Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2

The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).     

Determination of dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) in paper pulp mill defoamer additives and in paper pulp samples

An analytical procedure has been developed for quantitatively measuring dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) present at part-per-billion levels in paper mill defoamers and paper pulp using gas chromatography coupled with either low resolution mass spectrometry (GC-LRMS) or high resolution mass spectrometry (GC-HRMS).     

STABILITY AND REACH LENGTH IN WATER SURFACE PROFILE DETERMINATION1

ABSTRACT: Extension of basic step methods of backwater computation to reaches of finite length is examined. Accuracies of commonly accepted hydraulic loss equations under particular water surface profile conditions are compared. Simulation of energy lines within a reach by parabolic curves is found to minimize error provided orientation of the axis of the parabola is selected in accordance with prevailing hydraulic conditions. Theoretical basis for an index reach length beyond which single-step computation from end to end of the reach must be in error is developed. Reduction of this reach length by suitable factors tailored to hydraulic conditions yields a mathematically defined allowable reach length for backwater computation. When reach length does not exceed this allowable reach length, no significant error may be detected. Automatic insertion of synthetic cross sections interpolated between surveyed cross sections when these are inadvertently spaced too far apart enables computation to proceed. This device is error-free for prismatic channls but may introduce error for irregular natural channels. Preliminary trials indicate that results so obtained may be accepted provided the fall in the original reach does not exceed from one to two feet. When this is exceeded, additional cross sections should be surveyed.     

Physical resuspension and vertical mixing of sediments on a high energy continental margin (Sydney, Australia)

Four sediment cores from the continental margin adjacent to Sydney were analyzed for 210Pb, 137Cs, trace metals (Ag, Cd, Co, Cu, Mn, Ni, Pb, Zn), iron, dry bulk density, mud and moisture content. The concentrations of trace metals in the total sediment are low at all sites, although slightly elevated concentrations of Ag, Cu, Pb and Zn are present in the fine fraction of sediment (< 62.5 microns) near a major ocean outfall. Concentrations of trace metals in the fine fraction of sediment are similar in the upper 10-15 cm, indicating strong vertical mixing of the sediments, whereas an upward coarsening grain size in the upper 1-3 cm of sediment supports physical resuspension during storms. Sediment accumulation rates on the middle shelf adjacent to Sydney were estimated from downcore profiles of 210Pb and 137Cs and range between 0.2 and 0.4 cm yr-1. Although the mass fluxes of Cu, Pb and Zn within a distance of 2 km from the outfall (up to 36.1, 30.8 and 86.2 micrograms cm-2 yr-1, respectively) are greater than 20 km north of the outfall (< 23.5 micrograms cm-2 yr-1), the low concentrations of trace metals in sediments near the outfall support an efficient dispersal of anthropogenic contaminants on this continental margin.     

The use of amino compounds for binding 2,4,6-trinitrotoluene in water

Sites polluted with 2,4,6-trinitrotoluene (TNT) constitute a worldwide problem. In this work, chemical reactions for binding TNT to amino-compounds are proposed as an initial step for developing new remediation techniques to clean-up groundwater and soils contaminated with TNT. Indeed, addition of aniline and an amino acid-like cysteine caused a decrease in free TNT of 86% and 68-100%, respectively. Using 13C-NMR spectroscopy, it was shown that TNT chemically forms a Meisenheimer complex with cysteine and aniline in 1/1 (by vol.) H2O/d6-acetone.     

Reactive transport modeling of processes controlling the distribution and natural attenuation of phenolic compounds in a deep sandstone aquifer

Reactive solute transport modeling was utilized to evaluate the potential for natural attenuation of a contaminant plume containing phenolic compounds at a chemical producer in the West Midlands, UK. The reactive transport simulations consider microbially mediated biodegradation of the phenolic compounds (phenols, cresols, and xylenols) by multiple electron acceptors. Inorganic reactions including hydrolysis, aqueous complexation, dissolution of primary minerals, formation of secondary mineral phases, and ion exchange are considered. One-dimensional (1D) and three-dimensional (3D) simulations were conducted. Mass balance calculations indicate that biodegradation in the saturated zone has degraded approximately 1-5% of the organic contaminant plume over a time period of 47 years. Simulations indicate that denitrification is the most significant degradation process, accounting for approximately 50% of the organic contaminant removal, followed by sulfate reduction and fermentation reactions, each contributing 15-20%. Aerobic respiration accounts for less than 10% of the observed contaminant removal in the saturated zone. Although concentrations of Fe(III) and Mn(IV) mineral phases are high in the aquifer sediment, reductive dissolution is limited, producing only 5% of the observed mass loss. Mass balance calculations suggest that no more than 20-25% of the observed total inorganic carbon (TIC) was generated from biodegradation reactions in the saturated zone. Simulations indicate that aerobic biodegradation in the unsaturated zone, before the contaminant entered the aquifer, may have produced the majority of the TIC observed in the plume. Because long-term degradation is limited to processes within the saturated zone, use of observed TIC concentrations to predict the future natural attenuation may overestimate contaminant degradation by a factor of 4-5.