Characterization of urban and industrial wastewaters using excitation-emission matrix (EEM) fluorescence: Searching for specific fingerprints.

Excitation-emission matrix (EEM) fluorescence spectroscopy has been applied to characterize several urban and industrial wastewaters (effluents from different types of industries: brewery, winery, dairy, biscuit, tinned fish industry, slaughterhouse, pulp mill, textile dyeing and landfill leachates), searching for specific fluorescence fingerprints. Tryptophan protein-like peaks (T1 and T2) are the predominant fluorescence in urban and food industry wastewaters (brewery, winery, dairy/milk, biscuit and fish farm industries) but no special fingerprint has been found to discriminate among them. Protein-like fluorescence also dominates the spectra of meat/fish industries (effluents from a tinned fish industry and a slaughterhouse), but in this case tyrosine protein-like peaks (B1 and B2) also appear in the spectra in addition to tryptophan-like peaks. This fact might constitute a specific feature to differentiate these wastewaters from others, since the appearance of peaks B is quite uncommon in wastewaters. The textile dyeing effluent shows a characteristic triple humic-like fluorescence (peaks A, C1 and C2) that may represent a specific fingerprint for this kind of effluent. Leachates from medium-aged and old landfills might also show a specific fingerprint in their EEM spectra: the sole presence of the humic-like peak C with very high fluorescence intensity. This feature also allows differentiating them from young landfill leachates, which show predominance of protein-like peaks. The fluorescence index (FI) does not seem to be very appropriate to characterize wastewaters and its usefulness might be limited to the study of humic substances in natural waters, although further studies are needed on this topic. However, the humification index (HIX) and the biological index (BIX) do seem to be useful for studying wastewaters, since they have provided consistent results in the present work. This study shows the potential of EEM fluorescence to identify the origin of some industrial effluents, although more research is needed to check these preliminary results.

Comprehensive characterization of industrial wastewaters using EEM fluorescence, FT-IR and 1H NMR techniques.

The organic matter present in six industrial wastewaters (pulp and paper mill, brewery, textile, dairy, slaughterhouse effluents and a municipal landfill leachate) has been studied in this work using three analytical techniques: excitation-emission matrix fluorescence (EEMF), proton nuclear magnetic resonance spectroscopy (1H NMR) and Fourier transform infrared spectroscopy (FTIR). The pulp and paper mill effluent shows characteristic signals of the presence of lignins, carbohydrates and carboxylic acids, as well as sulfate, carbonate and sulfonates (coming from surfactants used in the cleaning of tanks). The main constituents of the brewery effluent are peptides and proteins coming mainly from spent yeast and diatomite filters (the presence of the latter was confirmed by SiO bands in the FTIR spectrum). The municipal landfill leachate is characterized by the majority presence of humic substances (typical of an old landfill) and a residual presence of small peptides, amino acids and carboxylic acids. Additionally, several inorganic compounds were identified by FTIR, such as nitrate, sulfate, phosphate and cyanide ions. The textile effluent from a cotton-based industry contains carbohydrates, carboxylic acids and sulfonates, which can act as auxochromes in the textile industry. The dairy effluent comprises amino acids and small peptides coming from the biodegradation of milk and whey in addition to carbohydrates (lactose) and carboxylic acids (mainly lactic acid). The presence of tyrosine-like peaks B in the EEMF spectrum of the slaughterhouse effluent indicates the existence of small peptides and amino acids coming from the biodegradation of blood proteins. Additionally, residual glucose, fatty acids, phosphate and sulfate were also identified in this effluent.

Using excitation-emission matrix fluorescence to evaluate the performance of water treatment plants for dissolved organic matter removal.

This study is aimed at assessing the performance of water treatment plants (both wastewater and drinking water treatment plants) for dissolved organic matter (DOM) removal using excitation-emission matrix fluorescence (EEMF) as the monitoring technique. The influent from the wastewater treatment plant (WWTP) of Burgos (Spain) is characterized from the presence of protein-like peaks (T1 and T2) and humic-like peaks (A and C), T2 and A showing the highest fluorescence intensity. The percentages of total removal in the effluent were in the following order: peak T1 (65%) > peak A (45%) > peak C (34%) > peak T2 (26%). The humic-like peaks were the most removed at the primary sedimentation stage, whereas peak T1 was by far the most removed in the biological reactor. Protein-like peaks T1 and T2 experienced a slight increase in the final effluent in comparison to their fluorescence at the previous stage (the exit of the biological reactor), an increase that can be explained by the release of SMP (soluble microbial products) from the biomass in the secondary clarifier. A poor correlation was obtained between peak T2 fluorescence and COD, BOD (r2 = 0.34-0.38). The natural water from the Úzquiza reservoir in Burgos (Spain) is characterized by the only presence of humic substances: a majority peak A (fulvic-like) and a weak peak C (humic-like). The whole fluorescent DOM was removed by coagulation-flocculation but a low fluorescence peak T2 appeared at the final stage, coming from protein-like SMPs released by the biomass attached to the filters.