ABSTRACT
This review summarises results of our pilot-scale experiments to find suitable inhibitors for preventing the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) during waste incineration and to specify the role of the main factors affecting the inhibition process, and is based on doctoral dissertation of Ruokojaärvi (2002). Results of previous experiments reported by other researchers are also presented and compared with ours. The detailed aims of our experiments were (1) to compare the effects of different inhibitors on PCDD/F formation during incineration in a pilot plant, (2) to investigate the role of the particle size distribution of the flue gas on the inhibition of PCDD/Fs, and (3) to find the main parameters affecting PCDD/F inhibition in waste incineration. Prevention of the formation of PCDD/Fs with chemical inhibitors and the effects of different supply points, feed temperatures and process parameters were studied in a pilot scale incinerator (50 kW) using light heating oil and refuse-derived fuel as test fuels. Various concentrations of the gaseous inhibitors (sulfur dioxide, ammonia, dimethylamine and methyl mercaptan) were sprayed into the flue gases after the furnace, in addition to which urea was dissolved in water and injected in at different concentrations. The residence time of the flue gas between the furnace and the PCDD/F sampling point was varied in the tests. In another set of urea tests, urea-water solutions at three concentrations were mixed with the RDF prior to incineration. PCDD/F and chlorophenol concentrations, together with other flue gas parameters (e.g. temperature, O2, CO, CO2 and NO), were analysed in the cooling flue gases. The gaseous and liquid inhibitors both notably reduced PCDD/F concentrations in the flue gas, the reductions achieved with the gaseous inhibitors varying from 50 to 78%, with dimethyl amine the most effective, while that produced with urea was up to 90%. The PCDD/F reductions were greater at increased inhibitor concentrations and with increased residence time of the flue gas between the furnace and the sampling point. PCDD/F concentrations in the particle phase decreased much more markedly than those in the gas phase. The urea inhibitor did not alter the particle size distribution of the PCDD/Fs when the amount of inhibitor was adequate. Chemical inhibitors seem to offer a very promising technique for preventing the formation of PCDD/Fs in waste incineration. The addition of urea to the fuel before combustion proved to be very effective approach and could be a useful technique even in the full-scale incinerators.
ABSTRACT
Quantitative structure-activity relationships (QSARs) have proved increasingly useful for predicting the biological activities of molecules (e.g., their binding affinities to different receptors) and can be used in environmental chemistry as a preliminary tool for screening the activities of untested molecules, producing valuable information on which compounds should be tested more thoroughly with experimental affinity assays or in animals. The predictive ability of the consensus kNN QSAR method is corroborated here using a diverse set of 245 compounds, which have been assayed for their relative binding affinities to the estrogen receptor of four species: human (ER alpha and ER beta), calf, mouse, and rat. Leave-one-out cross-validation (LOO-CV) and gamma-randomization tests were applied to the QSAR models for internal validation, and separate training and test sets were used for external validation. The internal predictive abilities of the consensus models for all five data sets were convincing, with cross-validated correlation coefficients (LOO-CV q2 values) varying from 0.69 (human ER beta data) to 0.79 (human ER alpha data). The external predictive abilities were also encouraging, as the predictive r2 scores (pr-r2 values) varied from 0.62 (human ER beta data) to 0.77 (calf and mouse data). The results indicate that consensus kNN QSAR is a feasible method for rapid screening of the estrogenic activity of organic compounds.
