Coupled abiotic-biotic mineralization of 2,4,6-trinitrotoluene (TNT)

Munitions wastes such as TNT are widespread contaminants in soils and ground waters. We investigated a coupled abiotic-biotic treatment scheme for remediation of aqueous solutions of TNT. Mineralization of aqueous TNT (0.22 mM) was initially optimized with minimum reactant use (Fe3+ and H2O2) in light-assisted and dark, modified Fenton reactions at acidic and neutral pH. Complete TNT degradation occurred under all reaction conditions within 24 h. Using the optimum reactant concentrations, coupled abiotic-biotic reactions showed an increase in TNT mineralization, from 47 to 80%, after biomass addition to the acidic, dark Fenton-like reaction. Comparable increases of TNT mineralization were observed under neutral pH with similar reaction conditions. In light-assisted Fenton-like reactions at neutral pH, no increase in cumulative TNT mineralization (66%) was seen in coupled abiotic-biotic reactions. Abiotic photo-Fenton-like reactions alone, at acidic pH, produced complete TNT mineralization and required no biotic assistance. While light-enhanced Fenton reactions alone can provide high levels of TNT mineralization, the dark abiotic-biotic reaction scheme has perhaps a wider use due to a similar extent of TNT mineralization in the absence of light, leading to possible applications in soil slurry and in situ processes in the subsurface.     

Chemical and biological characterization of non-extractable sulfonamide residues in soil

For sulfonamides, the formation of non-extractable residues has been identified by laboratory testing as the most relevant concentration determining process in manured soil. Therefore, the present study has been focused on the chemical and biological characterization of non-extractable residues of ¹⁴C-labeled sulfadiazine or sulfamethoxazole. In laboratory batch experiments, the test substances were spiked via standard solution or test slurry to microbially active soil samples. After incubation periods of up to 102 d, a sequential extraction technique was applied. Despite the exhaustive extraction procedure, sulfadiazine residues mainly remained non-extractable, indicating the high affinity to the soil matrix. The remobilization of non-extractable ¹⁴C-sulfadiazine residues was monitored in the activated sludge test and the Brassica rapa test. Only small amounts (<3%) were transferred into the extractable fractions and 0.1% was taken up by the plants. In the Lumbricus terrestris test A, the release of non-extractable ¹⁴C-sulfamethoxazole residues by the burrowing activity of the earthworms was investigated. The residues mainly remained non-extractable (96%). The L. terrestris test B was designed to study the immobilization of ¹⁴C-sulfamethoxazole in soil directly after the test slurry application. The mean uptake by earthworms was 1%. Extractable and non-extractable residues amounted to 5% and 93%, respectively. Consequently, the results of all tests confirmed the high affinity of the non-extractable sulfonamide residues to the soil matrix.     

High-molecular weight sulfur-containing aromatics refractory to weathering as determined by Fourier transform ion cyclotron resonance mass spectrometry

Biomarkers and low-molecular weight polyaromatic compounds have been extensively studied for their fate in the environment. They are used for oil spill source identification and monitoring of weathering and degradation processes. However, in some cases, the absence or presence of very low concentration of such components restricts the access of information to spill source. Here we followed the resistance of high-molecular weight sulfur-containing aromatics to the simulated weathering condition of North Sea crude oil by ultra high-resolution Fourier transform ion cyclotron resonance mass spectrometry. The sulfur aromatics in North Sea crude having double bond equivalents (DBE) from 6 to 14 with a mass range 188-674 Da were less influenced even after 6 months artificial weathering. Moreover, the ratio of dibenzothiophenes (DBE 9)/naphthenodibenzothiophenes (DBE 10) was 1.30 and 1.36 in crude oil and 6 months weathered sample, respectively reflecting its weathering stability. It also showed some differences within other oils. Hence, this ratio can be used as a marker of the studied crude and accordingly may be applied for spilled oil source identification in such instances where the light components have already been lost due to environmental influences.     

Microméthode de dosage simultané de l'alcool isopropylique et de son métabolite l'acétone

Simultaneous determination of Isopropyl Alcohol and Acetone prove to be necessary in cases of poisoning by this widely used alcohol. An aluminum capsule containing a sample of blood to be analyzed is introduced into a gas chromatograph equipped with a flameionization detector and a Carbowax 20 M - Chromosorb WHP column. Use of a small blood sample (0.50 μl) and high sensitivity of the method make it a selected procedure in the clinical diagosis of poisoning by Isopropyl Alcohol.     

High resolution proton NMR spectroscopy of human amniotic fluid

Human amniotic fluid (HAF) is a dynamic system whose characteristics depend on continuous interchanges between fetal and maternal circulations. HAF reflects not only the environment of the fetus but may also provide information about fetal development or pathology. The concentration of HAF constituents varies with gestational age and pathological states. The number of the compounds currently implicated in fetal developmental pathology are relatively few. Currently used assay methods are not adequate to totally explain or predict the complex biochemistry of the fetus. The purpose of this work was to investigate HAF with NMR spectroscopy. In the present study HAF was obtained from 47 women undergoing routine amniocentesis. Cells were separated for karyological analysis and the supernatant was acid-extracted, lyophilized and re-suspended in D₂0 resulting in a concentration increase over native fluid. ¹H NMR spectra were obtained at 360 MHz and 60 MHz. Eighteen compounds including several amino acids, were identified using parallel reference and standard addition protocols. NMR spectroscopy detected compounds of known clinical importance including glucose, leucine, isoleucine, lactate and creatinine. In conclusion, we have demonstrated that a number of physiologically relevant compounds are readily observable in HAF using ¹H NMR spectroscopy. This technique can currently provide valuable information regarding HAF composition and has the potential of being used in vivo in the future.     

Coupled abiotic-biotic mineralization of 2,4,6-trinitrotoluene (TNT) in soil slurry

The explosive 2,4,6-trinitrotoluene (TNT) is a contaminant of soils and ground waters worldwide. To help alleviate such environmental contamination, we investigated a coupled abiotic-biotic treatment scheme for remediating TNT-contaminated soil in slurry solutions. Two types of soil were used (sandy and silt loam) to simulate different soils that might be found at actual sites. These soils were subsequently contaminated with 5000 mg kg(-1) TNT. Mineralization of TNT was initially optimized for minimum reactant use (Fe(3+) and H(2)O(2)) and maximum soil slurry percentage (percent solids) using modified Fenton reactions conducted in the absence of light followed by the addition of an uncharacterized aerobic biomass. Greater than 97% TNT degradation was observed under optimum reaction conditions for both soils. Using two optimum reactant concentrations for each soil, coupled abiotic-biotic reactions showed an increase in TNT mineralization, from 41 to 73% and 34 to 64% in the sandy soil (10 and 20% slurry, respectively, 1470 mM H(2)O(2)), and increases from 12 to 23% and 13 to 28% in the silt loam soil (5% slurry, 294 and 1470 mM H(2)O(2), respectively). These results show promise in the use of combined abiotic-biotic treatment processes for soils contaminated with high concentrations of TNT.     

Do decreased trace metal concentrations in surficial skagerrak sediments over the last 15-30 years indicate decreased pollution?

Varying concentrations of Zn, Pb and Cu over the last 15-30 years (1963-1991) have been found in two undisturbed cores with preserved sediment-water interfaces from the Skagerrak (Station A: 645 m, Station B: 405 m water depth). Mass Accumulation Rates (MAR) in g/m2/year were used to resolve the question of increased or decreased supply. Station A-MAR increased exponentially: Zn from 0.05 to 0.28, Cu from 0.009 to 0.044, and Pb from 0.003 to 0.114 g/m2/year, while concentrations did not show this increase over the last 15-30 years. Station B-MAR increased exponentially: Zn from 0.07 to 0.29, Cu from 0.013 to 0.049, and Pb from 0.014 to 0.114 g/m2/year, while concentrations decreased over the same period. MAR indicated that both stations received similar trace metal flux. Release of trace metals from the sediment to the water column and/or dilution by water and organic matter within the upper few centimeters of the sediment accounted for the concentration decrease at both stations. MAR revealed an increase in trace metal supply, and thus an increase in pollution, over the last 15-30 years, although concentrations indicated the opposite.