Partie B | International audience | Incidental zinc sulfide nanoparticles (nano-ZnS) are spread on soils through organic waste (OW) recycling. Here we performed soil incubations with synthetic nano-ZnS (3 nm crystallite size), representative of the form found in OW. We used an original set of techniques to reveal the fate of nano-ZnS in two soils with different properties. 68 Zn tracing and nano-DGT were combined during soil incubation to discriminate the available natural Zn from the soil, and the available Zn from the dissolved nano-68 ZnS. This combination was crucial to highlight the dissolution of nano-68 ZnS as of the third day of incubation. Based on the extended X-ray absorption fine structure, we revealed faster dissolution of nano-ZnS in clayey soil (82% within 1 month) than in sandy soil (2% within 1 month). However, the nano-DGT results showed limited availability of Zn released by nano-ZnS dissolution after 1 month in the clayey soil compared with the sandy soil. These results highlighted: (i) the key role of soil properties for nano-ZnS fate, and (ii) fast dissolution of nano-ZnS in clayey soil. Finally, the higher availability of Zn in the sandy soil despite the lower nano-ZnS dissolution rate is counterintuitive. This study demonstrated that, in addition to nanoparticle dissolution, it is also essential to take the availability of released ions into account when studying the fate of nanoparticles in soil.

Metal pollution in estuaries represents a serious environmental challenge, especially in areas affected by industrial and mining activities. This study investigates the metal partitioning and availability of rare earth elements (REE), Y and other trace metals (Ag, Tl, U and Cs) in the Ria of Huelva estuary (SW Spain), strongly affected by mining and industrial activities. A 30 h monitoring campaign was performed collecting periodic water samples and deploying diffusive gradient in thin films (DGTs) devices to determine the main factors controlling metal availability. The dissolved concentrations of U (3118–3952 ng/L) and Cs (284–392 ng/L) were in the same order of magnitude than those reported in other estuaries and coastal waters worldwide, however, REE (26–380 ng/L), Y (15–109 ng/L), Ag (14–307 ng/L) and Tl (29–631 ng/L) concentrations exceeded these values for the same salinities. Unlike most metals (i.e. Ag, Tl, U, Cs), which were mainly found in the dissolved form (87–100% of total), REE and Y were found in the particulate phase (22–36% of total). Metal lability was mainly related to the concentration in the water column following this order: U>REE>Y>Ag>Tl. A similar binding mechanism was observed for Tl and Cd, due to its chemical affinity. This relationship between chemical properties and absorption by DGT-resin was also observed for REE (and Y), Rb and Sr, which may cause bioaccumulation upon persistent exposure, considering the ability of these metals to cross the biological membranes. The lability of metals predicted by geochemical codes did not coincide with absorption of labile metals by DGTs due probably to the instability of complexes in contact with the DGT membranes, the inability of metals to form thermodynamically stable complexes or the absorption of colloids. From this work it can be concluded that DGT passive sampling should complement traditional sampling to monitor metal availability in aquatic environments.

Sorbents amended to sediments in situ for sequestration of hydrophobic organic contaminants (HOCs) may be swept away from the treated sites due to hydrodynamic forces applied to the sediment surface. The purpose of this study is to examine the possibility of recovery of HOC availability in sorbent-amended sediment after complete removal of the sorbent. Sediment contact with an easily separable model sorbent Tenax beads for 28 days in a slurry phase resulted in 74–98% reduction in polycyclic aromatic hydrocarbon and polychlorinated biphenyl availability compared to the untreated controls. HOC availability in the sorbent-treated sediment slightly increased by sorbent removal and after one month of mixing in a slurry phase because the slowly-desorbing HOC fraction was released and repartitioned back to the sediment, partially replenishing the rapidly-desorbing HOC fraction. However, HOC availability did not further increase during an extended mixing period of 12 months suggesting that the repartitioning process was not an infinite source. HOC availability after the 12-month post-treatment mixing for the sorbent-treated sediment was 53–97% lower than that of the untreated sediment because of the combined effect of HOC mass removal from sediment (with the sorbent) and incomplete recovery of available HOC fraction in the sorbent-treated sediment.

The immobilization effectiveness between Pb and phosphorus in soil varies with soil types. To clarify the effect of phosphate on the availability of Pb in agricultural soil, a culture experiment with three types of paddy soil was performed with potassium dihydrogen phosphate (KDP) added. EDTA, DGT and in-situ solution extraction methods were used to represent different available Pb content. Results showed that the concentration of EDTA-Pb in HN soil was slightly elevated after exogenous KDP added. The supplement of 300 mg/kg KDP significantly increased the content of soluble Pb in both acid silty clay loam soil and neutral silty loam soil (increased by 104.65% and 65.12%, respectively). However, there was no significant influence of KDP on the concentration of DGT extracted Pb. XANES results showed that Pb(OH)2, PbHPO4, humic acid-Pb and GSH-Pb were the major speciation of Pb in soil colloids. The proportion of Pb(OH)2 and humic acid-bounded Pb in soil colloids were elevated after exogenous KDP added. Our results indicated that there was a mobilization effect of KDP on Pb by increasing the amount of colloidal Pb in soil solution, especially in acid silty clay loam paddy soil. Such colloid-facilitated transport might promote the uptake of Pb in rice and pose a potential threat to human health.

Phytoextraction is one of the most promising technologies for the remediation of metal contaminated soils. Changes in soil metal availability during phytoremediation have direct effects on removal efficiency and can also illustrate the interactive mechanisms between hyperaccumulators and metal contaminated soils. In the present study the changes in metal availability, desorption kinetics and speciation in four metal-contaminated soils during repeated phytoextraction by the zinc/cadmium hyperaccumulator Sedum plumbizincicola (S. plumbizincicola) over three years were investigated by chemical extraction and the DGT-induced fluxes in soils (DIFS) model. The available metal fractions (i.e. metal in the soil solution extracted by CaCl2 and by EDTA) decreased greatly by >84% after phytoextraction in acid soils and the deceases were dramatic at the initial stages of phytoextraction. However, the decreases in metal extractable by CaCl2 and EDTA in calcareous soils were not significant or quite low. Large decreases in metal desorption rate constants evaluated by DIFS were found in calcareous soils. Sequential extraction indicated that the acid-soluble metal fraction was easily removed by S. plumbizincicola from acid soils but not from calcareous soils. Reducible and oxidisable metal fractions showed discernible decreases in acid and calcareous soils, indicating that S. plumbizincicola can mobilize non-labile metal for uptake but the residual metal cannot be removed. The results indicate that phytoextraction significantly decreases metal availability by reducing metal pool sizes and/or desorption rates and that S. plumbizincicola plays an important role in the mobilization of less active metal fractions during repeated phytoextraction.