Jonathan R. Serbst

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.

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.

Predicting the toxicity of chromium in sediments

Chromium exists in sediments in two oxidation states: Cr(III), which is relatively insoluble and nontoxic, and Cr(VI), which is much more soluble and toxic. Chromium(VI) is thermodynamically unstable in anoxic sediments, and acid-volatile sulfide (AVS) is formed only in anoxic sediments; therefore sediments with measurable AVS concentrations should not contain toxic Cr(VI). If this hypothesis holds true, measuring AVS could form the basis for a theoretically based guideline for Cr in sediments. Ten-day water-only and spiked sediment toxicity tests with the amphipod Ampelisca abdita were performed with Cr(VI) and Cr(III), along with sediments collected from a site contaminated with high concentrations of Cr. In sediments where AVS exceeded analytical detection limits, Cr concentrations in interstitial water were very low (<100 microg/L) and no significant toxicity to A. abdita was observed. In sediments in which AVS was not significantly greater than zero, Cr concentrations in interstitial waters increased significantly, with greater than 90% of the Cr present as Cr(VI), and mortality of A. abdita was elevated. These results demonstrate that measurements of AVS and interstitial water chromium can be useful in predicting the absence of acute effects from Cr contamination in sediments.

Evaluation of the effects of coal fly ash amendments on the toxicity of a contaminated marine sediment.

Approaches for cleaning up contaminated sediments range from dredging to in situ treatment. In this study, we discuss the effects of amending reference and contaminated sediments with coal fly ash to reduce the bioavailability and toxicity of a field sediment contaminated with polycyclic aromatic hydrocarbons (PAHs). Six fly ashes and a coconut charcoal were evaluated in 7-d whole sediment toxicity tests with a marine amphipod (Ampelisca abdita) and mysid (Americamysis bahia). Fly ashes with high carbon content and the coconut charcoal showed proficiency at reducing toxicity. Some of the fly ashes demonstrated toxicity in the reference treatments. It is suspected that some of this toxicity is related to the presence of ammonia associated with fly ashes as a result of postoxidation treatment to reduce nitrous oxide emissions. Relatively simple methods exist to remove ammonia from fly ash before use, and fly ashes with low ammonia content are available. Fly ashes were also shown to effectively reduce overlying water concentrations of several PAHs. No evidence was seen of the release of the metals cadmium, copper, nickel, or lead from the fly ashes. A preliminary 28-d polychaete bioaccumulation study with one of the high-carbon fly ashes and a reference sediment was also performed. Although preliminary, no evidence was seen of adverse effects to worm growth or lipid content or of accumulation of PAHs or mercury from exposure to the fly ash. These data show fly ashes with high carbon content could represent viable remedial materials for reducing the bioavailability of organic contaminants in sediments.

Mercury and stable isotopes of carbon and nitrogen in mink

Total Hg concentrations and values of stable isotopes (delta(15)N, delta(13)C) in tissues of mink (Mustela vison) captured in Rhode Island (USA) during winters of 1999 to 2004 were statistically distinct based on location. Mink captured in salt marsh environments (salt marsh group mink [SMGM]) had significantly lower mean Hg concentrations in liver and muscle tissue, and significantly higher delta(15)N and delta(13)C values in muscle, than those in corresponding samples of mink from upland freshwater locations (upland group mink [UPGM]). Stomach content samples obtained from the mink carcasses showed that fish, frogs, and crayfish were the dominant food items in UPGM, but in SMGM, fish predominated. Significant correlations were found for total Hg concentrations and stable isotope values between stomach contents and tissues. Comparisons of increases in Hg concentrations and delta(15)N values from stomach contents to muscle tissue showed nonsignificant differences between UPGM and SMGM for Hg concentrations (SMGM, factor of 4.2; UPGM, factor of 3.9) and delta(15)N values (SMGM, difference of 3.9 per thousand; UPGM, difference of 3.1 per thousand). These results suggest that the length of the trophic step and the extent of accumulation of Hg were approximately equal in both mink groups despite the differences in dietary composition and possible differences in accumulation of organic and inorganic Hg. The correspondence of stable isotope values and Hg concentrations between mink tissues and their stomach contents indicates that use of stomach content analysis to identify major prey items, followed by collection and analysis of appropriate field prey, may represent an approach for estimating Hg exposure to mink.

Marine sediment toxicity identification evaluation methods for the anionic metals arsenic and chromium

Marine sediments accumulate a variety of contaminants and, in some cases, demonstrate toxicity because of this contamination. Toxicity identification evaluation (TIE) methods provide tools for identifying the toxic chemicals causing sediment toxicity. Currently, whole-sediment TIE methods are not available for anionic metals like arsenic and chromium. In the present paper, we describe two new anion-exchange resins used in the development of whole-sediment TIE methods for arsenic and chromium. Resins were shown to reduce whole-sediment toxicity and overlying water concentrations of the anionic metals. Sediment toxicity, expressed as the median lethal concentration, was reduced by a factor of two to a factor of nearly six between amended sediment treatments containing resin and those without resin. Aqueous concentrations of arsenic and chromium in the toxicity exposures decreased to less than the detection limits or to concentrations much lower than those measured in treatments without resin. Interference studies indicated that the anion-exchange resins had no significant effect on concentrations of the representative pesticide endosulfan and minimal effects on concentrations of ammonia. However, the anion-exchange resins did significantly reduce the concentrations of a selection of cationic metals (Cd, Cu, Ni, Pb, and Zn). These data demonstrate the utility of anion-exchange resins for determining the contribution of arsenic and chromium to whole-sediment toxicity. The present results also indicate the importance of using TIE methods in a formal TIE structure to ensure that results are not misinterpreted. These methods should be useful in the performance of marine whole-sediment TIEs.

Biological responses of the sea urchin, Arbacia punctulata, to lead contamination for an estuarine ecological risk assessment

An estuarine ecological risk assessment for thePortsmouth Naval Shipyard (PNS) Kittery, ME, wasconducted utilizing the U.S. EPAs Framework forEcological Risk Assessment (ERA). As part of theanalysis phase of the ERA, laboratory studies wereconducted to develop quantitative exposure-responserelationships for lead (Pb), a key contaminant ofconcern for PNS, in order to evaluate the role of Pbin the ecological stress observed near PNS, and toestimate the probability of ecological risk associatedwith Pb contamination at the site. Biological effectsof exposure to Pb via sediment or diet were evaluatedusing several life stages of the sea urchin, Arbacia punctulata. This strategy was employedbecause echinoderm species, including A.punctulata, are amenable to laboratory testing andhave been used frequently to assess the toxicity ofestuarine waters and sediments. In addition, lifestage-specific biological effects could be comparedand integrated into projections of population-levelresponses to Pb. Results indicated that adult seaurchins accumulated Pb in direct proportion toexposure medium Pb concentration, whether exposureoccurred via sediment or diet. High Pb concentrationsreduced survival and gamete production in females, buthad no effect on the viability of produced gametes. Aqueous Pb exposure concentrations that producedadverse effects on adult sea urchin survival andreproduction were also directly toxic to early lifestages. In addition to their utility for this ERA,these results have applicability for the prediction ofbiological effects or the retrospective analysis ofcausal relationships at other estuarine sites.

Assessment of caudal fin clip as a non-lethal technique for predicting muscle tissue mercury concentrations in largemouth bass

Environmental context. In the development of fish consumption advisories, fisheries biologists routinely sacrifice fish and analyse muscle fillets in order to determine the extent of mercury contamination. Such lethal techniques may not be suitable for endangered species or limited fish populations from smaller-sized water bodies. We compared the measured total mercury concentrations in tail fin clips to that of muscle fillets and illustrated that tail fin clips may be used as an accurate tool for predicting mercury in muscle tissue. This is the first study on the use of tail fin clips to predict mercury levels in the muscle tissue of largemouth bass with minimal impact on the fish. Abstract. The statistical relationship between total mercury (Hg) concentration in clips from the caudal fin and muscle tissue of largemouth bass (Micropterus salmoides) from 26 freshwater sites in Rhode Island, USA was developed and evaluated to determine the utility of fin clip analysis as a non-lethal and convenient method for predicting mercury concentrations in tissues. The relationship of total Hg concentrations in fin clips and muscle tissue showed an r2 of 0.85 and may be compared with an r2 of 0.89 for Hg concentrations between scales and muscle tissue that was determined in a previous study on largemouth bass. The Hg concentration in fin clip samples (mean = 0.261 μg g–1 (dry)) was more than a factor of twenty greater than in the scale samples (mean = 0.012 μg g–1 (dry)). Therefore, fin clips may be a more responsive non-lethal predictor of muscle-Hg concentrations than scale in fish species which may have reduced Hg concentrations.

Interlaboratory comparison of a reduced volume marine sediment toxicity test method using the amphipod Ampelisca abdita

The U.S. Environmental Protection Agency has standardized methods for performing acute marine amphipod sediment toxicity tests. A test design reducing sediment volume from 200 to 50 ml and overlying water from 600 to 150 ml was recently proposed. An interlaboratory comparison was conducted to evaluate the precision of this reduced sediment volume toxicity test method using the marine amphipod Ampelisca abdita. A negative control and three sediment samples of varying degrees of toxicity ranging from low to high were tested by six laboratories. Complete agreement was reached in rank of relative toxicity for all samples tested by five out of six laboratories. Test acceptability for control survival was achieved by all laboratories, and 69% agreement in classification of the sediments as toxic or nontoxic was documented. Coefficients of variation in all test samples were similar to those reported in other interlaboratory studies using marine amphipods. Results of this study indicate that the reduced sediment volume test using A. abdita is a reliable and precise measure of acute toxicity in marine sediment samples.