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.

Hazards and Landscape Changes(Degradations) on Hungarian Karst Mountains Due to Natural and Human Effects

In order to study the karstological processes within the karst ecological system,the geohazards and degradation of karst landscapes on the karst areas of the Bakony mountains(Hungary),we investigated the abiotic elements of the environment,soil and cover deposits,erosion soil decay;the changes in the quantity and quality of karst waters:contamination at swallow holes,contamination of karst springs;and the biogenic factors:surface vegetation coverage by the corine land cover method,plant-ecological examinations,qualification of surface waters with the help of biological water labeling.We recognized that the increasing human activities during the past few centuries have had significant impact on the investigated landscapes of karst areas because of their spatial sensitivity.In the scope of our research we concluded that the landscape changes due to natural and human effects can vary strongly on the different karst areas.These differences can arise from the climatic and geomorphologic situation,the coverlayer's qualities,etc.,but primarily from the different utilization of the investigated karst areas(e.g.the intensity,characteristics and territorial extension of utilization).On the spot investigation we detected traces of new and fast geomorphological processes(gully formation,landslides,collapses,new sinkhole development) and landforms(sinkholes,gullies,swallow holes),which are clear evidences of the effect of climatic changes.

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.

The Degradation Rate of Straw Returned to Limestone Soil and the Effect on Soil Fertility

Limestone soil is a poor quality soil with a low rate of nutrient supply due to the accumulation of organic carbon. Here, we examined the degradation of maize straw in limestone soil and red soil using indoor simulation. Dynamic testing was conducted on soil chemical properties and soil fertility. We found that the degradation rate of straw in karst soil is higher than for non-karst soil. The highest degradation rate of straw occurred during the first 60 d, after which it rose slowly and balanced out at 98 d. The peak value of degradation of straw in karst soil was found at 28 d, while that in non-karst soil occurred at 42 d. The total period of degradation lasted 160 d; the degradation rate of straw in karst soil and non-karst soil was 77% and 75%, respectively. During the period of straw degradation, the pH of soil tended to decrease in the early stage and rise slowly in later stages and this is consistent with the pattern of degradation products during different stages of straw degradation. Straw return to fields can increase soil fertility, and the growth rate of available N and K content is significant. Compared to karst soil, the content of various fertility indicators in non-karst areas were lower according to total content tests, although the increase （percentage） in nonkarst area was higher; available P and K content were found to be higher in non-karst areas according to availability tests. Some available nutrients Jn straw return can be more readily released in non-karst soil, while karst soil can contribute to the accumulation of total nutrient content due to its special soil texture features, the firm binding of many nutrients with clay minerals and the slow supply of nutrients.

Soil Organic Carbon Mineralization as Affected by Cyclical Temperature Fluctuations in a Karst Region of Southwestern China

The diurnal fluctuation in soil temperature may influence soil organic carbon （SOC） mineralization, but there is no consensus on SOC mineralization response to the cyclical fluctuation in soil temperature. A 56-d incubation experiment was conducted to investigate the effects of constant and variable temperatures on SOC mineralization. Three soils were collected from the karst region in western Guizhou Province, southwestern China, including a limestone soil under forest, a limestone soil under crops and a yellow soil under crops. According to the World Reference Base （WRB） classification, the two limestone soils were classified as Haplic Luvisols and the yellow soil as a Dystric Luvisol. These soils were incubated at three constant temperatures （15, 20 and 25 ℃） and cyclically fluctuating temperatures （diurnal cycle between 15 and 25 ℃）. The results showed that the 56-d cumulative SOC mineralized （C56） at the fluctuating temperatures was between those at constant 15 and 25 ℃, suggesting that the cumulative SOC mineralization was restricted by temperature range. The SOC mineralization responses to the fluctuating temperatures were different among the three soils, especially in contrast to those at constant 20 ~C. Compared with constant 20 ℃, significant （P 〈 0.05） decreases and increases in C56 value were found in the limestone soil under forest and yellow soil under crops at the fluctuating temperatures, respectively. At the fluctuating temperatures, the forest soil with lower temperature coefficient Q10 （the relative change in SOC mineralization rate as a result of increasing the temperature by 10 ℃） had a significantly （P 〈 0.05） lower SOC mineralization intensity than the two cropland soils. These indicated that differences in temperature pattern （constant or fluctuating） could significantly influence SOC mineralization, and SOC mineralization responses to the fluctuating temperatures might be affected by soil characteristics. Moreover, the warmer temperatures might improve the ability of soil microbes to decompose the recalcitrant SOC fraction, and cyclical fluctuations in temperature could influence SOC mineralization through changing the labile SOC pool size and the mineralization rate of the recalcitrant SOC in soils.