Phototransformations of selected pharmaceuticals under low-energy UVA-vis and powerful UVB-UVA irradiations in aqueous solutions--the role of natural dissolved organic chromophoric material.

The kinetics of simulated low-energy daylight (UVA-vis) and powerful combined ultraviolet B and A (UVB-UVA) induced direct and indirect phototransformations of four pharmaceuticals, i.e., ibuprofen, metoprolol, carbamazepine, and warfarin, which were investigated in dilute solutions of pure laboratory and natural humic waters. The results strengthen the essential function of natural chromophores in dissolved organic material (CDOM) as principal photosensitizer toward indirect phototransformations of pharmaceuticals in natural conditions under available low-energy UVA-vis and slight UVB radiations. The results confirmed that organic micropollutants are able to undergo a direct photolysis if their absorbance spectra overlap the spectral range of the available radiation but only if the radiation is strong enough, e.g., ibuprofen is able to undergo only indirect photolysis via different pathways in all realistic conditions. The action of nitrate anions as photosensitizers in the applied conditions proved to be of little importance. High-performance size-exclusion chromatographic experiments verified that the rate constants obtained under the low-energy UVA-vis and powerful UVB-UVA irradiations for the decreased amounts of the two largest molecular size fractions of CDOM were quite close to the rate constants detected for the increased amounts of the next five molecular size fractions with smaller molecular sizes. The decreased contents of the two largest molecular size fractions correlated quite well with the decreased contents of the studied pharmaceuticals under the low-energy UVA-vis irradiation process but somewhat less under the powerful UVB-UVA irradiation. The photochemically induced decomposition of the CDOM aggregates appears to increase the amounts of smaller molecular size fractions and simultaneously produce via CDOM-stimulated radical reactions indirect structural transformations of pharmaceuticals. Apparent quantum yields were estimated for the transformation-degradation of the two largest molecular-size CDOM aggregates under low-energy UVA-vis and powerful UVB-UVA irradiations.

ESI-MS analyses of lake dissolved organic matter in light of supramolecular assembly.

A high-performance size-exclusion chromatography (SEC) system was coupled on-line to an electrospray ionization (ESI) interface to detect gas-phase ions by an API 365 LC/MS/MS triple quadrupole analyzer. The SEC fractions of a strongly coloured freshwater solution containing dissolved organic matter-humic substances (DOM-HS) were screened both by UV(254) and by ESI mass spectrometry (ESI-MS) in the full-scan mode within the m/z range of 100-2,900 amu in negative and positive polarities. The ESI-MS spectra were also collected by direct infusion of the DOM-HS solution in both polarities. ESI-MS spectra did not primarily favour low mass compounds, and negative and positive total ion chromatograms were parallel to the SEC elution profile obtained by UV(254) detection from DOM-HS solution. The UV(254) detection overestimated the SEC portion of higher size/mass solutes and underestimated that of solutes of smaller sizes/masses as compared with the total ion chromatogram intensities in negative or positive polarities. The change of mass-weighted and number-weighted average sizes/masses (M(w) and M(n)) of different SEC fractions was fairly small, in contrast to UV(254) detection, with increasing elution volume. A reasonable explanation for the great differences between M(w) and M(n) values, obtained by UV(254) and ESI-MS detections for eight different SEC fractions, seems to be a supramolecular-type association of relatively small components through weak dispersive forces. M(n) values obtained by vapour-pressure osmometry for different SEC fractions were to some extent analogous with those of negative and positive ESI-MS. The shapes obtained by either negative or positive polarities and calculated M(w) and M(n) values indicated a close structural similarity between each SEC fraction. Positive ion and negative ion spectra of different humic fractions represented quite similar components, and there was no evidence for noteworthy occurrence of multiply charged ions being able to lower mass distributions of negative ion spectra. The effect of nitrogen on the mass spectra seemed to be unimportant, and the weak ions observed at even m/z values correspond most likely to the (13)C counterparts of the more abundant (12)C odd ions. No uncontrolled ESI fragmentation was observable and humic solutes seemed to be quite heat-resistant. Direct infusion of the untreated DOM-HS solution and statistical calculation verified that the SEC-separated different fractions really represent distinct entities of the original DOM-HS mixture. ESI-MS results support the opinion that the structural composition of humic solutes in their original combined mixture resembles supramolecular-type associations of smaller molecular size entities possessing similar structural functionalities.

Comparisons of sorption of aquatic humic matter by DAX-8 and XAD-8 resins from solid-state (13)C NMR spectroscopy's point of view.

Aquatic humic solutes were separated in parallel by the non-ionic macroporous DAX-8 and XAD-8 resins from four different fresh water sources. On average, the sorptive power of the DAX-8 resin does not differ systematically from that of the XAD-8 resin. The DAX-8 resin seems to have more precise column characteristics compared with the XAD-8 resin. There was no significant difference between the major elemental compositions of the parallel humic-solute bulks obtained by these two resins. According to the (13)C NMR spectroscopy the content and quality of aliphatic carbons, especially those representing terminal methyl groups or methylene carbons, were the most systematic and powerful discriminating factors between the humic extracts obtained by these two resins. Generally speaking the DAX-8 and XAD-8 resins seem to isolate humic-solute bulks almost equally, although the content of aliphatics is slightly greater for the former, producing mixtures with similar structural compositions for general purposes. The structural composition and quantity of the humic-solute mixture isolable with a weakly basic DEAE-cellulose anion exchange resin differs partially from any humic fraction obtained by non-ionic sorbing solids. The environmental impact was also visible on the quality of the structural fine-chemistry of the different humic isolates obtained both by the DAX-8 and XAD-8 resins.