Sol-gel immunosorbents (IS) prepared by encapsulation of polyclonal antibodies in silica were packed in cartridges and evaluated for selective immunoaffinity extraction (IAE) of malathion and triazines from aqueous samples. Encapsulated atrazine antibodies highly cross-reacted with simazine and propazine but did not recognize prometon and prometryn. No cross-reactivity of malathion antibodies was observed with the closely related metabolites oxomalathion and isomalathion. Mean IS binding capacities per milligram of entrapped antibody were 0.33 nmol of malathion and 0.47 nmol of atrazine (approximately 100 ng each). This capacity remained constant for at least 10 weeks, and the cartridge reusability was excellent (>60 IAE runs); also, high preconcentration factors were feasible because the breakthrough of analytes from IS cartridges did not occur up to the 250 mL sample volumes, provided that the capacity was not surpassed. Simple and rapid methods for determination of malathion or three triazines in surface water were developed using off-line IAE and HPLC-UV. The application to 50 mL dam water samples spiked at approximately 1 ng/mL of pesticides resulted in recoveries of approximately 90% and RSD < 5% (n=7). LODs for this sample volume (direct injection of IS eluates) were in the range of 0.15-0.50 ng/mL. Lower LODs (0.03-0.1 ng/mL) were achieved by online analysis of whole eluates previously loaded in RP precolumns.

Trace organic precursors remaining in water after primary treatment can originate a variety of toxic disinfection by-products during chlorination. Therefore, knowledge of conditions leading to their persistence or transformation in chlorinated media is crucial for human health protection. Using phenol as model compound at trace level (50 ppb), the short term formation and degradation of chlorophenols (CPs) in plain water and buffered water (pH 4.8, 7 and 9) treated with typical chlorine doses (1-5 ppm) was investigated. Total phenol consumption and quantitative degradation of formed CPs occurred in < or =5h with 5 ppm chlorine in plain water and alkaline buffer, and with 1 ppm chlorine in phosphate buffer of pH 7. The enhanced reactivity in this buffer was attributed to high ionic strength (0.18 M). On the contrary, phenol was only slowly transformed to monochlorophenols (MCPs) in acidic media. Analysis of phenol and CPs concentration profiles indicated the coexistence of two competing reaction pathways in neutral and alkaline conditions: 1) successive ortho-para chlorination of aromatic ring up to 2,4,6-trichlorophenol followed by ring cleavage, 2) direct oxidation of MCPs to rapidly degradable oxygenated aromatics (dihydroxybenzenes, benzoquinones). Ionic strength and pH had some influence on preferred pathway but chlorine dose was determinant.