. Converting to molar-based concentrations provides the practitioner greater insight into groundwater plume behavior including better evaluation of degradation processes, remedial progress, possible commingling, and/or sourcing. For example, this paper provides a tank analogy to evaluate whether the commonly misinterpreted observation of “DCE-stall” may be occurring at a site. Multiple examples of the benefits of using molar-based concentration data are also summarized in a project case study presented herein. As demonstrated in this paper, molarity does provide better clarity and can be a powerful evaluation tool in the groundwater practitioner’s toolbox.     

The identification of three previously unreported lindane metabolites from mammals

Previously unreported metabolites from the urine of rats treated with lindane have been identified as configurational isomers of 2,4,5,6- and 2,3,4,6-tetrachloro-2-cyclohexen-1-ol. In addition, an intermediate metabolite from the incubation of lindane with liver preparations, under N₂, has been identified as the configurational isomer γ-3,4,5,6-tetrachlorocyclohex-1-ene. The pathways leading to these metabolites appear to have an important role in the metabolism of lindane by mammals.     

Modeling radium and radon transport through soil and vegetation

A one-dimensional flow and transport model was developed to describe the movement of two fluid phases, gas and water, within a porous medium and the transport of 226Ra and 222Rn within and between these two phases. Included in this model is the vegetative uptake of water and aqueous 226Ra and 222Rn that can be extracted from the soil via the transpiration stream. The mathematical model is formulated through a set of phase balance equations and a set of species balance equations. Mass exchange, sink terms and the dependence of physical properties upon phase composition couple the two sets of equations. Numerical solution of each set, with iteration between the sets, is carried out leading to a set-iterative compositional model. The Petrov-Galerkin finite element approach is used to allow for upstream weighting if required for a given simulation. Mass lumping improves solution convergence and stability behavior. The resulting numerical model was applied to four problems and was found to produce accurate, mass conservative solutions when compared to published experimental and numerical results and theoretical column experiments. Preliminary results suggest that the model can be used as an investigative tool to determine the feasibility of phytoremediating radium and radon-contaminated soil.     

Atmospheric volatilization and distribution of (Z)- and (E)-1,3-dichloropropene in field beds with and without plastic covers

The fumigant 1,3-dichloropropene (1,3-D) is considered to be a potential replacement for methyl bromide when methyl bromide is phased out in 2005. This study on surface emissions and subsurface diffusion of 1,3-D in a Florida sandy soil was conducted in field beds with or without plastic covers. After injection of the commercial fumigant Telone II by conventional chisels to field beds at 30cm depth which were covered with polyethylene film (PE), virtually impermeable film, or no cover (bare), (Z)- and (E)-1,3-D rapidly diffused upward. Twenty hours after injection, majority of (Z)- and (E)-1,3-D had moved upward from 30 cm depth to the layer of 5-20 cm depth. Downward movement of the two isomers in the beds with or without a plastic cover was not significant. (Z)-1,3-D diffused more rapidly than (E)-1,3-D. Virtually impermeable films (VIF) had a good capacity to retain (Z)- and (E)-1,3-D in soil pore air space. Vapor concentrations of the two isomers in the shallow subsurface of the field bed covered with VIF were greater than that in the two beds covered with polyethylene film (PE) or no cover (bare). In addition, VIF cover provided more uniform distribution of (Z)- and (E)-1,3-D in shallow subsurface than PE cover or no cover. Virtually impermeable film also had a better capability to retard surface emissions of the two isomers from soil in field beds than PE cover or no cover.     

Oxygenated fuel induced cosolvent effects on the dissolution of polynuclear aromatic hydrocarbons from contaminated soil

The cosolvent-induced dissolution of polynuclear aromatic hydrocarbons (PAHs) from contaminated soil caused by oxygenated fuel spills was studied. Oxygenated fuel induces a solvent flushing effect on the contaminated soil due to the high content of oxygenated compounds (i.e., methanol, ethanol, and methyl tert butyl ether (MTBE)). The miscible displacement techniques were applied to evaluate the increased potential for secondary contamination in an impacted site. Significant solubility enhancement of the 18 PAHs monitored during fuel spill simulation and cosolvent flushing is clearly evident when compared to normal water dissolution. The breakthrough concentration profile for each PAH constituent was integrated over the cumulative effluent volume (i.e., the zeroth moment) to determine the total PAH mass removed during the experiment. The removal efficiency of PAHs ranges from 46.6% to 99.9% in three oxygenated fuels (i.e., M85, E85, and oxygenated gasoline) during the fuel spill. Several factors including hydrophobicity of compounds, nonequilibrium dissolution due to nonuniform coal tar distribution, and heterogeneous media properties affect the oxygenated compound-induced dissolution process. This study provides a basis to predict the facilitated transport of hydrophobic organic compounds from subsurface environment due to the cosolvent effects of oxygenated fuels.     

Persistent organic pollutants in source-separated compost and its feedstock materials--a review of field studies

Composting and the application of compost to the soil follow the principle of recycling and sustainability. Compost can also have a positive effect on physical, chemical, and biological soil parameters. However, little is known about the origin, concentration, and transformation of persistent organic pollutants (POPs) in compost. We therefore compiled literature data on some priority POPs in compost and its main feedstock materials from more than 60 reports. Our data evaluation suggests the following findings. First, median concentrations of Sigma 16 polycyclic aromatic hydrocarbons (PAHs), Sigma 6 polychlorinated biphenyls (PCBs), and Sigma 17 polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) were higher in green waste (1803, 15.6 microg/kg dry wt., and 2.5 ng international toxicity equivalent [I-TEQ]/kg dry wt.) than in organic household waste (635, 14.6 microg/kg dry wt., and 2.2 ng I-TEQ/kg dry wt.) and kitchen waste (not available [NA], 14.9 microg/kg dry wt., 0.4 ng I-TEQ/kg dry wt.). The POP concentrations in foliage were up to 12 times higher than in other feedstock materials. Second, in contrast, compost from organic household waste and green waste contained similar amounts of Sigma 16 PAHs, Sigma 6 PCBs, and Sigma 17 PCDD/Fs (1915, 39.8 microg/kg dry wt., and 9.5 ng I-TEQ/kg dry wt., and 1715, 30.6 microg/kg dry wt., and 8.5 ng I-TEQ/kg dry wt., respectively). Third, concentrations of three-ring PAHs were reduced during the composting process, whereas five- to six-ring PAHs and Sigma 6 PCBs increased by roughly a factor of two due to mass reduction during composting. Sigma 17 PCDD/Fs had accumulated by up to a factor of 14. Fourth, urban feedstock and compost had higher POP concentrations than rural material. Fifth, the highest concentrations of POPs were usually observed in summer samples. Finally, median compost concentrations of POPs were greater by up to one order of magnitude than in arable soils, as the primary recipients of compost, but were well within the range of many urban soils. In conclusion, this work provides a basis for the further improvement of composting and for future risk assessments of compost application.     

MODELING NITROGEN TRANSPORT IN THE IPSWICH RIVER BASIN,MASSACHUSETTS, USING A HYDROLOGICAL SIMULATION PROGRAM IN FORTRAN (HSPF)1

ABSTRACT: Increased riverine nitrogen (N) fluxes have been strongly correlated with land use changes and are now one of the largest pollution problems in the coastal region of the United States. In the present study, the Hydrological Simulation Program‐FORTRAN (HSPF) is used to simulate transport of N in the Ipswich River basin in Massachusetts and to evaluate the effect of future land use scenarios on the water quality of the river. Model results show that under a land use change scenario constructed with restrictions from environmental protection laws, where 44 percent of the forest in the basin was converted to urban land, stream nitrate concentrations increased by about 30 percent of the present values. When an extreme land use scenario was used, and 100 percent of the forest was converted to urban land, concentrations doubled in comparison to present values. Model simulations also showed that present stream nitrate concentrations might be four times greater than they were prior to urbanization. While pervious lands with high density residential land use generated runoff with the highest N concentrations in HSPF simulations, the results suggested that denitrification in the riparian zone and wetlands coupled with the hydrology of the basin are likely to control the magnitude of nitrate loads to the aquatic system. The simulation results showed that HSPF can predict the general patterns of inorganic N concentrations in the Ipswich River and tributaries. Nevertheless, HSPF has some difficulty simulating the extreme variability of the observed data throughout the main stem and tributaries, probably because of limitations in the representation of wetlands and riparian zones in the model, where N processes such as denitrification seem to play a major role in controlling the transport of N from the terrestrial system to the river reaches.     

AQUATIC TRANSPORT OF HEAVY METALS IN THE URBAN ENVIRONMENT1

ABSTRACT: A study has been conducted for the past two years on a 4.6 mile stretch of the Saddle River near Lodi, New Jersey. The primary objectives of this study were two fold; initially, the amounts of various heavy metals being contributed to the Saddle River by stormwater runoff, rainfall, and individual tributaries, etc., were investigated to better delineate the distribution of various sources of heavy metals to the aquatic environment. Secondly, a series of benthal deposits from the Saddle River were analyzed to determine the fate of these metals once introduced into the receiving stream. A mass balance analysis of heavy metals in the Saddle River was performed to determine the amount of these materials contributed from unrecorded sources. The results of this study seemed to demonstrate the importance of considering the potential scouring of river sediments as a secondary source of metals in determinations of this type. The distribution of metals in precipitation samples collected in this study was found to be similar to that in runoff, with lead and zinc predominating. Relative concentrations of metals in precipitation as compared to those of stormwater were relatively insignificant. Metal concentrations of bottom sediments were found to vary considerably from sample to sample.