Toxicological and chemical assessment of ordinance compounds in marine sediments and porewaters.

Toxicological and chemical studies were performed with a silty and a sandy marine sediment spiked with 2,6-dinitrotoluene (2,6-DNT), 2,4,6-trinitrophenylmethylnitramine (tetryl), or 2,4,6-trinitrophenol (picric acid). Whole sediment toxicity was analyzed by the 10-day survival test with the amphipod Ampelisca abdita, and porewater toxicity tests assessed macro-algae (Ulva fasciata) zoospore germination and germling growth, sea urchin (Arbacia punctulata) embryological development, and polychaete (Dinophilus gyrociliatus) survival and reproduction. Whole sediments spiked with 2,6-DNT were not toxic to amphipods. The fine-grained sediment spiked with tetryl was also not acutely toxic. The tetryl and picric acid LC50 values in the sandy sediment were 3.24 and 144 mg/kg dry weight, respectively. The fine-grained sediment spiked with picric acid generated a U-shaped concentration-response curve in the amphipod test, with increased survival both in the lowest and highest concentration. Grain-size distribution and organic carbon content strongly influenced the behavior of ordnance compounds in spiked sediments. Very low concentrations were measured in some of the treatments and irreversible binding and biodegradation are suggested as the processes responsible for the low measurements. Porewater toxicity varied with its sedimentary origin and with ordnance compound. The sea urchin embryological development test tended to be the least sensitive. Tetryl was the most toxic chemical in all porewater tests, and picric acid the least toxic. Samples spiked with 2,6-DNT contained a degradation product identified as 2-methyl-3-nitroaniline (also known as 2-amino-6-nitrotoluene), and unidentified peaks, possibly degradation products, were also seen in some of the picric acid- and tetryl-spiked samples. Degradation products may have played a role in observed toxicity.

Influence of potentially confounding factors on sea urchin porewater toxicity tests.

The influence of potentially confounding factors has been identified as a concern for interpreting sea urchin porewater toxicity test data. The results from >40 sediment-quality assessment surveys using early-life stages of the sea urchin Arbacia punctulata were compiled and examined to determine acceptable ranges of natural variables such as pH, ammonia, and dissolved organic carbon on the fertilization and embryological development endpoints. In addition, laboratory experiments were also conducted with A. punctulata and compared with information from the literature. Pore water with pH as low as 6.9 is an unlikely contributor to toxicity for the fertilization and embryological development tests with A. punctulata. Other species of sea urchin have narrower pH tolerance ranges. Ammonia is rarely a contributing factor in pore water toxicity tests using the fertilization endpoint, but the embryological development endpoint may be influenced by ammonia concentrations commonly found in porewater samples. Therefore, ammonia needs to be considered when interpreting results for the embryological development test. Humic acid does not affect sea urchin fertilization at saturation concentrations, but it could have an effect on the embryological development endpoint at near-saturation concentrations. There was no correlation between sediment total organic carbon concentrations and porewater dissolved organic carbon concentrations. Because of the potential for many varying substances to activate parthenogenesis in sea urchin eggs, it is recommended that a no-sperm control be included with every fertilization test treatment.

Sediment quality assessment survey and toxicity identification evaluation studies in Lavaca Bay, Texas, a marine Superfund site.

A sediment quality assessment survey was conducted in Lavaca Bay, Texas, in proximity to a marine Superfund National Priority List (NPL) site. Previous studies at this site had focused primarily on the degree and extent of mercury contamination. The purpose of this survey was to determine the potential ecotoxicological impacts of contaminants, using sensitive sediment toxicity tests in conjunction with a comprehensive chemical analysis of the sediments. In addition, phase I toxicity identification evaluation (TIE) studies were conducted at several of the more toxic sites. Sea urchin (Arbacia punctulata) fertilization and embryological development tests with sediment pore water were employed to assess the toxicity of the sediments. Elevated levels of mercury were found in a number of samples as much as 10-20 times that of background. Six stations had total polycyclic aromatic hydrocarbon (PAH) concentration above the probable effect level (PEL) guideline value, and some stations had concentrations as much as 1000 times above background levels. Eighteen of the 24 stations exhibited toxicity in one of the toxicity tests, while 14 stations were toxic in both tests. A number of stations within the fish closure area exceeded 8-16 of the PEl guidelines. Both aeration and the C18 column treatments were effective in reducing toxicity from the pore water of the two stations included in the TIE. This information, in conjunction with the fact that two of the four stations with the highest mercury concentrations were not toxic, suggests that the toxicity observed in this study is primarily due to organics, probably PAHs, and not mercury. We recommend that these other contaminants of concern be considered in any remedial actions that are planned for this NPL site and that impacts on the ecosystem, as well as human health issues, also be considered.

Sediment quality triad assessment survey of the Galveston Bay, Texas system.

To characterize the quality of sediments at key sites in the Galveston Bay Estuary, sediment samples were collected concurrently for chemical and physical analyses, toxicity testing and an assessment of benthic community structure. Significant toxicity, as determined by the sea urchin (Arbacia punetulata) pore water embryological development assay, was observed at 12 of the 24 sites investigated in this study. No toxicity was observed at any of the sites with the amphipod (Grandidierella japonica) solid-phase test. There were a number of sites with elevated levels of trace metals and petroleum hydrocarbons. The chemistry, toxicity and benthic data were ranked by station and a scaled rank sum was calculated to facilitate comparisons among the stations. Five sites exhibited strong evidence of contaminant-induced degradation, while 15 stations showed no evidence of contaminant-induced degradation. At eight additional sites the sediment quality triad (SQT) data indicated that unmeasured chemicals or conditions were stressing the system. Contaminant impacts could be reduced or eliminated by alternative regulatory and management practices, including the restriction of produced water discharges into coastal estuaries and the use of dredge material disposal practices that minimize the reintroduction of sediment-associated contaminants to the bays.

Sediment toxicity identification evaluation (TIE) studies at marine sites suspected of ordnance contamination.

A sediment quality assessment survey and subsequent toxicity identification evaluation (TIE) study was conducted at several sites in Puget Sound, Washington. The sites were previously suspected of contamination with ordnance compounds. The initial survey employed sea urchin porewater toxicity tests to locate the most toxic stations. Sediments from the most toxic stations were selected for comprehensive chemical analyses. Based on the combined information from the toxicity and chemical data, three adjacent stations in Ostrich Bay were selected for the TIE study. The results of the phase I TIE suggested that organics and metals were primarily responsible for the observed toxicity in the sea urchin fertilization test. In addition to these contaminants, ammonia was also contributing to the toxicity for the sea urchin embryological development test. The phase II TIE study isolated the majority of the toxicity in the fraction containing nonpolar organics with high log K(ow), but chemical analyses failed to identify a compound present at a concentration high enough to be responsible for the observed toxicity. The data suggest that some organic or organometallic contaminant(s) that were not included in the comprehensive suite of chemical analyses caused the observed toxicological responses.

Development of marine toxicity data for ordnance compounds.

A toxicity database for ordnance compounds was generated using eight compounds of concern and marine toxicity tests with five species from different phyla. Toxicity tests and endpoints included fertilization success and embryological development with the sea urchin Arbacia punctulata; zoospore germination, germling length, and cell number with the green macroalga Ulva fasciata; survival and reproductive success of the polychaete Dinophilus gyrociliatus; larvae hatching and survival with the redfish Sciaenops ocellatus; and survival of juveniles of the opossum shrimp Americamysis bahia (formerly Mysidopsis bahia). The studied ordnance compounds were 2,4- and 2,6-dinitrotoluene, 2,4,6-trinitrotoluene, 1,3-dinitrobenzene, 1,3,5-trinitrobenzene, 2,4,6-trinitrophenylmethylnitramine (tetryl), 2,4,6-trinitrophenol (picric acid), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). The most sensitive toxicity test endpoints overall were the macroalga zoospore germination and the polychaete reproduction tests. The most toxic ordnance compounds overall were tetryl and 1,3,5-trinitrobenzene. These were also the most degradable compounds, often being reduced to very low or below-detection levels at the end of the test exposure. Among the dinitro- and trinitrotoluenes and benzenes, toxicity tended to increase with the level of nitrogenation. Picric acid and RDX were the least toxic chemicals tested overall.