Zinc uptake and replenishment mechanisms during repeated phytoextraction using Sedum plumbizincicola revealed by stable isotope fractionation

Improving phytoremediation techniques requires a thorough understanding of the mechanisms of plant uptake and the replenishment of the bioavailable pool of the target element, and this may be effectively explored using stable isotope methods. A repeated phytoextraction experiment over five successive crops of cadmium (Cd) and zinc (Zn) hyperaccumulator Sedum plumbizincicola X.H. Guo et S.B. Zhou ex L.H. Wu (Crassulaceae) was conducted using four agricultural soils differing in soil pH and clay content. The isotopic composition of total Zn and NH4OAc-extractable Zn in soils before phytoextraction and after the fifth crop were determined, together with Zn in shoot samples in the first crop. S. plumbizincicola preferentially took up light Zn isotopes from the NH4OAc-extractable pool (Delta 66Znshoot-extract = -0.42 to -0.16%0), indicating the predominance of Zn lowaffinity transport. However, after long-term phytoextraction NH4OAc-extractable Zn became isotopically lighter than prior to phytoextraction in three of the soils (Delta 66Znextract: P5-P0 = -0.39 to -0.10%0). This was resulted from the equilibrium replenishment of Zn bound to iron (Fe) and manganese (Mn) oxides based on Zn isotopic and chemical speciation analysis. Zinc showed opposite fractionation patterns to Cd in the same plant-soil system with heavy Cd isotope enrichment in S. plumbizincicola (Delta 114/110Cdshoot-extract = 0.02-0.17%0) and in the NH4OAc-extractable pool after repeated phytoextraction (Delta 114/110Cdextract: P5-P0 = 0.07-0.18%0). This indicates different mechanisms of membrane transport (high-affinity transport of Cd) and supplementation of the bioavailable pool in soil (Cd supplied mainly through complexation with root-derived organic ligands) of the two metals. The combination of chemical speciation and stable Zn isotope ratios in the plant and the bioavailable soil pool reveal that the Zn pool related to Fe and Mn oxides became increasingly bioavailable with increasing crop generations. Capsule: Stable isotope analysis indicates that soil Fe- and Mn-oxide bound Zn replenishment boosted Zn uptake by the hyperaccumulator Sedum plumbizincicola during long-term remediation. (c) 2021 Elsevier B.V. All rights reserved.