Solubility and reactivity of surfactant-enhanced alkaline hydrolysis of organophosphorus pesticide DNAPL.

The study presented in this paper evaluated the effectiveness of surfactants in enhancing mass removal of organophosphorus pesticides (OPPs) from soil under highly alkaline conditions and potential for enhancing in situ alkaline hydrolysis for treatment of OPPs, particularly parathion (EP3) and methyl parathion (MP3). In control and surfactant experiments, hydrolysis products EP2 acid, MP2 acid, and PNP were formed in non-stoichiometric amounts indicating instability of these compounds. MP3 and malathion were found to have faster hydrolysis rates than EP3 under the conditions studied. All surfactants evaluated increased solubility of OPPs under alkaline conditions with four nonionic alcohol ethoxylate products providing the greater affect over the polyglucosides, sulfonate, and propionate surfactants evaluated. The alcohol ethoxylates were shown to provide substantial mass removal of OPPs from soil. Hydrolysis rates were typically slower in the presence of surfactant, despite the relatively higher aqueous concentrations of OPPs; this was likely due to micellar solubilization of the OPPs which were therefore less accessible for hydrolysis. The results of this study support the use of surfactants for contaminant mass removal from soil, particularly under alkaline conditions, and may have implications for use of some surfactants in combination with other technologies for treatment of OPPs.

The influence of cosolvent and heat on the solubility and reactivity of organophosphorous pesticide DNAPL alkaline hydrolysis.

The presented research concerned the compatibility of cosolvents with in situ alkaline hydrolysis (ISAH) for treatment of organophosphorous (OPP) pesticide contaminated sites. In addition, the influence of moderate temperature heat increments was studied as a possible enhancement method. A complex dense non-aqueous phase liquid (DNAPL) of primarily parathion (~50 %) and methyl parathion (~15 %) obtained from the Danish Groyne 42 site was used as a contaminant source, and ethanol and propan-2-ol (0, 25, and 50 v/v%) was used as cosolvents in tap water and 0.34 M NaOH. Both cosolvents showed OPP solubility enhancement at 50 v/v% cosolvent content, with slightly higher OPP concentrations reached with propan-2-ol. Data on hydrolysis products did not show a clear trend with respect to alkaline hydrolysis reactivity in the presence of cosolvents. Results indicated that the hydrolysis rate of methyl-parathion (MP3) decreased with addition of cosolvent, whereas the hydrolysis rate of ethyl-parathion (EP3) remained constant, and overall indications were that the hydrolysis reactions were limited by the rate of hydrolysis rather than NAPL dissolution. In addition to cosolvents, the influence of low-temperature heating on ISAH was studied. Increasing reaction temperature from 10 to 30 °C provided an average rate of hydrolysis enhancement by a factor of 1.4-4.8 dependent on the base of calculation. When combining 50 v/v% cosolvent addition and heating to 30 °C, EP3 solubility was significantly enhanced and results for O,O-diethyl-thiophosphoric acid (EP2 acid) showed a significant enhancement of hydrolysis as well. However, this could not be supported by para-nitrophenol (PNP) data indicating the instability of this product in the presence of cosolvent.