Speciation, bioaccumulation, and toxicity of the newly deposited atmospheric heavy metals in soil-earthworm (Eisenia fetida) system near a large copper smelter.

The speciation, bioaccumulation, and toxicity of the newly deposited atmospheric heavy metals in the soil-earthworm (Eisenia fetida) system were investigated by a fully factorial atmospheric exposure experiment using soils exposed to 0.8-year and 1.8-year atmospheric depositions. The results shown that the newly deposited metals (Cu, Cd, and Pb) primarily accumulated in the topsoil (0-6 cm) and were present as the highly bioavailable speciation. They can migrate further to increase the concentrations of Cu, Cd, and Pb in soil solution of the deeper layer (at 10 cm) by 12 %-436 %. Earthworms tended to preferentially accumulate the newly deposited metals, which contributed 10 %-61 % of Cu, Cd, and Pb in earthworms. Further, for the unpolluted and moderately polluted soils, the newly deposited metals induced the significant oxidative stress in earthworms, resulting in significant increases in antioxidant enzyme activities (SOD, CAT, and GSH-Px). No significant differences were observed in the levels of heavy metals in soil solutions, bioaccumulation, and enzyme activities in earthworms exposed to 0.8-year and 1.8-year depositions, indicating the bioavailability of atmospheric metals deposited into soils was rapidly decreased with time. This study highlights the high bioaccumulation and toxicity of heavy metals to earthworm from the new atmospheric deposition during the earthworm growing period.

Impacts of atmospheric deposition on the heavy metal mobilization and bioavailability in soils amended by lime.

Atmospheric deposition is an important source of heavy metal in agricultural soils, but there is limited research on the mobility of these metals in soil and their impact on soil amendment. Here, we performed a dust incubation experiment in soils in the laboratory and a factorial transplant experiment at three field sites with a gradient of atmospheric deposition to examine the impacts of atmospherically deposited heavy metals (Cu, Cd, and Pb) on the mobility and bioavailability in soils with and without lime applications. Results showed that the atmospherically deposited heavy metals showed high mobility and were primarily presented in the soluble ionic fractions in the wet part and acid-exchangeable and reducible fractions in the dry part of atmospheric deposition. Atmospheric dust addition caused the 2p3/2 and 2p1/2 electrons of Cu atoms in uncontaminated soils to transition the 3d vacant states, resulting in similar copper absorption peaks as atmospheric particles by the observation of X-ray absorption near-edge spectroscopy (XANES). In the field, atmospheric deposition can only increase the mobile fractions in the surface soils, but not in the deeper layers. However, the deposition can increase the soluble and diffusive gradients in thin films (DGT)-measured bioavailable fractions in profile along with the soil depth. Lime applications cannot significantly reduce the mobile fractions of heavy metals in the surface soils exposed to atmospheric deposition, but significantly reduce the heavy metal concentrations in soil solutions and the DGT-measured bioavailable concentrations, particularly in the deeper layer (6-10 cm). The major implication is that atmospherically deposited heavy metals can significantly increase their bioavailable concentrations in the plough horizon of soil and constrain the effects of soil amendments on heavy metal immobilization, thereby increasing the risks of crop uptake.

Stable Isotope Ratios Trace the Rice Uptake of Cadmium from Atmospheric Deposition via Leaves and Roots.

Cadmium (Cd) stable isotopes provide a novel technique to investigate the fate of Cd in the environment, but challenges exist for tracing the sources in the plants. We performed individual rice leaf and root exposures to dry and wet deposition using customized open-top chambers (OTCs) in the greenhouse and in the field next to a smelter, respectively. The field experiment also included a control without Cd deposition and a "full" treatment. The exposure experiments and isotope signatures showed that leaves can directly take up atmospheric Cd and then translocate within rice plants to other tissues, contributing 52-70% of Cd in grains, which exceeded the contribution (30-48%) by root exposure. The Cd isotopes in leaves, nodes, internodes, and grains demonstrate that roots preferentially take up Cd from wet deposition, but leaves favor uptake of Cd from dry deposition. The Cd uptake by leaves is redistributed via nodes, allowing for upward transport to the grains but preventing downward transport to the roots. Leaves favor uptake of heavy isotopes from atmospheric deposition (ΔCd114/110Leaf-Dust: 0.10 ± 0.02‰) but retain light isotopes and transport heavy isotopes to the nodes and further to grains. These findings highlight the contribution of atmospheric deposition to rice and Cd isotopes as a useful tracer for quantifying sources in plants when different isotopic compositions are in sources.

Machine learning method for predicting cadmium concentrations in rice near an active copper smelter based on chemical mass balance.

Identification the sources of heavy metals can effectively control and prevent agricultural soil pollution. Here we performed a three-year mass balance study along a gradient of soil pollution near a smelter to quantify the potential contribution and net cadmium (Cd) fluxes and predict Cd concentration in rice grains by multiple regression (MR) and back propagation (BP) neural network. The Cd inputs were mainly from the irrigation water (54.6-60.8%) in the moderately polluted and background sites but from atmospheric deposition (90.9%) in the highly polluted site. The Cd outputs were mainly from the surface runoff (55.8-59.5%) in the moderately polluted and background sites, but from Sedum plumbizincicola phytoextraction (83.6%) in the highly polluted site. The soil Cd concentrations, the annual fluxes of atmospheric deposition, pesticides and fertilizers, irrigation water, surface runoff, and leaching water were selected as the dependent factors to predict Cd concentrations in rice grains. The genetic algorithms (GA)-BP neural network model gives the best prediction accuracy compared to the BP neural network model and multivariate regression analysis. The major implication is that the health risks through the consumption of rice can be rapidly assessed based on the Cd concentrations in rice grains predicted by the model.

Soil ammonium (NH4+) toxicity thresholds for restoration grass species.

Ionic rare earth mining has resulted in large amounts of bare soils, and revegetation success plays an important role in mine site rehabilitation and environmental management. However, the mining soils still maintain high NH4+ concentrations that inhibit plant growth and NH4+ toxicity thresholds for restoration plants have not been established. Here we investigated the NH4+ toxicological effects and provided toxicity thresholds for grasses (Lolium perenne L. and Medicago sativa L.) commonly used in restoration. The results show that high NH4+ concentration not only reduces the plant biomass and soluble sugars in leaves but also increases the H2O2 and MDA content, and SOD, POD, and GPX activities in roots. The SOD activities and root biomass can be adopted as the most NH4+ sensitive biomarkers. Six ecotoxicological endpoints (root biomass, soluble sugars, proline, H2O2, MDA, and GSH) of ryegrass, eight ecotoxicological endpoints (root biomass, soluble sugars, proline, MDA, SOD, POD, GPX, and GSH) of alfalfa were selected to determine the threshold concentrations. The toxicity thresholds of NH4+ concentrations were proposed as 171.9 (EC5), 207.8 (EC10), 286.6 (EC25), 382.3 (EC50) mg kg-1 for ryegrass and 171.9 (EC5), 193.2 (EC10), 234.7 (EC25), 289.6 (EC50) mg kg-1 for alfalfa. The toxicity thresholds and the relation between plant physiological indicators and NH4+ concentrations can be used to assess the suitability of the investigated plants for ecological restoration strategies.

Nodes play a major role in cadmium (Cd) storage and redistribution in low-Cd-accumulating rice (Oryza sativa L.) cultivars.

Rice cadmium (Cd) contamination is one of the critical agricultural issues. Breeding of low-Cd-accumulating cultivar is an effective approach to reduce Cd bioaccumulation in rice. To investigate the molecular mechanism underlying Cd transport in rice, the functions of nodes in Cd transport are explored. The results show that different nodes have different functions of Cd transport in the rice plant and the physiological structure of the first node under panicle (N1) determine the Cd accumulation in the brown rice. The upper nodes can redistribute the Cd transport in aboveground tissues. The expressions of Cd-efflux transporter genes (OsLCT1 and OsHMA2) located on the plasma-membrane are the main factors affecting the Cd transport form node to brown rice, which are more depended on the node functions but not the node Cd concentrations. Lower expressions of OsLCT1 and OsHMA2 in N1 result in lower Cd transport from node to brown rice. The size of vascular-bundle (VB) areas in the junctional node with the flag leaf can determine the expression of OsHMA2 and the expression of OsLCT1 positively correlated with the Cd transport ability of first node (N1). The expressions of OsVIT2 and OsABCC1 cannot allow Cd to be immobilized into the vacuoles in node. The VB structure and Cd transporter gene expression level of N1 proved that the Cd concentration of N1 can be used as an important indicator for screening low-Cd-accumulating cultivars. The major implication is that selecting or breeding cultivars with lower Cd accumulations in N1 could be an effective strategy to reduce Cd accumulation in rice grains.

Dynamic Behaviors of Newly Deposited Atmospheric Heavy Metals in the Soil-Pak Choi System.

Dynamic behaviors of the newly deposited atmospheric heavy metals in the soil-pak choi (Brassica chinensis L.) system are investigated by a fully factorial atmospheric exposure experiment using soils exposed to 0.5-year and 1.5-year atmospheric depositions. The results showed approximately 17-87%, 19-64%, and 43-84% of the Cu, Cd, and Pb in pak choi edible parts were contributed from the new depositions, respectively. For the newly deposited metals, foliar uptake was the key pathway of shoot bioaccumulation rather than from root uptake of the deposited metals in soils, resulting in no significant soil contribution differences between pak chois growing in 0.5-year and 1.5-year exposed soils. Indeed, highly bioavailable metals in atmospheric deposition significantly increased the soil plant-bioavailable Cu, Cd, and Pb fractions; however, soil aging resulted in similar percentages of the plant-bioavailable fractions in 0.5-year and 1.5-year exposed soils, which indicated the bioavailability of metals deposited into soils rapidly decreased with aging. The soil aging process of the deposited metals was well fitted with the first-order exponential decay model, and soil organic matter and clay were the major driving factors. Our findings highlight high plant bioaccumulation rates and the rapid soil aging process of newly deposited metals during the plant growth period.

Adsorption and immobilization of soil lead by two phosphate-based biochars and phosphorus release risk assessment.

Phosphorus-based biochar can effectively immobilize lead (Pb) in soils, but the effects of soluble and insoluble phosphate on the remediation efficiency of Pb and phosphorus (P) release risks remain largely unknown. In this study, three biochars were produced from reed (Phragmites australis L.) straw, potassium dihydrogen phosphate (PDP, soluble) and hydroxyapatite (HAP, insoluble) modified reed straws and marked as BC, BCP, and BCH, respectively. Pb adsorptions and immobilizations by the three biochars and their P release risks were investigated. The P release kinetics of the three biochars were all fitted with the pseudo-second-order kinetic model and the P-release capacity followed the order of BCP > BCH > BC. The sorption isotherms of Pb2+ by three biochars were better described using the Langmuir model and the maximum adsorption capacities of BCP (59.3 mg/g) and BCH (58.8 mg/g) were higher than that of BC (48.1 mg/g). However, the P concentrations remained in BCP treated solution were significantly higher than those in BCH and BC under initial Pb2+ concentrations in the ranges of 5-25 mg/L. Soil pH and available P were increased with the increasing dosage of BCP and BCH, decreasing CaCl2-extractable Pb concentrations. BCH was more effective to decrease the exchangeable Pb and transform it into iron/manganese oxides and residual fractions. Compared to BC, BCH applications in the range of 2-5% can significantly increase labile P by 15.2-17.7%, but 21.0-33.6% for BCP, indicating BCP had a higher P release risk. The major implication is that HAP-modified biochar can effectively immobilize Pb and decrease P release risks compared to soluble P-modified biochar.