Kay T. Ho

Issues in sediment toxicity and ecological risk assessment

This paper is based on a facilitated Workshop and Roundtable Discussion of key issues in sediment toxicology and ecological risk assessment (ERA) as applied to sediments that was held at the Conference on Dredged Material Management: Options and Environmental Considerations. The issues addressed included how toxicity is defined and perceived, how it is measured, and how it should be used within the context of ERA to support management decisions. The following conclusions were reached regarding scientific considerations of these issues. Toxicity is a measure of hazard and not a risk per se. Thus, toxicity testing is a means but not the end to understand risks of sediments. Toxicity testing cannot presently be replaced by chemical analyses to define hazard. Toxicity test organisms need to be appropriate to the problem being addressed, and the results put into context relative to both reference and baseline comparisons to understand hazard. Use of toxicity tests in sediment ERAs requires appropriate endpoints and risk hypotheses, considering ecological not just statistical significance, and recognizing that hazard does not equate to risk. Toxicity should be linked to population and community response to support decision-making, assessing possible genotypic adaptations that can influence risk estimates, and addressing uncertainty. Additionally, several key scientific issues were identified to improve future sediment ERAs, including the need to improve basic understanding of ecological mechanisms and processes, recognition of variability in the assessment process, and an improved focus and ability to assess risks to populations and communities.

An overview of toxicant identification in sediments and dredged materials

The identification of toxicants affecting aquatic benthic systems is critical to sound assessment and management of our nations waterways. Identification of toxicants can be useful in designing effective sediment remediation plans and reasonable options for sediment disposal. Knowledge of which contaminants affect benthic systems allows managers to link pollution to specific dischargers and prevent further release of toxicant(s). In addition, identification of major causes of toxicity in sediments may guide programs such as those developing environmental sediment guidelines and registering pesticides, while knowledge of the causes of toxicity which drive ecological changes such as shifts in benthic community structure would be useful in performing ecological risk assessments. To this end, the US Environmental Protection Agency has developed tools (toxicity identification and evaluation (TIE) methods) that allow investigators to characterize and identify chemicals causing acute toxicity in sediments and dredged materials. To date, most sediment TIEs have been performed on interstitial waters. Preliminary evidence from the use of interstitial water TIEs reveals certain patterns in causes of sediment toxicity. First, among all sediments tested, there is no one predominant cause of toxicity; metals, organics, and ammonia play approximately equal roles in causing toxicity. Second, within a single sediment there are multiple causes of toxicity detected; not just one chemical class is active. Third, the role of ammonia is very prominent in these interstitial waters. Finally, if sediments are divided into marine or freshwater, TIEs perforMed on interstitial waters from freshwater sediments indicate a variety of toxicants in fairly equal proportions, while TIEs performed on interstitial waters from marine sediments have identified only ammonia and organics as toxicants, with metals playing a minor role. Preliminary evidence from whole sediment TIEs indicates that organic compounds play a major role in the toxicity of marine sediments, with almost no evidence for either metal or ammonia toxicity. However, interpretation of these results may be skewed because only a small number of interstitial water (n = 13) and whole sediment (n = 5) TIEs have been completed. These trends may change as more data are collected.

Effects-directed analysis (EDA) and toxicity identification evaluation (TIE): Complementary but different approaches for diagnosing causes of environmental toxicity.

Currently, 2 approaches are available for performing environmental diagnostics on samples like municipal and industrial effluents, interstitial waters, and whole sediments to identify anthropogenic contaminants causing toxicological effects. One approach is toxicity identification evaluation (TIE), which was developed primarily in North America to determine active toxicants to whole-organism endpoints. The second approach is effects-directed analysis (EDA), which has origins in both Europe and North America. Unlike TIE, EDA uses primarily in vitro endpoints with an emphasis on organic contaminants as the cause of observed toxicity. The 2 approaches have fundamental differences that make them distinct techniques. In EDA, the sophisticated and elegant fractionation and chemical analyses performed to identify the causes of toxicity with a high degree of specificity often compromise contaminant bioavailability. In contrast, in TIE, toxicant bioavailability is maintained and is considered critical to accurately identifying the causes of environmental toxicity. However, maintaining contaminant bioavailability comes with the cost of limiting, at least until recently, the use of the types of sophisticated fractionation and elegant chemical analyses that have resulted in the high specificity of toxicant diagnosis performed in EDA. The present study provides an overview of each approach and highlights areas where the 2 approaches can complement one another and lead to the improvement of both.

Use of powdered coconut charcoal as a toxicity identification and evaluation manipulation for organic toxicants in marine sediments

We report on a procedure using powdered coconut charcoal to sequester organic contaminants and reduce toxicity in sediments as part of a series of toxicity identification and evaluation (TIE) methods. Powdered coconut charcoal (PCC) was effective in reducing the toxicity of endosulfan-spiked sediments by 100%. Powdered coconut charcoal also was effective in removing almost 100% of the toxicity from two field sediments contaminated with polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). Powdered coconut charcoal did not change the toxicity of ammonia or metal-spiked sediments; however, there was some quantitative reduction in the concentrations of free metals (element specific) in metal-spiked sediments. Powdered coconut charcoal is an effective, relatively specific method to sequester and remove toxicity from sediments contaminated with organic contaminants.

Removal of ammonia toxicity in marine sediment TIEs: a comparison of Ulva lactuca, zeolite and aeration methods

Toxicity Identification Evaluations (TIEs) can be used to determine the specific toxicant(s), including ammonia, causing toxicity observed in marine sediments. Two primary TIE manipulations are available for characterizing and identifying ammonia in marine sediments: Ulva lactuca addition and zeolite addition. In this study, we compared the efficacy of these methods to (1) remove NH(x) and NH(3) from overlying and interstitial waters and (2) reduce toxicity to the amphipod Ampelisca abdita and mysid Americamysis bahia using both spiked and environmentally contaminated sediments. The utility of aeration for removing NH(x) and NH(3) during a marine sediment TIE was also evaluated preliminarily. In general, the U. lactuca and zeolite addition methods performed similarly well at removing spiked NH(x) and NH(3) from overlying and interstitial waters compared to an unmanipulated sediment. Toxicity to the amphipod was reduced approximately the same by both methods. However, toxicity to the mysid was most effectively reduced by the U. lactuca addition indicating this method functions best with epibenthic species exposed to ammonia in the water column. Aeration removed NH(x) and NH(3) from seawater when the pH was adjusted to 10; however, very little ammonia was removed at ambient pHs ( approximately 8.0). This comparison demonstrates both U. lactuca and zeolite addition methods are effective TIE tools for reducing the concentrations and toxicity of ammonia in whole sediment toxicity tests.

Bioaccumulation and toxicity of single-walled carbon nanotubes to benthic organisms at the base of the marine food chain

As the use of single-walled carbon nanotubes (SWNTs) increases over time, so does the potential for environmental release. This research aimed to determine the toxicity, bioavailability, and bioaccumulation of SWNTs in marine benthic organisms at the base of the food chain. The toxicity of SWNTs was tested in a whole sediment exposure with the amphipod Ampelisca abdita and the mysid Americamysis bahia. In addition, SWNTs were amended to sediment and/or food matrices to determine their bioavailability and bioaccumulation through these routes in A. abdita, A. bahia, and the estuarine amphipod Leptocheirus plumulosus. No significant mortality to any species via sediment or food matrices was observed at concentrations up to 100 ppm. A novel near-infrared fluorescence spectroscopic method was utilized to measure and characterize the body burdens of pristine SWNTs in nondepurated and depurated organisms. We did not detect SWNTs in depurated organisms but quantified them in nondepurated A. abdita fed SWNT-amended algae. After a 28-d exposure to [(14) C]SWNT-amended sediment (100 µg/g) and algae (100 µg/g), [(14) C]SWNT was detected in depurated and nondepurated L. plumulosus amphipods at 0.50 µg/g and 5.38 µg/g, respectively. The results indicate that SWNTs are bioaccessible to marine benthic organisms but do not appear to accumulate or cause toxicity.

pH dependent toxicity of five metals to three marine organisms

The pH of natural marine systems is relatively stable; this may explain why metal toxicity changes with pH have not been well documented. However, changes in metal toxicity with pH in marine waters are of concern in toxicity testing. During porewater toxicity testing pH can change 1–2 units as porewater is transferred from in situ to a test container. These changes in pH may alter metal toxicity. Also, deliberately altering the sample pH is an important toxicity identification and evaluations (TIE) manipulation designed to detect changes in ammonia toxicity. If altering pH also changes metal toxicity, this may confound interpretation of TIE manipulation results. This study demonstrates that alteration of pH can also change the toxicity of Cu, Cd, Ni, Pb, and Zn to Mysidopsis bahia (mysid), Ampelisca abdita (amphipod) and Vibrio fischerii [Microtox solid phase test (MSP)]. Changes in toxicity with respect to pH were metal and organism specific with the following trends. For the MSP assay, as pH decreased there was a decrease in toxicity for Pb, Ni, Cd, and Zn and an increase in toxicity for Cu. For mysids, as pH decreased, there was a decrease in toxicity for Pb and an increase in toxicity for Cu and Ni. For amphipods, Cu was the only metal that showed decreased toxicity with decreasing pH; the toxicity of all other metals for amphipods remained constant. Results of this study indicate changes in metal toxicity with respect to pH must be considered for porewater testing and TIE interpretation. ©1999 John Wiley & Sons, Inc. Environ Toxicol 14: 235–240, 1999

Toxicity characterization of an industrial and a municipal effluent discharging to the marine environment

Toxicity Identification Evaluation (TIE) methods have proven very useful in characterizing, identifying and confirming toxicants in environmental samples. This report describes the characterization of toxicants present in two effluents, industrial and municipal, discharged into the marine environment. A toxicity characterization consists of dividing an effluent sample into several relatively unique chemical fractions. Manipulations used to generate these fractions include aeration, filtration, chelation, oxidant reduction, reverse phase chromatography, and graduated pH adjustments. Marine toxicity tests used include mysids (Mysidopsis bahia), fish (Menidia beryllina and Cyprinodon variegatus), macroalga (Champia parvula) and sea urchins (Arbacia punctulata). Results of this TIE demonstrated that both effluents contained toxicity predominantly due to metals and organic contaminants. Ammonia toxicity in the municipal effluent was sample dependent. This study illustrates that the use of marine toxicity tests, TIE procedures and historical data can be combined to better understand the nature of toxicity discharged to the marine environment.

Stability and aggregation of silver and titanium dioxide nanoparticles in seawater: Role of salinity and dissolved organic carbon

The behavior and fate of nanoparticles (NPs) in the marine environment are largely unknown and potentially have important environmental and human health implications. The aggregation and fate of NPs in the marine environment are greatly influenced by their interactions with seawater and dissolved organic carbon (DOC). In the present study, the stability and aggregation of 30-nm-diameter silver nanoparticles (AgNPs) capped with citrate and polyvinylpyrrolidone (PVP; AgNP-citrate and AgNP-PVP) and 21-nm-diameter titanium dioxide (TiO(2)) NPs as affected by seawater salinity and DOC were investigated by measuring hydrodynamic diameters and zeta potentials. The added DOC (in humic acid form) stabilized the 3 types of NPs when the seawater salinities were ≤5 parts per thousand (ppt), but the stabilizing effect of DOC was reduced by a higher salinity (e.g., 30 ppt). In addition, AgNP-PVP was more stable than AgNP-citrate in seawater, indicating that surface capping agents and stabilization mechanisms govern the stability and aggregation of NPs. Statistical analysis showed that salinity is the most dominant influence on the stability and aggregation of AgNPs and TiO(2) NPs, followed by DOC. These findings expand our knowledge on the behavior of AgNPs and TiO2 NPs in seawater and indicate that the fate of these NPs will be primarily to aggregate in the water column, precipitate, and accumulate in sediments following release into the marine environment.

Effects of triclosan on marine benthic and epibenthic organisms

Triclosan is an antimicrobial compound that has been widely used in consumer products such as toothpaste, deodorant, and shampoo. Because of its widespread use, triclosan has been detected in various environmental media, including wastewater, sewage sludge, surface waters, and sediments. Triclosan is acutely toxic to numerous aquatic organisms, but very few studies have been performed on estuarine and marine benthic organisms. For whole sediment toxicity tests, the sediment-dwelling estuarine amphipod, Ampelisca abdita, and the epibenthic mysid shrimp, Americamysis bahia, are commonly used organisms. In the present study, median lethal concentration values (LC50) were obtained for both of these organisms using water-only and whole sediment exposures. Acute 96-h water-only toxicity tests resulted in LC50 values of 73.4 and 74.3 µg/L for the amphipod and mysid, respectively. For the 7-d whole sediment toxicity test, LC50 values were 303 and 257 mg/kg (dry wt) for the amphipod and mysid, respectively. Using equilibrium partitioning theory, these whole sediment values are equivalent to interstitial water LC50 values of 230 and 190 µg/L for the amphipod and mysid, respectively, which are within a threefold difference of the observed 96-h LC50 water-only values. Triclosan was found to accumulate in polychaete tissue in a 28-d bioaccumulation study with a biota-sediment accumulation factor of 0.23 kg organic carbon/kg lipid. These data provide some of the first toxicity data for triclosan with marine benthic and epibenthic species while also indicating a need to better understand the effects of other forms of sediment carbon, triclosan ionization, and organism metabolism of triclosan on the chemicals behavior and toxicity in the aquatic environment.