Heavy metal immobilization
Pb immobilization by zeolite appeared to be dose dependent, as evidenced by the increasing immobilization observed with the high dose. Additionally, Pb concentration in the shoots was found to be directly correlated with the amount of zeolite or related agents added to particular soils in earlier studies (El-Eswed et al. 2015; H. Li et al. 2009; Shi et al. 2009). Generally speaking, the rise in plant Pb concentration matched the soil's soluble Pb concentration. Furthermore, earlier research has shown a positive correlation between plant and soil Pb concentrations (Schmidt 2003; H. Li et al. 2009; Shi et al. 2009; Shen et al. 2002). Metals from various soil components or their surfaces are extracted or desorbed by cation exchange regulated by particle diffusion with zeolite.Additionally, metal promotes the creation of complexes, oxides, and metal-carbonate precipitates, all of which reduce metal mobility (Chlopecka and Adriano 1996; Hamidpour et al. 2010; H. Wang et al. 2016). This is explained by the poor adsorption of lead (Pb) by soil and the formation of sediment with zeolite, which increases Pb stabilization more readily (Sarkar et al. 2008; Hamidpour et al. 2017).
Pb content in 1:3 and 1:4 humus:sand ratio soils in the current study was more than that of 1:1 and 1:2 ratio soils in almost all zeolite treatments (Fig. 2), suggesting that soils with different humus:sand ratios had different stabilization patterns. Regarding the function of humus in the remediation of heavy-metal-contaminated soils, opinions are currently divided. Humus is a heterogeneous substance, and small structural and chemical differences can concurrently exert mobilizing and stabilizing effects. due to the improvement of the cation exchange capacity of soils, the adsorption of Pb ions to the humic acid in the complex will be increased, which results in reducing mobility of Pb, thus permitting the re-establishment of vegetation at contaminated sites (Chaturvedi et al. 2007; Narwal and Singh 1998). These opinions are supported by more research, and our results are similar to these reports. However, acid humus reduces soil pH, which could increase the soluble Pb fraction concentration in soil (Schmidt 2003). This is opposite to the experimental results of the present study, so that this explanation should be discarded.
At the lowest and highest zeolite doses, respectively, zeolite clearly immobilized more soluble Pb at 1:1 and 1:2 than at 1:3 and 1:4 humus:sand media, ranging from 5–40 g kg-1. These results imply that there were substantial differences in the distribution patterns following zeolite treatment amongst the different humus treatments. It is well known that the complex structure of humus can interact, via complex formation or chelation, with heavy metals. The adsorption in a metal-humus-zeolite system is influenced by the complexing of metal ions with humus and the competitive adsorption of heavy metal ions and humus on zeolite surfaces. The results of this experiment show that there is no difference in Pb immobilization between the 1:1 and 1:2 humus:sand media. This indicates that Pb and humus complexing is considerably weaker and that Pb and humus competitive adsorption is stronger. According to Wang et al. (2008), Pb > humus is the sequence in which the adsorptive affinity of Pb and humus to the zeolite is followed. It follows that Pb immobilization is greatly increased by Pb adsorption on zeolite and Pb complexing with humus in the 1:1 ration soil. Strong Pb adsorption on zeolite prevents Pb from complexing with humus in the presence of low humus, which may be the cause of the greater insoluble Pb in the soil with a 1:4 ratio. On the zeolite, there is a kinetic curve showing dynamic Pb uptake. Pb adsorption on zeolite is progressively enhanced during the adsorption process, reaching equilibrium adsorption after 140 hours (S. B. Wang et al. 2008).
At 1:1, 1:2, 1:3 humus:sand media, Pb immobilization increased and plant uptake in aboveground tissues decreased for two applications of 20 g zeolite kg− 1 moreso than one application of 40 g kg− 1 (Fig. 2). The mechanism is not known for greater Pb stability in soil associated with repeated application of zeolite. The difference in Pb immobilization between one and two zeolite applications might be due to the effective adsorption capability of zeolite. Effective adsorption capability is defined as the change in heavy metal immobilization by soil amendments. For all treatments, Pb adsorption on the zeolite in binary component systems, which Pb immobilization initially continued to increase with time after zeolite treatment and then tended to be stable. This lag-phase, which was the decrease in cation exchange effect before the second sampling point onwards, must be taken into account. For zeolite this lag-phase is about 3 weeks (H. Wang et al. 2016) or 9 weeks (Shi et al. 2013). With a lag-phase of 9 weeks, the leachate Pb concentration of 20 g·kg− 1 zeolite was reduced to about 25% of highest Pb concentration with on zeolite treatment. There was lesser decrease for 10 g kg− 1 zeolite treatment and rate of decrease was about only 40%. The high persistence of the cation exchange effect at higher dosage may have been present because of more suface area of sorption.
The immobilization within this initial period is assumed to be caused by forming insoluble Pb fraction. The water soluble fraction, exchangeable fraction and carbonate-bound fraction of Pb were the main Pb solubility-controlling phases in the treated soil, nevertheless zeolite treatment caused a reduction of the above three fractions in the Pb- contaminated soil (H. Li et al. 2009; Wen et al. 2016). According to previous research (Lin et al. 2010), Pb carbonate, Pb Fe-Mn oxide and Pb organically bound fractions account for as much as 5%, 43%, and 52% of the total Pb, respectively. Although the Pb Fe-Mn oxide and Pb organically bound fraction accounts for the greatest proportion, both are immobilizable- only if they transform into the Pb water soluble fraction, Pb exchangeable fraction, and Pb carbonate fraction (Querol et al. 2006). However, the mechanism that zeolite treatment resulted in a reduction of the carbonate bound Pb fraction is not thoroughly understood (Castaldi et al. 2005; Basaldella et al. 2007; Lei et al. 2008). For an equal dose of zeolite, the lag-phase of two zeolite applications is longer than a single application, which makes Pb immobilization with two applications more effective. From the lag-phase, zeolite is a sufficiently long-lived substance to be appropriate for phytostabilization: its longevity will increase Pb immobility, even long after harvest. Therefore, it is suitable option for phytostabilization that high dose and second application after the initial treatment.
Plant uptake
Composition of the soil medium significantly affected biomass production, but there was no effect of zeolite (Fig. 1). This was attributed to detoxication to plants with zeolite and humus treatment. Pb content in the controls was 3.11 ± 0.16 mg plant− 1. Pb uptake was significant in all zeolite treatments, 30–70% less than in the untreated controls.
Zeolite amendments resulted in significant differences, and the observed differences are considered sufficient for enhanced phytostabilization. Compared to low nutrient levels, significantly less of the Pb pool was allocated to aboveground (leaves and stems) in high nutrient levels. Also, the effect on Pb uptake by zeolite was dose dependent, except for the low nutrient treatment. Because the fraction of Pb absorbed by zeolite varies considerably in high nutrition soil (Sarkar et al. 2008; Schmidt 2003), previous studies have also noted that the concentration of soluble Pb should correlate well with plant Pb concentration (Cui et al. 2007; Hamidpour et al. 2010; Shen et al. 2002).
Humus has a high organic matter content, which forms stable complexes with heavy metals, which increase with zeolite application (Shi et al. 2009). Soil with high humus content was significantly affected by zeolite. Besides humus directly affecting Pb solubility in soils, humus can promote plant growth in poor soils, providing a higher nutrient and water supply. The higher Pb accumulations may have been a side effect of higher biomass (Lin et al. 2010). However, the level of uptake in our experiment may be unduly high because of the short time between soil zeolite treatments and transplanting of seedlings (7 d). Wang et al. (2013) found that there were the similar leachate Pb concentration patterns with and without zeolite addition for the first 3 weeks, which increased the damage to seedlingswith heavy metal stress. Longer periods between zeolite addition and transplanting of seedlings may be required to redistribute the amendment throughout the upper soil profile and subsequent heavy metal translocation. Therefore, it is absolutely essential that the interval between zeolite addition and transplanting of seedlings exceeds 3 weeks.