Ulf Trommler

Aromatic intermediate formation during oxidative degradation of Bisphenol A by homogeneous sub-stoichiometric Fenton reaction.

The elimination of Bisphenol A (BPA) from contaminated waters is an urgent challenge. This contribution focuses on BPA degradation by homogeneous Fenton reagent based on reactive ()OH radicals. Pronounced sub-stoichiometric amounts of H(2)O(2) oxidant were used to simulate economically viable processes and operation under not fully controlled conditions, as for example in in situ groundwater remediation. Aside from the most abundant benzenediols and the monohydroxylated BPA intermediate (which were detected as stable intermediates in earlier contributions), a wide array of aromatic products in the molecular weight range between 94 Da (phenol) and approximately 500 Da could be detected, the overwhelming majority of which have not been reported thus far. The identification was carried out by GC/MS analysis of trimethylsilyl ethers. The structural assignments were confirmed through the use of fully deuterated [(2)H(16)] BPA as the substrate, as well as using retention indices calculated on the basis of the increment system. The occurrence of aromatic intermediates larger than BPA, which typically share either a biphenyl- or a diphenylether structure, can be explained by oxidative coupling reactions of stabilized free radicals or by the addition of organoradicals (organocations) onto BPA molecules or benzenediols. The hydroxycyclohexadienyl radical of BPA was recognized to play central role in the degradation pathways. Ring opening products, including lactic, acetic and dicarboxylic acids, could be detected in addition to aromatic intermediates. Since some of those intermediates and products are recalcitrant to further oxidation under the conditions of sub-stoichiometric Fenton reaction, they should be carefully considered when designing and optimizing Fenton-driven remediation systems.

Formation of chlorinated biphenyls, diphenyl ethers and benzofurans as a result of Fenton-driven oxidation of 2-chlorophenol

Homogeneous catalytic Fenton oxidation proved to be very efficient in the degradation of high concentrations (3.9 mM) of 2-chlorophenol (2-CP) in aqueous matrices. When using [H(2)O(2)](0)/[2-CP](0) substoichiometric molar ratios of 4 and 16, the detected aromatic intermediates included mainly chlorinated benzenediols, with the virtual absence of condensation products of higher molecular weight. At even lower substoichiometric ratios of [H(2)O(2)](0)/[2-CP](0) (< or =2.2), hydroxylated chlorobiphenyls, hydroxylated chlorodiphenyl ethers and hydroxylated chlorinated dibenzofurans were formed in addition to chlorinated benzenediols. The aromatic intermediates were identified as trimethylsilyl ethers and dimethyl-t-butyl silyl ethers. A reaction scheme was proposed to describe the formation of aromatic intermediates based on coupling reactions of resonance-stabilized 2-CP radicals generated by electrophilic attack of reactive hydroxyl radicals. The pattern of aromatic intermediates identified in the Fenton solutions coincided well with that predicted on the basis of oxidative coupling reactions. In addition to coupling of stabilized radicals, aromatic intermediates can be formed by addition of organoradicals onto neutral analyte molecules. The findings presented in this contribution are considered crucial for the design and optimization of Fenton-based remediation devoted either to wastewater treatment under economically feasible conditions or to in situ groundwater treatment where poorly controlled reaction conditions prevail.

Influence of salt impregnation on the initiation of thermo-chromatographic pulses by dielectric heating.

Selective dielectric heating using the influence of a coupling medium such as water can lead to the formation of combined temperature-mass transport pulses moving through a packed bed. Depending on the dielectric and sorption properties of the material, these so-called thermo-chroma-tographic pulses (TCP) can cause large temperature differences between the starting temperature and the peak temperature in the pulse. The impregnation of porous substances with various salts was shown to be a simple methodfor improving material properties leading to the formation of stable TCP. This procedure was proven to only slightly reduce the specific surface area and the sorption capacity towards organic compounds of the investigated sorbents. Consequently, a wide spectrum of silica gels, zeolites and porous alumina can be applied as matrices for TCP-based processes in chemical engineering and environmental technology.