Rami B. Naddy

The biotic ligand model: a historical overview

During recent years, the biotic ligand model (BLM) has been proposed as a tool to evaluate quantitatively the manner in which water chemistry affects the speciation and biological availability of metals in aquatic systems. This is an important consideration because it is the bioavailability and bioreactivity of metals that control their potential to cause adverse effects. The BLM approach has gained widespread interest amongst the scientific, regulated and regulatory communities because of its potential for use in developing water quality criteria (WQC) and in performing aquatic risk assessments for metals. Specifically, the BLM does this in a way that considers the important influences of site-specific water quality. This journal issue includes papers that describe recent advances with regard to the development of the BLM approach. Here, the current status of the BLM development effort is described in the context of the longer-term history of advances in the understanding of metal interactions in the environment upon which the BLM is based. Early developments in the aquatic chemistry of metals, the physiology of aquatic organisms and aquatic toxicology are reviewed first, and the degree to which each of these disciplines influenced the development of water quality regulations is discussed. The early scientific advances that took place in each of these fields were not well coordinated, making it difficult for regulatory authorities to take full advantage of the potential utility of what had been learned. However, this has now changed, with the BLM serving as a useful interface amongst these scientific disciplines, and within the regulatory arena as well. The more recent events that have led to the present situation are reviewed, and consideration is given to some of the future needs and developments related to the BLM that are envisioned. The research results that are described in the papers found in this journal issue represent a distinct milestone in the ongoing evolution of the BLM approach and, more generally, of approaches to performing ecological assessments for metals in aquatic systems. These papers also establish a benchmark to which future scientific and regulatory developments can be compared. Finally, they demonstrate the importance and usefulness of the concept of bioavailability and of evaluative tools such as the BLM.

Effect of pulse frequency and interval on the toxicity of chlorpyrifos to Daphnia magna

Due to the episodic nature in which organisms are exposed to non-point source pollutants, it is necessary to understand how they are affected by pulsed concentrations of contaminants. This is essential, as standard toxicity tests may not adequately simulate exposure scenarios for short-lived hydrophobic compounds, such as chlorpyrifos (CPF), a broad-spectrum organophosphate insecticide. Studies were conducted with 7-day old Daphnia magna for 7 days to evaluate the effect of pulse frequency and interval among multiple CPF exposures. Daphnids were exposed to a total exposure of either 12 h at 0.5 microg/l or 6 h at 1.0 microg/l nominal CPF, respectively, in all studies. For interval studies, D. magna were exposed to two pulses of CPF at each concentration, with 0-96-h intervals between pulses. For frequency studies, D. magna were exposed to each CPF concentration altering the pulse scheme by decreasing the exposure duration but increasing the number of pulses, keeping the total exposure time the same. The pulse interval between multiple pulses in these experiments was 24 h. Our results suggest that D. magna can withstand an acutely lethal CPF exposure provided that there is adequate time for recovery between exposures.

Evaluating the role of ion composition on the toxicity of copper to Ceriodaphnia dubia in very hard waters.

The mitigating effect of increasing hardness on metal toxicity is reflected in water quality criteria in the United States over the range of 25-400 mgl(-1) (as CaCO(3)). However, waters in the arid west of the US frequently exceed 400 mgl(-1) hardness, and the applicability of hardness-toxicity relationships in these waters is unknown. Acute toxicity tests with Ceriodaphnia dubia were conducted at hardness levels ranging from approximately 300 to 1,200 mgl(-1) using reconstituted waters that mimic two natural waters with elevated hardness: (1) alkaline desert southwest streams (Las Vegas Wash, NV), and (2) low alkalinity waters from a CaSO(4)-treated mining effluent in Colorado. The moderately-alkaline EPA synthetic hard water was also included for comparison. Copper toxicity did not consistently vary as a function of hardness, but likely as a function of other water quality characteristics (e.g., alkalinity or other correlated factors). The hardness equations used in regulatory criteria, therefore, may not provide an accurate level of protection against copper toxicity in all types of very hard waters. However, the mechanistic Biotic ligand model generally predicted copper toxicity within +/-2X of observed EC(50) values, and thus may be more useful than hardness for modifying water quality criteria.

The interactive toxicity of cadmium, copper, and zinc to Ceriodaphnia dubia and rainbow trout (Oncorhynchus mykiss).

Traditionally, aquatic toxicity studies examine the toxicity of a single chemical to an organism. Organisms in nature, however, may be exposed to multiple toxicants. Given this is a more realistic exposure scenario in situ, the authors sought to understand the interactive toxicity of multiple metals to aquatic organisms. The authors performed a series of studies using equitoxic mixtures of cadmium, copper, and zinc to 2 aquatic organisms, rainbow trout (Oncorhynchus mykiss) and the waterflea, Ceriodaphnia dubia. Single metal toxicity tests were conducted to determine the acute median lethal concentration (LC50) values for O. mykiss and short-term, chronic median effective concentration (EC50) values for C. dubia. All 3 metals were then combined in equitoxic concentrations for subsequent mixture studies using a toxic unit (TU) approach (i.e., 1 TU = EC50 or LC50). For C. dubia, the mixture study showed greater-than-additive effects in hard water (TU-based EC50 = 0.74 TU), but less-than-additive effects in soft water (TU-based EC50 = 1.93 TU). The mixture effects for O. mykiss showed less-than-additive effects in both hard and soft waters, with TU-based LC50 values of 2.33 total TU and 2.22 total TU, respectively. These data are useful in helping understand metal mixture toxicity in aquatic systems and indicate that although in most situations the assumption of additivity of metal mixture toxicity is valid, under certain conditions it may not be sufficiently protective.

Effects of sodium chloride on chronic silver toxicity to early life stages of rainbow trout (Oncorhynchus mykiss)

The chronic (early life stage) toxicity of silver to rainbow trout (Oncorhynchus mykiss) was determined in flow-through exposures. Rainbow trout embryos were exposed to silver (as AgNO3) from 48 h or less postfertilization to 30 d postswimup in soft water in the presence and absence of 49 mg/L of NaCl (30 mg/L of Cl). The studies determined effect levels for rainbow trout exposed throughout an extended development period and assessed possible protective effects of sodium chloride. Lowest-observed-effect concentrations were greater than 1.25 microg/L of dissolved silver for survival, mean day to hatch, mean day to swimup, and whole-body sodium content in both studies. Whole-body silver concentrations increased significantly at 0.13 microg/L of dissolved silver in unmodified water and at 1.09 microg/L of dissolved silver in amended water. The maximum-acceptable toxicant concentration for growth was greater than 1.25 microg/L of dissolved silver in unmodified water and 0.32 microg/L of dissolved silver in amended water. Whole-body silver concentrations were more sensitive than survival and growth end points in unmodified water. Interpretation of sodium chloride effects on chronic silver toxicity to rainbow trout was complicated by differences in measured effect levels that were potentially the result of strain differences between test organisms in the two studies.

Passive sampling devices for rapid determination of soil contaminant distributions

The effective remediation of contaminated waste sites requires accurate identification of chemical distributions. A rapid sampling method using passive sampling devices (PSDs) for soil contaminant characterization can provide a more thorough site assessment. We evaluated a PSD to estimate polychlorinated biphenyl (PCB) levels in contaminated soils in both laboratory and field studies. PSD sampling increased with soil analyte concentration and decreased moisture content. For PSD calibration, we compared PCB concentrations in 36 PSDs and 18 soil samples. PSD uptake and soil concentration demonstrated a linear relationship with an r2 value of 0.86 and a slope of 0.88. PSD concentrations were then used to predict soil contaminant distributions at a hazardous waste site. Predicted soil concentrations ranged from 0.01 to 200 ppm as total aroclor 1254.

Identifying the cause of toxicity in an algal whole effluent toxicity study - an unanticipated toxicant.

Toxicity was observed in whole effluent toxicity (WET) studies with the freshwater alga, Pseudokirchneriella subcapitata, in three consecutive monthly studies, (NOEC=50-75%). Toxicity was not observed to Ceriodaphnia dubia or the fathead minnow, Pimephales promelas in concurrent studies. Selected toxicity identification evaluation (TIE) tests were conducted in a tiered approach to eliminate possible toxicants and progressively identify the causative agent. Filtration following alkaline adjustment (pH 10 or 11) was effective in eliminating significant growth effects and also reduced phosphate concentration. The TIE studies confirmed that the observed effluent toxicity was caused by excess ortho-phosphate in the effluent not by overstimulation or related to unfavorable N:P ratios; but due to direct toxicity. The 96-h 25% inhibition concentration (IC25) of ortho-phosphate to P. subcapitata was 3.4 mg L⁻¹ while the maximum acceptable toxicant concentration was 4.8 mg L⁻¹. This study illustrates the value of multi-species testing and also provides an example of an effective TIE using algae identifying an unanticipated toxicant.

Effects of in situ selenium exposure and maternal transfer on survival and deformities of brown trout (Salmo trutta) fry

Offspring of wild adult brown trout exposed to a range of Se concentrations were reared in a laboratory setting to primarily assess effects on survival and deformities. Maternal whole-body Se concentrations ranged from 4.7 to 22.6 mg/kg dry weight for wild fish. Corresponding Se concentrations in embryos ranged from 6.2 to 40.3 mg/kg dry weight. Significant relationships were found between embryo and whole-body tissue concentrations. Increasing egg Se concentrations were correlated with decreasing survival; however, hatch success was not significantly correlated with increasing embryo Se. The best fit effect concentration, 10% (EC10) for survival in the hatch to swim-up period was 20.6 mg/kg dry weight, and the EC10 for hatch to test termination at 88 d was 20.5 mg/kg dry weight egg Se. The best fit model for deformities was based on a baseline-adjusted severity index and resulted in an EC10 of 21.8 mg/kg dry weight egg Se. Both the best fit model EC10s represent more sensitive values than the published range of trout species EC10s. An egg to whole-body tissue conversion factor derived from the paired data resulted in a conversion factor for brown trout of 1.46, which resulted in a whole-body tissue EC10 of 14.04 mg/kg dry weight at an egg tissue EC10 of 20.5 mg/kg dry weight. Environ Toxicol Chem 2018;37:1396-1408.