Biosurfactant (Monorhamnolipid) Complexation of Metals and Applications for Aqueous Metalliferous Waste Remediation

Abstract

Biosurfactants are compounds that exhibit surface activity (e.g., reduce surface and interfacial tension) and are derived from natural, biological sources. They are considered green substances due to their natural derivation, biodegradability, and relatively low toxicity. Biosurfactants from multiple classes have been shown to interact with metals, and a review of these interactions is provided. Rhamnolipids produced by Pseudomonas aeruginosa are attracting attention for metal remediation applications. The purpose of this dissertation is to evaluate rhamnolipids' ability to complex rare earth elements, determine the environmental compatibility of novel rhamnolipid diastereomers, and assess the efficacy of rhamnolipid as a collector in ion flotation. Previous research shows rhamnolipids selectively bind elements of environmental concern over common soil and water cations, but there had been no examination of transition metals from the f-block of the periodic table. The f-block elements include the rare earth elements, which are a vital component of nearly every modern technology and subject to supply risk. The interaction between monorhamnolipids and the rare earth elements was investigated by determining conditional stability constants using a resin-based ion exchange method. For the 27 metals examined, the conditional stability constants could be divided into three groups, albeit somewhat subjectively: weakly, moderately, and strongly bound. UO22+, Eu3+, Nd3+, Tb3+, Dy3+, La3+, Cu2+, Al3+, Pb2+, Y3+, Pr3+, and Lu3+are strongly bound with conditional stability constants ranging from 9.82 to 8.20; Cd2+, In3+, Zn2+, Fe3+, Hg2+, and Ca2+ are moderately bound with stability constants ranging from 7.17 to 4.10; and Sr2+, Co2+, Ni2+, UO22+, Cs+, Ba2+, Mn2+, Mg2+, Rb+, and K+ are weakly bound with stability constants ranging from 3.95 to 0.96. The uranyl ion is reported twice due to the ion demonstrating two distinct binding regions. The conditional stability constants were demonstrated to be an effective predictor of metal removal order. The metal parameters of enthalpy of hydration and ionic charge to radius ratio were shown to be determinants of complexation strength. Naturally produced rhamnolipids are a mixture of congeners. Synthetic rhamnolipid synthesis has recently enabled production of four monorhamnolipid diastereomers of a single congener. The biodegradability, acute toxicity (Microtox assay), embryo toxicity (Zebrafish assay), and metal binding capacity of the diastereomers was investigated and compared to natural monorhamnolipid. Biodegradability testing showed all the diastereomers were inherently biodegradable. By the Microtox assay, all of the monorhamnolipids were categorized as slightly toxic by Environmental Protection Agency ecotoxicity categories. Out of 22 parameters tested, the zebrafish toxicity assay showed only diastereomer toxicity for the mortality parameter, except for diastereomer R,R which showed no toxic effects. All the monorhamnolipids interacted with both Cd2+ and Pb2+. Ion flotation is one possible technology for metal recovery and remediation of metal contaminated waters. Ion flotation utilizes charged surfactants to collect and concentrate non-surface active ions at the surface of an aerated solution. Rhamnolipid's suitability as a collector in ion flotation was investigated. A flotation column was designed to test monorhamnolipid efficacy as a collector. Monorhamnolipids form foams and effectively remove Cs+, Cd2+, and La3+ from solution. The efficacy of the flotation process relies on the collector:colligend ratio and valency of the colligend. Flotation of metal solutions showed a removal order of Cd2+>La3+>>Cs+ when the metals were present individually and mixed at equimolar concentrations. When mixed at order of magnitude different concentrations, the flotation order was Cd2+>>Cs+>>La3+. These studies show rhamnolipid has potential to be used for environmentally-compatible metal recovery and metalliferous water remediation, especially for the rare earth elements.