Comparative assessment of the fate and toxicity of chemically and biologically synthesized silver nanoparticles to juvenile clams.

Nanoparticles (NPs) can be produced via physical, chemical, or biological approaches. Yet, the impact of the synthesis approaches on the environmental fate and effects of NPs is poorly understood. Here, we synthesized AgNPs through chemical and biological approaches (cit-AgNPs and bio-AgNPs), characterized their properties, and toxicities relative to commercially available Ag nanopowder (np-AgNPs) to the clam Mercenaria mercenaria. The chemical synthesis is based on the reduction of ionic silver using sodium borohydride as a reducing agent and trisodium citrate as a capping agent. The biological synthesis is based on the reduction of ionic silver using biomolecules extracted from an atoxigenic strain of a filamentous fungus Aspergillus parasiticus. The properties of AgNPs were determined using UV-vis, dynamic light scattering, laser Doppler electrophoresis, (single particle)-inductively coupled plasma-mass spectroscopy, transmission electron microscopy, and asymmetric flow-field flow fractionation. Both chemical and biological synthesis approaches generated spherical AgNPs. The chemical synthesis produced AgNPs with narrower size distributions than those generated through biological synthesis. The polydispersity of bio-AgNPs decreased with increases in cell free extract (CFE):Ag ratios. The magnitude of the zeta potential of the cit-AgNPs was higher than those of bio-AgNPs. All AgNPs formed aggregates in the test media i.e., natural seawater. Based on the same total Ag concentrations, all AgNPs were less toxic than AgNO3. The toxicity of AgNPs toward the juvenile clam, Mercenaria mercenaria, decreased following the order np-AgNPs > cit-AgNPs > bio-AgNPs. Expressed as a function of dissolved Ag concentrations, the toxicity of Ag decreased following the order cit-AgNPs > bio-AgNPs > AgNO3 ~ np-AgNPs. Therefore, the toxicity of AgNP suspensions can be attributed to a combined effect of dissolved and particulate Ag forms. These results indicate that AgNP synthesis methods determine their environmental and biological behaviors and should be considered for a more comprehensive environmental risk assessment of AgNPs.