Next-Generation Complex Metal Oxide Nanomaterials Negatively Impact Growth and Development in the Benthic Invertebrate Chironomus riparius upon Settling

Abstract

Most studies of nanomaterial environmental impacts have focused on relatively simple first-generation nanomaterials, including metals or metal oxides (e.g., Ag, ZnO) for which dissolution largely accounts for toxicity. Few studies have considered nanomaterials with more complex compositions, such as complex metal oxides, which represent an emerging class of next-generation nanomaterials used in commercial products at large scales. Importantly, many nanomaterials are not colloidally stable in aqueous environments and will aggregate and settle, yet most studies use pelagic rather than benthic-dwelling organisms. Here we show that exposure of the model benthic species Chironomus riparius to lithium cobalt oxide (Li x Co1–x O2, LCO) and lithium nickel manganese cobalt oxide (Li x Ni y Mn z Co1–y–z O2, NMC) at 10 and 100 mg·L–1 caused 30–60% declines in larval growth and a delay of 7–25 d in adult emergence. A correlated 41–48% decline in larval hemoglobin concentration and related gene expression changes suggest a potential adverse outcome pathway. Metal ions released from nanoparticles do not cause equivalent impacts, indicating a nanospecific effect. Nanomaterials settled within 2 days and indicate higher cumulative exposures to sediment organisms than those in the water column, making this a potentially realistic environmental exposure. Differences in toxicity between NMC and LCO indicate compositional tuning may reduce material impact.

Environmental impacts, pollution sources and pathways of spent lithium-ion batteries

“…Chironomus riparius 253 by inhibiting growth and development. The increased toxicity of these materials was associated with quick sedimentation of nanoparticles and thus faster interaction with benthic organisms.…”

Nanoparticle-Biological Interactions in a Marine Benthic Foraminifer

“…Smaller particles are commonly more toxic than larger ones due to their ability to pass biological barriers, bioaccumulate and affect metabolism 27–29 . Most studies of the impacts of ENM use pelagic rather than benthic-dwelling organisms 30 . The uptake of NP by benthic invertebrates serving as food for higher trophic-level organisms may promote transfer of ENM through the food web 31 .…”

First-Principles and Thermodynamics Comparison of Compositionally-Tuned Delafossites: Cation Release from the (001) Surface of Complex Metal Oxides

“…12,13 While compositionally tuned variants of LCO and NMC have been advantageous because of their improved properties and ease of manufacturing, they also contain transition metals whose release has been shown to be potentially toxic to a wide variety of organisms. [14][15][16][17][18][19][20][21] The proposed mechanisms of To better understand the thermodynamics of surface transformations that enable cation release, we evoke a DFT+ solvent ion model. 7,23 Our test cases included compositionally tuned variants of NMC (equistoichiometric and Mn-rich NMC) that contain multiple cations whose oxidation states depended upon atomistic composition, surface termination, and the formation of vacancies.…”