Sorption of apolar aromatic compounds to soil humic acid particles affected by aluminum(III) ion cross-linking

• Published in: Journal of environmental quality 2004-07, Vol.33 (4), p.1314-1321
• Main Authors: Lu, Y, Pignatello, J.J
• Format: Article
• Language: English
• Subjects: Adsorption; Agronomy. Soil science and plant productions; Aluminum; Aluminum - chemistry; Applied sciences; Aromatic compounds; Biological and medical sciences; cation exchange capacity; Chlorobenzenes - chemistry; crosslinking; desorption; dichlorobenzene; Earth sciences; Earth, ocean, space; Engineering and environment geology. Geothermics; equations; Exact sciences and technology; exchangeable aluminum; Flocculation; Fundamental and applied biological sciences. Psychology; glass transition temperature; Humic acids; Humic Substances - analysis; hydrophobic bonding; hysteresis; Ions; mathematical models; Metal ions; Naphthalene; Naphthalenes - chemistry; Organic chemicals; Organic compounds; Organic matter; Particle Size; Pollution; Pollution, environment geology; Polymers; Polymers - chemistry; Soil organic matter; Soils; Solutes; Sorption; sorption isotherms; Transition temperatures; trichlorobenzene
• ISSN: 0047-2425; 1537-2537
• DOI: 10.2134/jeq2004.1314

Sorption of hydrophobic compounds in soils often shows nonlinearity, competition, and hysteresis. Since such behaviors have been associated with organic polymers in glassy state, it has been postulated that some forms of soil humic substances are glassy. The glassy state is favored by properties that decrease the flexibility of macromolecules, such as cross-linking, presence of unsaturated bonds, and high molecular weight. Polyvalent metal ions, which are abundant in soils, may cross-link humic substances by coordinating to multiple functional groups on different strands. Accordingly, we prepared an Al3+-cross-linked humic acid (Al-HA) from the H+ form (H-HA) of a soil humic acid by a flocculation technique that leaves Al ions bound to organic groups. Sorption of naphthalene and 1,2,4-trichlorobenzene (TCB) on H-HA was nonlinear, competitive, and slightly hysteretic, in agreement with previous studies showing glass transition temperatures of humic acids that lie above room temperature. Nonlinearity, competition, and hysteresis were all enhanced in Al-HA, validating the hypothesis that metal ion cross-linking enhances nonideal sorption. Application of a glassy polymer sorption model reveals that cross-linking increases the affinity of solutes for the hole domain relative to the dissolution domain. The results (i) indicate that isolated, purified soil humic acid behaves like a glassy solid, (ii) indicate that metal-ion cross-linking creates a more rigid-chain structure and supports a link between nonideal sorption and the glassy character of soil organic matter, and (iii) underscore the importance of metal ions on humic structure in relation to sorption of hydrophobic organic compounds.