Ionic-strength and pH effects on the sorption of cadmium and the surface charge of soils

Two Oxisols (Mena and Malanda), a Xeralf and a Xerert from Australia and an Andept (Patua) and a Fragiaqualf (Tokomaru) from New Zealand were used to examine the effect of pH and ionic strength on the surface charge of soil and sorption of cadmium. Adsorption of Cd was measured using water, 0.01 mol dmp^?3 Ca(NO₃)₂, and various concentrations of NaNO₃ (0.01–1.5 mol dm^?3) as background solutions at a range of pH values (3–8). In all soils, the net surface charge decreased with an increase in pH. The pH at which the net surface charge was zero (point of net zero charge, PZC) differed between the soils. The PZC was higher for soils dominated by variable-charge components (Oxisols and Andept) than soils dominated by permanent charge (Xeralf, Xerert and Fragiaqualf). For all soils, the adsorption of Cd increased with an increase in pH and most of the variation in adsorption with pH was explained by the variation in negative surface charge. The effect of ionic strength on Cd adsorption varied between the soils and with the pH. In Oxisols, which are dominated by variable-charge components, there was a characteristic pH below which increasing ionic strength of NaNO₃ increased Cd adsorption and above which the reverse occurred. In all the soils in the normal pH range (i.e. pH>PZC), the adsorption of Cd always decreased with an increase in ionic strength irrespective of pH. If increasing ionic strength decreases cation adsorption, then the potential in the plane of adsorption is negative. Also, if increasing ionic strength increases adsorption below the PZC, then the potential in the plane of adsorption must be positive. These observations suggest that, depending upon the pH and PZC, Cd is adsorbed when potential in the plane of adsorption is either positive or negative providing evidence for both specific and non-specific adsorption of Cd. Adsorption of Cd was approximately doubled when Na rather than Ca was used as the index cation.     

Degradation of chlorsulfuron and triasulfuron in alkaline soils under laboratory conditions

The degradation of chlorsulfuron and triasulfuron was investigated in alkaline soils (pH 7.1–9.4) spiked at 40 μg a.i. kg^–1 under laboratory conditions at 25 °C and a moisture content corresponding to 70% field capacity (–33 kPa), using high-performance liquid chromatography. Degradation data for the two herbicides did not follow first-order kinetics, and observed DT₅₀ values in surface soils ranged from 19 to 42 days and from 3 to 24 days for chlorsulfuron and triasulfuron respectively. Disappearance of both chlorsulfuron and triasulfuron was faster in non-sterile than in sterile soil, demonstrating the importance of microbes in the breakdown process. The persistence of chlorsulfuron increased with increasing depth, which can be attributed to the decline in the microbial populations down the profile. The DT₅₀ value for chlorsulfuron at 30–40 cm depth was nearly four times higher than that in the top-soil. The results obtained show that persistence of these herbicides in alkaline surface soils at 25 °C and at a moisture content of 70% field capacity is similar to those reported in other European and North American soils. The study shows that if these herbicides are contained in surface soil layers, the risk of residue carry-over under southern Australian conditions is small. However, the rate of their degradation in alkaline subsoils is very slow, and under conditions conducive to leaching their prolonged persistence in the soil profile is possible.