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.

Carbon and hydrogen isotope analysis of parathion for characterizing its natural attenuation by hydrolysis at a contaminated site.

The applicability of compound-specific isotope analysis (CSIA) for assessing in situ hydrolysis of parathion was investigated in a contaminated aquifer at a former pesticide wastes landfill site. Stable isotope analysis of parathion extracted from groundwater taken from different monitoring wells revealed a maximum enrichment in carbon isotope ratio of +4.9‰ compared to the source of parathion, providing evidence that in situ hydrolysis took place. Calculations based on the Rayleigh-equation approach indicated that the natural attenuation of parathion was up to 8.6% by hydrolysis under neutral and acidic conditions. In degradation experiments with aerobic and anaerobic parathion-degrading microbes, no carbon and hydrogen isotope fractionation of parathion were observed. For the first time, CSIA has been applied for the exclusive assessment of the hydrolysis of phosphorothioate-containing organophosphorus pesticides at a contaminated field site.

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.

Association between cadmium and calcium uptake and distribution during the moult cycle of female shore crabs, Carcinus maenas: an in vivo study.

Net influxes into the haemolymph and tissue distribution of 45Ca and 109Cd were studied in vivo in female Carcinus maenas at different moult stages. Net influxes of 45Ca and 109Cd from water were higher in postmoult (A and B) C. maenas than in C3- and C4-intermoult crabs and the net influx of calcium was higher in C3-intermoult crabs than in C4-intermoult crabs. The net influxes of 45Ca and 109Cd increased in postmoult C. maenas with decreasing external calcium concentrations at constant salinity. At all external calcium concentrations a significant correlation existed between 45Ca and 109Cd accumulated in the haemolymph of individual animals. In vivo exposure of postmoult C. maenas to external lanthanum decreased the 45Ca and 109Cd uptake rates to 30 and 10%, respectively, of the control values. About 30% of injected 109Cd were found in the midgut gland, 10-20% in the gills and only a few (1-2) percent was lost to the seawater 24 h after injection. No major variations in tissue distribution of 109Cd were observed between moult stages in these tissues. Premoult crabs retained more cadmium in the haemolymph 24 h after injection than other moult stages, and postmoult crabs retained more in muscle. Between 20 and 40% of the injected 45Ca were excreted to the water, while only a few percent of the injected 45Ca were found in the soft tissues 24 h after injection. Large moult stage variations, however, were observed in the tissue distribution of internalised 45Ca. This study demonstrates that cadmium and calcium uptakes are elevated in postmoult C. maenas. The results indicate that cadmium and calcium in this stage are taken up via Ca2+-channels located in the apical membrane of gill epithelium cells. When internalised, however, cadmium and calcium are metabolised in fundamentally different ways, determined by the chemical properties and biological significance of the two metals.

In vivo and in vitro cadmium accumulation during the moult cycle of the male shore crab Carcinus maenas--interaction with calcium metabolism.

The effect of moult stage on cadmium accumulation and distribution was investigated in vivo in male shore crabs Carcinus maenas exposed to 1 mg Cd l(-1) for 7 days. The accumulation of cadmium in all tissues examined was markedly higher in postmoult (A(1-2) and B(1-2)) compared to intermoult (C1, C3 and C4) and premoult (D(0-3)). In addition, elevated levels of cadmium were found in gills of late premoult (D(2-3)) animals. The total amount of cadmium accumulated in the tissues (haemolymph, gills, midgut gland and muscle) increased from 43 microg Cd in early premoult (D(0-1)) to 391 microg Cd in late postmoult (B(1-2)). Gills and midgut gland were the primary cadmium accumulating tissues in C4-intermoult and premoult (D(0-3)); in early postmoult (A(1-2)) haemolymph and midgut gland were the main cadmium containing tissues, while midgut gland dominated in late postmoult (B(1-2)) and early intermoult (C1 and C3). A detailed account of calcium distribution in haemolymph, gills, midgut gland, muscle and exoskeleton during the moult cycle is presented. Mechanistic links between cadmium and calcium uptake in posterior gills of C4-intermoult and early postmoult (A(1-2)) crabs were explored using an in vitro gill perfusion technique. Calcium and cadmium influxes were markedly higher in postmoult compared to intermoult. No differences between intermoult and postmoult effluxes were found for either calcium or cadmium. From intermoult to postmoult net influx increased from 2.4 to 29 micromol Ca2+ g(-1) ww(gill) h(-1) and from 0.24 to 25 nmol Cd2+ g(-1) ww(gill) h(-1). The results indicate that the postmoult increase in cadmium influx is due to increased active transport of cadmium, at least partly, by accidental uptake via calcium transporting proteins. The in vitro net influx rates corresponded accurately to the observed in vivo accumulation of both cadmium and calcium. Although cadmium accumulation and distribution are clearly linked to changes in calcium requirements, cadmium did not interfere with calcium accumulation or distribution at any stage during the moult cycle.