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Evaluation of environmental risks posed by potentially hazardous substances requires achieving a balance between over‐ and underprotection, i.e., between societal benefits posed by the use of particular substances and their potential risks. Uncertainty (e.g., only laboratory data may be available, field or epidemiological data may be limited and less than clear‐cut, etc.) will always exist and is often conservatively dealt with by the use of so‐called “safety” or “uncertainty” factors, some of which remain relatively little changed since their origin in 1945. Extrapolations involving safety factors for both aquatic and terrestrialenvironments include inter‐ and intraspecies, acute‐to‐chronic, lowest‐ to no‐observed‐effect concentration (NOEC), and laboratory‐to‐field extrapolation (e.g., extrapolation of laboratory results to the field). To be realistic, such extrapolations need to have a clear relationship with the field effect of concern and to be based on good science. The end result is, in any case, simply an estimate of a field NOEC, not an actual NOEC. Science‐based versus policy‐driven safety factors, including their uses and limitations, are critically examined in the context of national and international legislation on risk assessment. Key recommendations include providing safety factors as a potential threshold effects range instead of a discrete number and using experimental results rather than defaulting to safety factors to compensate for lack of information. This latter recommendation has the additional value of rendering safety factors predictive rather than simply protective. We also consider the so‐called “Precautionary Principle”, which originated in 1980 and effectively addresses risk by proposing that the safety factor should be infinitely large.

Major metal-binding phases in the aerobic layer of sediments are iron and manganese oxyhydroxides (FeOOH and MnOOH) and particulate organic carbon (POC). The acid-volatile sulfide (AVS) model proposed for predicting nontoxicity from metals-contaminated sediments is only applicable to anaerobic sediments. In other sediments, normalization by POC or FeOOH and MnOOH may be predictive, but binding constants are not well understood. Metal mobilization is enhanced by ligand complexation and oxidation of anaerobic sediments. Free metal ion is the most bioavailable species, but other labile metal species and nonchemical variables also determine metal bioavailability; biotic site binding models have shown promise predicting toxicity for systems of differing chemistry. Hazard identification and ecological risk assessment (ERA) depend on determining bioavailability, from water (overlying, interstitial) and food, which can be done prospectively (e.g., normalized sediment chemistry, laboratory bioassays) or retrospectively (e.g., in situ bioassays, field studies). ERA of sediment-bound metals requires primary emphasis on toxicity and consideration of the three separate transformation processes for metals in the aquatic environment, the differences between essential and nonessential metals, the complex interactions that control bioavailability, adaptation, which may occur relatively simply without appreciable cost to the organism, weight of evidence, and causality.

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Major metal-binding phases in the aerobic layer of sediments are iron and manganese oxyhydroxides (FeOOH and MnOOH) and particulate organic carbon (POC). The acid-volatile sulfide (AVS) model proposed for predicting nontoxicity from metals-contaminated sediments is only applicable to anaerobic sediments. In other sediments, normalization by POC or FeOOH and MnOOH may be predictive, but binding constants are not well understood. Metal mobilization is enhanced by ligand complexation and oxidation of anaerobic sediments. Free metal ion is the most bioavailable species, but other labile metal species and nonchemical variables also determine metal bioavailability; biotic site binding models have shown promise predicting toxicity for systems of differing chemistry. Hazard identification and ecological risk assessment (ERA) depend on determining bioavailability, from water (overlying, interstitial) and food, which can be done prospectively (e.g., normalized sediment chemistry, laboratory bioassays) or retrospectively (e.g., in situ bioassays, field studies). ERA of sediment-bound metals requires primary emphasis on toxicity and consideration of the three separate transformation processes for metals in the aquatic environment, the differences between essential and nonessential metals, the complex interactions that control bioavailability, adaptation, which may occur relatively simply without appreciable cost to the organism, weight of evidence, and causality

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