Environmental Context. The chemical speciation of trace metals greatly influences their biological effects. Nonetheless, no clear consensus currently exists as to when metal complexes are bioavailable, especially for field conditions. Recently, the USA EPA has incorporated the biotic ligand model (BLM) into their regulatory framework and many other countries are now examining the implications of following suit. This review examines the fundamental basis of the BLM in order to provide the reader with an understanding of its potential uses and limitations. The biotic ligand model is a useful construct both for predicting the effects of metals to aquatic biota and for increasing our mechanistic understanding of their interactions with biological surfaces. Since biological effects due to metals are always initiated by metal bioaccumulation, the fundamental processes underlying bio-uptake are examined in this review. The model assumes that the metal of interest, its complexes, and metal bound to sensitive sites on the biological surface are in chemical equilibrium. Therefore, many of the equilibrium constants required for the model have been compiled and their methods of determination evaluated. The underlying equilibrium assumption of the BLM is also examined critically. In an attempt to identify which conditions are appropriate for its application, several documented examples of failures of the BLM are discussed. Finally, the review is concluded by identifying some important future research directions.

Silver, ZnO and CuO nanoparticles (NPs) are increasingly used as biocides. There is however increasing evidence of their threat to "non-target" organisms. In such a context, the understanding of the toxicity mechanisms is crucial for both the design of more efficient nano-antimicrobials, i.e. for "toxic by design" and at the same time for the design of nanomaterials that are biologically and/or environmentally benign throughout their life-cycle (safe by design). This review provides a comprehensive and critical literature overview on Ag, ZnO and CuO NPs' toxicity mechanisms on the basis of various environmentally relevant test species and mammalian cells in vitro. In addition, factors modifying the toxic effect of nanoparticles, e.g. impact of the test media, are discussed. Literature analysis revealed three major phenomena driving the toxicity of these nanoparticles: (i) dissolution of nanoparticles, (ii) organism-dependent cellular uptake of NPs and (iii) induction of oxidative stress and consequent cellular damages. The emerging information on quantitative structure-activity relationship modeling of nanomaterials' toxic effects and the challenges of extrapolation of laboratory results to the environment are also addressed.

Nanotechnology has revolutionised many areas of modern life, technology and research, which is reflected in the steadily increasing global demand for and consumption of engineered nanomaterials and the inevitable increase of their release into the environment by human activity. The overall long-term impact of engineered nanomaterials on ecosystems is still unknown. Various inorganic nanoparticles have been found to exhibit bactericidal properties and cause growth inhibition in model aquatic microalgae, but the mechanisms of toxicity are not yet fully understood. The causal link between particle properties and biological effects or reactive oxygen species generation is not well established and represents the most eminent quest of nanoecotoxicological investigation. In this review, the current mechanistic understanding of the toxicity of inorganic metal and metal oxide engineered nanomaterials towards bacterial and aquatic microalgal model organisms based on the paradigm of oxidative stress is presented along with a detailed compilation of available literature on the major toxicity factors and research methods.

Several washing agents (EDTA, CDTA, NTA, 8 HQS, Ti‐EDTA‐citrate, Ca²⁺, and H⁺) were tested for their ability to extract adsorbed metal from biological surfaces to distinguish between internalized and total cellular metal (Pb, Ni, Cd, Zn, and Cu) for a green alga, Chlorella kesslerii. Although a single extraction protocol cannot be provided that would be acceptable for all biological species and metals, several guidelines are proposed that should facilitate the interpretation of metal bioaccumulation data. It was shown that for the studied metals, a thermodynamic explanation was generally sufficient to explain the metal extraction results. At pH 6.0, a solution of 5 × 10⁻³ M ethylenediaminetetraacetic acid (EDTA) was an acceptable washing agent in most cases, whereas Ca or proton exchange solutions did not appear to quantitatively remove adsorbed metals. Conditions of ligand excess could be attained with relatively small concentrations of added ligand, effectively minimizing potential damage to the organism, including modifications in membrane permeability. Potential deleterious effects of the wash agents were verified. For example, a Ti‐EDTA‐citrate or an EDTA wash at high concentrations resulted in perturbations of algal membrane permeability. In spite of potential difficulties interpreting extraction data, the usefulness of the extraction protocols was clearly demonstrated for several organisms.