title: Influence of sorption to dissolved humic substances on transformation reactions of hydrophobic organic compounds in water. Part II: hydrolysis reactions.
abstract: The effect of dissolved humic acid (HA) on two types of hydrolysis reactions was investigated: (I) dehydrochlorination of gamma-hexachlorocyclohexane (HCH) and 1,1,2,2-tetrachloroethane (TeCA) as a reaction involving hydroxide ions (OH(-)) and (II) hydrolysis of 1-octyl acetate (OA) which is catalyzed by H(+) at the applied pH value (pH 4.5). The rate of TeCA hydrolysis was not affected by addition of 2 g l(-1) of HA at pH 10 (k' = 0.33 h(-1)) but HCH hydrolysis was significantly inhibited (k' = 4.6 x 10(-3) h(-1) without HA and 2.8 x 10(-3)h(-1) at 2 g l(-1) HA). HCH is sorbed by 51% whereas TeCA sorption is insignificant at this HA concentration. Sorbed HCH molecules are effectively protected due to electrostatic repulsion of OH(-) by the net negative charge of the HA molecules. In contrast, OA hydrolysis at pH 4.5 (k' = 1.6 x 10(-5) h(-1)) was drastically accelerated after addition of 2 g l(-1) HA (k' = 1.1 x 10(-3) h(-1)). The ratio of the pseudo-first-order rate constants of the sorbed and the freely dissolved ester fraction is about 70. H(+) accumulation in the microenvironment of the negatively charged HA molecules was suggested to contribute to the higher reaction rate for the sorbed fraction in case of this H(+)-catalyzed reaction. Analogous effects from anionic surfactants are known as micellar catalysis.
authors.affiliation: UFZ, Helmholtz Center for Environmental Research - UFZ, Department of Environmental Technology, Permoserstrasse 15, 04318 Leipzig, Germany. anett.georgi@ufz.de
authors.forename: Anett
authors.initials: A
authors.lastname: Georgi
authors.forename: Ulf
authors.initials: U
authors.lastname: Trommler
authors.forename: Annett
authors.initials: A
authors.lastname: Reichl
authors.forename: Frank-Dieter
authors.initials: FD
authors.lastname: Kopinke
mesh_terms: D000327:Adsorption; D006812:Humic Substances; D006868:Hydrolysis; D057927:Hydrophobic and Hydrophilic Interactions; D009930:Organic Chemicals / Q000737:chemistry*
chemical_list: D006812:Humic Substances; D009930:Organic Chemicals