Silver nanoparticles: behaviour and effects in the aquatic environment.

A eview of the literature revealed that bioaccumulation of silver in soil is rather low, even if the soil is amended with silver-containing sewage sludge. Plants grown on tailings of silver mines were found to have silver primarily in the root systems. In marine and freshwater systems, the highest reported bioconcentration factors (BCFs) were observed in algae (>105), probably because of adsorption of the dissolved silver (<0.45 μm fraction) to the cell surface. In herbivorous organisms (e.g., zooplankton and bivalves), the BCF was lower by about two orders of magnitude. Low amounts of silver were assimilated from food with no substantial biomagnification. In carnivores (e.g., fish), the BCF was also lower by one order of magnitude with no indication of biomagnification. Toxicity of silver occurs mainly in the aqueous phase and depends on the concentration of active, free Ag+ ions. Accordingly, many processes and water characteristics reduce silver toxicity by stopping the formation of free Ag+, binding Ag+, or preventing binding of Ag+ to the reactive surfaces of organisms. The solubility of a silver compound, and the presence of complexing agents (e.g., thiosulfate or chloride), dissolved organic carbon, and competing ions are important. In soil, sewage sludge, and sediments, in which silver sulfide predominates, the toxicity of silver, even at high total concentrations, is very low. The highly soluble silver thiosulfate complex has low toxicity, which can be attributed to the silver complexed by thiosulfate. Silver nitrate is one of the most toxic silver compounds. The toxic potential of silver chloride complexes in seawater is and will be an important issue for investigation. Aquatic chronic tests, long-term tests, and tests including sensitive life stages show lower toxicity thresholds (˜1 μg Ag+/L). The organisms viewed as most sensitive to silver are small aquatic invertebrates, particularly embryonic and larval stages.

https://setac.onlinelibrary.wiley.com/doi/epdf/10.1002/etc.5620180112

Bioaccumulation and toxicity of silver compounds: A review

Silver nanoparticles (Ag NPs) are widely used as antibacterial agents. This antibacterial property carries with it a potential environmental risk once these NPs are discharged into the environment. This study investigated the impact on Pseudomonas fluorescens over a 24 h exposure of well characterized Ag NPs at pH values of 6−9, in the presence and absence of Suwannee River humic acids (SRHA). Ag NPs were characterized by size, aggregation, morphology, dissolution, and surface properties under all conditions. Solubility was low (less than 2%) for all Ag NP concentrations (2−2000 ppb) and under all conditions was less than 40 ppb (0.38 μM). SRHA caused a partial disaggregation of Ag NP aggregates by nanoscale film formation, with individual NPs stabilized by charge and entropically driven steric effects. Dissolved Ag reduced bacterial growth entirely at 2000 ppb (19 μM) under all conditions and adversely affected growth at 200 ppb (1.9 μM) under some conditions, indicating some toxicity. The Ag NPs showed ...

Silver nanoparticle impact on bacterial growth: effect of pH, concentration, and organic matter.

The biotic ligand model (BLM) is a mechanistic approach that greatly improves our ability to generate site-specific ambient water quality criteria (AWQC)for metals in the natural environment relative to conventional relationships based only on hardness. The model is flexible; all aspects of water chemistry that affect toxicity can be included, so the BLM integrates the concept of bioavailability into AWQC--in essence the computational equivalent of water effect ratio (WER) testing. The theory of the BLM evolved from the gill surface interaction model (GSIM) and the free ion activity model (FIAM). Using an equilibrium geochemical modeling framework, the BLM incorporates the competition of the free metal ion with other naturally occurring cations (e.g., Ca2+, Na+, Mg2-, H+), togetherwith complexation by abiotic ligands [e.g., DOM (dissolved organic matter), chloride, carbonates, sulfide] for binding with the biotic ligand, the site of toxic action on the organism. On the basis of fish gill research, the biotic ligands appear to be active ion uptake pathways (e.g., Na+ transporters for copper and silver, Ca2+ transporters for zinc, cadmium, lead, and cobalt), whose geochemical characteristics (affinity = log K, capacity = Bmax) can be quantified in short-term (3-24 h) in vivo gill binding tests. In general, the greater the toxicity of a particular metal, the higher the log K. The BLM quantitatively relates short-term binding to acute toxicity, with the LA50 (lethal accumulation) being predictive of the LC50 (generally 96 h for fish, 48 h for daphnids). We critically evaluate currently available BLMs for copper, silver, zinc, and nickel and gill binding approaches for cadmium, lead, and cobalt on which BLMs could be based. Most BLMs originate from tests with fish and have been recalibrated for more sensitive daphnids by adjustment of LA50 so as to fit the results of toxicity testing. Issues of concern include the arbitrary nature of LA50 adjustments; possible mechanistic differences between daphnids and fish that may alter log K values, particularly for hardness cations (Ca2+, Mg2+); assumption of fixed biotic ligand characteristics in the face of evidence that they may change in response to acclimation and diet; difficulties in dealing with DOM and incorporating its heterogeneity into the modeling framework; and the paucity of validation exercises on natural water data sets. Important needs include characterization of biotic ligand properties at the molecular level; development of in vitro BLMs, extension of the BLM approach to a wider range of organisms, to the estuarine and marine environment, and to deal with metal mixtures; and further development of BLM frameworks to predict chronic toxicity and thereby generate chronic AWQC.

Biotic Ligand Model, a Flexible Tool for Developing Site-Specific Water Quality Guidelines for Metals

Silver nanoparticles in the environment: Sources, detection and ecotoxicology.

The effects of various chemical manipulations of test water on acute toxicity of silver to fathead minnows (Pimephales promelas) were investigated. Increases in hardness and organic carbon substantially reduced toxicity. Toxicity was also inversely related to pH and alkalinity when these parameters were jointly changed by addition of strong acid or base. The addition of 2 meq/L sodium sulfate had no significant effects, but the addition of 0.2 meq/L sodium chloride increased toxicity, perhaps related to the formation of the dissolved AgCl0 complex. We also evaluated the effects of static versus flow-through test conditions, feeding during exposure, and aging of test solutions before exposure on the acute toxicity of silver to fathead minnows and Daphnia magna. Static conditions and feeding reduced toxicity, likely as a result of accretion of organic carbon. Aging of test solutions had little effect. For both juvenile fathead minnows and D. magna, silver was much less toxic in water from the St. Louis River than in our normal laboratory water, presumably because of the much higher organic carbon content of the river water. This study identified some aspects of test conditions that are important in assessing the risk of silver to aquatic biota, but improved assessments will require information for more conditions, species, and endpoints. More importantly, if toxicity test results are to be extrapolated among waters with different chemistries, adequate characterization of the chemical speciation of silver and a better understanding of the mechanisms of silver toxicity and its relationship to silver speciation and other chemical factors are needed.

Effects of laboratory test conditions on the toxicity of silver to aquatic organisms

1Center for Lake Superior Environmental Studies, University of Wisconsin-Superior, Superior, Wisconsin 54880 and 2Environmental Research Laboratory-Duluth, U.S. Environmental Protection Agency, Duluth, Minnesota 55804 3,4-Dichloroaniline (3,4-DCA) is a chemical which may enter surface waters as a contaminant in applications of agricultural herbicides, as a metabolite of several herbicides, or in industrial effluents from dye manufacturing plants. 3,4-DCA is an intermediate in the synthesis of certain urea and acylanilide herbicides, such as diuron, linuron, neburon, and propanil (DiMuccio et al. 1984). These herbicides are degraded to 3,4-DCA by microorganisms in the soil or water (Bartha and Pramer 1967; Deuel et al. 1977; Ei-Dib and Aly 1976).

Sandra L. Harting

Papers

Effects of laboratory test conditions on the toxicity of silver to aquatic organisms

Toxicity of 3,4-dichloroaniline to fathead minnows, Pimephales promelas, in acute and early life-stage exposures.

Toxicity of phenanthrene to several freshwater species