Particle size of biochar significantly regulates the chemical speciation, transformation, and ecotoxicity of cadmium in biochar.

The pyrolysis of biomass containing excessive heavy metals is likely to produce heavy metal contaminated biochar (BC). Although multiple lines of evidence indicate that higher charring temperature leads to enhanced immobilization of heavy metals in BC, we find that particle size could also play a critical role in the content of heavy metals in BC and BC ecotoxicity. Here, BC derived from cadmium (Cd) enriched rice straw was prepared at different temperatures (300-600 °C) and divided into macro-, colloidal-, and nano-sized fractions, respectively. The content and chemical forms of Cd in BC fractions as well as related algal toxicity were examined. The results show that for the same temperature BC the content of Cd followed an order of colloidal-BC > macro-BC > nano-BC; and the residual fractions of Cd significantly decreased (3.47-16.08%) while that of acid soluble and reducible fractions significantly increased (4.13-16.51% and 0.24-1.71%, respectively) with decreasing particle size of BC. Consistently, colloidal-BC exhibited the highest ecotoxicity for Scenedesmus obliquus. The acid soluble fractions of Cd in macro- and colloidal-BC played a dominating role in their algal toxicity (p < 0.05). However, the ecotoxicity of nano-BC was more dependent on the total content of Cd than specific fractions probably due to the phagocytosis by algal cells. These results indicate that the chemical forms and ecotoxicity of Cd in BC could be remarkably modified by its particle size, which has profound implications for understanding the behavior and potential risk of heavy metal contaminated BC in the environment.

Effect of root exudates on the release, surface property, colloidal stability, and phytotoxicity of dissolved black carbon.

In this study, the release of dissolved black carbon (DBC) from bulk-BC, its surface properties, colloidal stability, and oxidative stress to rice seedlings in the presence and absence of rice root exudates were compared. The bulk-BCs were prepared at 550 °C and derived from wood chips and pig manure, respectively. The release of DBC from bulk-BC was significantly enhanced (20.19-23.63%) by the introduction of root exudates, where low molecular weight organic acids played a dominating role in the dissociation of DBC from carbon skeleton. The surface properties of DBC were greatly modified by root exudates including decreases in the surface area (18.13%) and mineral contents (43.90-69.57%). The O-containing groups and graphitization were also enhanced by 11.46% and 18.65%, respectively. Meanwhile, the presence of root exudates not only reduced the colloidal stability of DBC but also lowered the intensity of free radicals (19.44-22.22%) in DBC. Consequently, the oxidative stress of DBC to rice seedlings was significantly (p < 0.05) alleviated, evidenced by reduced antioxidative enzyme activities (5.67-29.25%) and soluble protein content (15.75-46.79%) in rice plants. These results indicate that the interaction between DBC and root exudates could remarkably modify the surface properties and reactivity of DBC, which has profound implications for understanding the behavior and functions of DBC in the environment.

Photochemical Transformation and Catalytic Activity of Dissolved Black Nitrogen Released from Environmental Black Carbon.

Biomass combustion results in the formation and wide distribution of black carbon (BC) in soils, wherein the dissolved fractions are among the most active components. Although the presence of dissolved black nitrogen (DBN) in BC has been identified, its environmental behavior and implication are not understood. This study investigated the photochemical transformation and catalytic activity of DBN under simulated solar irradiation. DBN is more easily transformed than dissolved BC due to its photoactive heteroaromatic N structure, and the half-life of DBN produced at 500 °C (8.6 h) is two times shorter than that of the dissolved BC counterpart (23 h). Meanwhile, solar irradiation is favorable for the homoaggregation of DBN. During irradiation, DBN generates not only reactive oxygen species (e.g., 1O2, O2-, and •OH) but also reactive nitrogen species (mainly •ON), which account for its higher photocatalytic degradation of bisphenol A than dissolved BC. These findings shed new light on the impact of heteroatoms on the phototransformation and activity of BC as well as cycling of N in terrestrial systems.

Variety-dependent responses of rice plants with differential cadmium accumulating capacity to cadmium telluride quantum dots (CdTe QDs): Cadmium uptake, antioxidative enzyme activity, and gene expression.

The excess release of engineered nanomaterials into farmland poses a serious threat to food security. Although rice varieties exhibit substantial variation in cadmium accumulation, their responses to Cd-based nanoparticles are largely unknown. In this work, we investigated the accumulation of cadmium telluride quantum dots (CdTe QDs at 0.5, 1.0, 2.5, 5.0mg-Cd/L) in two rice varieties with different Cd accumulation capacity. It was found that 5.0mg-Cd/L of CdTe QDs had minor growth inhibition to the high-Cd-accumulating variety (T705) relative to the low-Cd-accumulating variety (X24) after 7-day exposure. The two rice varieties had comparable Cd content in roots; however, T705 exhibited higher Cd content in shoots than X24. Transmission electron and confocal laser scanning microscopic observations demonstrated that more CdTe QDs can be transported and accumulated from roots to shoots in T705. The activities and gene expression of antioxidative enzymes in leaves of T705 increased more significantly than those of X24. Our findings for the first time validated that Cd accumulation divergence exists in different rice varieties when they are exposed to Cd-based QDs, the genetic basis for which needs to be further examined.