Interaction of Ca^(2+) and soil humic acid characterized by a joint experimental platform of potentiometric titration, UV–visible spectroscopy, and fluorescence spectroscopy

Rocky desertification has become a major environmental issue in the karst region of southwestern China.Karst rocky desertification was more severe in regions of limestone soil than in adjacent regions of other soils,despite the relatively higher soil organic matter(SOM)content in limestone soil.The underlying mechanism remains ambiguous.We speculated that the geochemical characteristics of limestone soils in the karst region plays an essential role,especially the high calcium content of limestone soil.To test this hypothesis,we collected limestone soil samples from a limestone soil profile in the southwestern China karst region and extracted humic acid(HA)from these limestone soil samples.We investigated the interaction of Ca^(2+)and three HA samples on a joint experimental platform,which consists of an automatic potentiometric titrator,a UV–visible spectrometer,and a Fluorescence spectrometer.HA solutions were titrated by Ca^(2+)and optical spectra of the HA solutions were monitored during the titration experiments.The results indicated that:(1)the interaction of Ca^(2+)and HA is a combined process of adsorption and complexation.Adsorption dominated the overall distribution behavior of Ca^(2+),which could be fit by Langmuir and Freundlich isotherm models.Complexation was distinguished only when the concentration of Ca2+is low;(2)the changes of UV–visible spectroscopy and excitation–emission matrix fluorescencespectroscopy spectra of HA samples when they were binding with Ca^(2+)implied the apparent molecular size and structure of HA became larger and more complex;(3)the combination of Ca^(2+)and HA plays an important role in the SOM preservation of limestone soils but the stability of the Ca–HA association was relatively weak.The present study draws attention to maintaining the relatively higher Ca^(2+)concentration in limestone soils in ecologic restoration attempts in karst regions.

Effects of geosorbent and solution properties on sorption and desorption of PAHs

Characteristics of phenanthrene and pyrene’s sorption and desorption on two local soils in solutions of simulated groundwater,simulated lung fluid,and simulated saliva were studied with batch equilibrium experiments to understand the fate of PAHs in the karst region of southwestern China and to assess the environmental exposure and the health risk of PAHs.The results showed that the sorption and desorption isotherms of phenanthrene and pyrene on two target soils in the three solution systems could be adequately described by the Freundlich model,while the fitted isotherm parameters for the simulated groundwater solution distinguished notably from those for the simulated body fluid solutions.For the sorption experiments,in the simulated groundwater,the n values were 0.722 and 0.672 for phenanthrene and were 0.724 and0.663 for pyrene,respectively,on the yellow soil and the limestone soil;The log KF values were 3.118 and 3.323 for phenanthrene and were 3.648 and 3.846 for pyrene,respectively,on the yellow soil and the limestone soil.In the simulated body fluids,the n values for phenanthrene and pyrene ranged from 0.622 to 0.836 and from 0.590 to0.865,respectively,and the log KF values of phenanthrene and pyrene ranged from 2.845 to 3.327 and from 3.344 to3.779,respectively.For the desorption experiments,in the simulated groundwater,the n values were 0.662 and 0.744 for phenanthrene and were 0.702 and 0.647 for pyrene,respectively,on the yellow soil and the limestone soil.The log KF values were 3.666 and 3.686 for phenanthrene and were 4.128 and 4.225 for pyrene,respectively,on the yellow soil and the limestone soil.In the simulated body fluids,the n values for phenanthrene and pyrene ranged from 0.612 to 0.668 and from 0.631 to 0.819,respectively,and the log KF values of phenanthrene and pyrene ranged from 3.134 to 3.407 and from 3.533 to 3.839,respectively.The limestone soil had relatively higher log KF values but lower KOC values compared to those of the yellow soil,indicated that the nature of sorbent soils played the dominant role in sorption and desorption behaviors of PAHs.The experimental results showed a remarkable differences in sorption and desorption behaviors of PAHs in simulated body fluids and groundwater.The nonlinearities of measured isotherms and the measured sorption capacities of soils in simulated body fluids were significantly lower than corresponding those in the simulated groundwater,and HI values for simulated body fluids systems were significantly smaller than corresponding those for the simulated groundwater systems.The results underscore cautions in assessing environmental exposure and health risks of PAHs based on their sorption-desorption data in simulated groundwater as this is traditionally done.