Development of a whole-sediment toxicity test using a benthic marine microalga

An acute whole-sediment toxicity test with a benthic marine microalga was developed and optimized using flow cytometry to distinguish algae (based on their chlorophyll a autofluorescence) from sediment particles. Of seven benthic marine algae screened, the diatom Entomoneis cf punctulata was most suitable because of its tolerance of a wide range of water and sediment physicochemical parameters, including salinity, pH, ammonia, and sulfide. A whole-sediment and water-only toxicity test based on inhibition of esterase activity in this species was developed. Enzyme activity rather than growth was used as the test endpoint, as nutrient release from sediments has previously been found to stimulate algal growth, potentially masking contaminant toxicity. The sensitivity of the bioassay to a range of metals (copper, zinc, cadmium, lead, arsenic, manganese) and phenol in water-only exposures was compared to the standard 72-h growth rate inhibition test. The esterase enzyme inhibition test was sensitive to copper, with a 3-h inhibitory concentration to cause a 50% (IC50) reduction in a fluorescein diacetate fluorescence value of 97 +/- 39 microg Cu/L. A concentration-dependent response was also observed in the presence of sediment particles (copper tailings), with and without dilution, using a control clean sediment. The primary route of exposure to copper was via pore water rather than by direct contact with tailings particles. This is the first whole-sediment bioassay developed with a benthic alga suitable for sediment quality assessment in marine/estuarine systems, and its advantages and limitations are discussed.     

Development and application of whole-sediment toxicity test using immobilized freshwater microalgae Pseudokirchneriella subcapitata

A method for a whole-sediment toxicity test using alginate immobilized microalgae Pseudokirchneriella subcapitata was developed using spiked sediments and applied to contaminated field sediment samples. For method development, a growth inhibition test (72 h) with algal beads was conducted for the sediments spiked with Cu or diuron. The method was validated by determining dose-response relationships for Cu and diuron in both fine-grained and coarse-grained sediments. The results of a spiked sediment toxicity test suggested that sediment particle size distribution (clay content) had a significant effect on the growth of P. subcapitata. The developed method using immobilized microalgae P. subcapitata beads was applied successfully in the toxicity test and toxicity identification evaluation (TIE) for the four field sediment samples. After a series of extractions with 0.01 M CaCl(2) solution, acetone, and dichloromethane, the extracted sediment, which was shown to be nontoxic to algae, was used as the control and diluent for the same sediment in the whole-sediment toxicity test. The results showed that all investigated field sediment samples were found to be toxic to the immobilized algae P. subcapitata, with their median effective concentration (EC50) values ranging from 41.4 to 79.0% after 72 h exposure. In the whole sediment TIE, growth of P. subcapitata was improved to varying degrees after adding zeolite, resin, or activated charcoal, suggesting different contributions to toxicity from ammonia, metals, and organic contaminants in the tested sediments.     

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.     

Toxicity of Sediment Cores Collected from the Ashtabula River in Northeastern Ohio,USA, to the Amphipod <Emphasis Type="Italic">Hyalella azteca</Emphasis>

This study was conducted to support a Natural Resource Damage Assessment and Restoration project associated with the Ashtabula River in Ohio. The objective of the study was to evaluate the chemistry and toxicity of 50 sediment samples obtained from five cores collected from the Ashtabula River (10 samples/core, with each 10-cm-diameter core collected to a total depth of about 150 cm). Effects of chemicals of potential concern (COPCs) measured in the sediment samples were evaluated by measuring whole-sediment chemistry and whole-sediment toxicity in the sediment samples (including polycyclic aromatic hydrocarbons [PAHs], polychlorinated biphenyls [PCBs], organochlorine pesticides, and metals). Effects on the amphipod Hyalella azteca at the end of a 28-day sediment toxicity test were determined by comparing survival or length of amphipods in individual sediment samples in the cores to the range of responses of amphipods exposed to selected reference sediments that were also collected from the cores. Mean survival or length of amphipods was below the lower limit of the reference envelope in 56% of the sediment samples. Concentrations of total PCBs alone in some samples or concentrations of total PAHs alone in other samples were likely high enough to have caused the reduced survival or length of amphipods (i.e., concentrations of PAHs or PCBs exceeded mechanistically based and empirically based sediment quality guidelines). While elevated concentrations of ammonia in pore water may have contributed to the reduced length of amphipods, it is unlikely that the reduced length was caused solely by elevated ammonia (i.e., concentrations of ammonia were not significantly correlated with the concentrations of PCBs or PAHs and concentrations of ammonia were elevated both in the reference sediments and in the test sediments). Results of this study show that PAHs, PCBs, and ammonia are the primary COPCs that are likely causing or substantially contributing to the toxicity to sediment-dwelling organisms. An erratum to this article can be found at     

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.     

Assessment of supercritical fluid extraction use in whole sediment toxicity identification evaluations

Supercritical fluid extraction (SFE) with pure CO(2) was assessed as a confirmatory tool in phase III of whole sediment toxicity identification evaluations (TIEs). The SFE procedure was assessed on two reference sediments and three contaminated sediments by using a combination of toxicological and chemical measurements to quantify effectiveness. Sediment toxicity pre- and post-SFE treatment was quantified with a marine amphipod (Ampelisca abdita) and mysid (Americamysis bahia), and nonionic organic contaminants (NOCs) polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were measured in sediments, overlying waters, and interstitial waters. In general, use of SFE with the reference sediments was successful, with survival averaging 91% in post-SFE treatments. Substantial toxicity reductions and contaminant removal from sediments and water samples generated from extracted sediments of up to 99% in two of the contaminated sediments demonstrated SFE effectiveness. Furthermore, toxicological responses for these SFE-treated sediments showed comparable results to those from the same sediments treated with the powdered coconut charcoal addition manipulation. These data demonstrated the utility of SFE in phase III of a whole sediment TIE. Conversely, in one of the contaminated sediments, the SFE treatments had no effect on sediment toxicity, whereas sediment concentrations of PCBs and PAHs were reduced. We propose that, for some sediments, the SFE treatment may result in the release of otherwise nonbioavailable cationic metals that subsequently cause toxicity to test organisms. Overall, SFE treatment was found to be effective for reducing the toxicity and concentrations of NOCs in some contaminated sediments. However, these studies suggest that SFE treatment may enhance toxicity with some sediments, indicating that care must be taken when applying SFE and interpreting the results.     

Greatly reduced bioavailability and toxicity of polycyclic aromatic hydrocarbons to Hyalella azteca in sediments from manufactured-gas plant sites

The toxicity of polycyclic aromatic hydrocarbons (PAHs) to Hyalella azteca, was measured in 34 sediment samples collected from four manufactured-gas plant (MGP) sites ranging in total PAH16 (sum of 16 U.S. Environmental Protection Agency priority pollutant PAHs) concentrations from 4 to 5700 mg/kg, total organic carbon content from 0.6 to 11%, and soot carbon from 0.2 to 5.1%. The survival and growth of H. azteca in 28-d bioassays were unrelated to total PAH concentration, with 100% survival in one sediment having 1,730 mg/kg total PAH16, whereas no survival was observed in sediment samples with concentrations as low as 54 mg/kg total PAH16. Twenty-five of the 34 sediment samples exceeded the probable effects concentration screening value of 22.8 mg/kg total PAH13 (sum of 13 PAHs) and equilibrium partitioning sediment benchmarks for PAH mixtures (on the basis of the measurement of 18 parent PAHs and 16 groups of alkylated PAHs, [PAH34]); yet, 19 (76%) of the 25 samples predicted to be toxic were not toxic to H. azteca. However, the toxicity of PAHs to H. azteca was accurately predicted when either the rapidly released concentrations as determined by mild supercritical fluid extraction (SFE) or the pore-water concentrations were used to establish the bioavailability of PAHs. These results demonstrate that the PAHs present in many sediments collected from MGP sites have low bioavailability and that both the measurement of the rapidly released PAH concentrations with mild SFE and the dissolved pore-water concentrations of PAHs are useful tools for estimating chronic toxicity to H. azteca.     

Sediment Contamination of Residential Streams in the Metropolitan Kansas City Area, USA: Part II. Whole-Sediment Toxicity to the Amphipod Hyalella azteca

This is the second part of a study that evaluates the influence of nonpoint sources on the sediment quality of five adjacent streams within the metropolitan Kansas City area, central United States. Physical, chemical, and toxicity data (Hyalella azteca 28-day whole-sediment toxicity test) for 29 samples collected in 2003 were used for this evaluation, and the potential causes for the toxic effects were explored. The sediments exhibited a low to moderate toxicity, with five samples identified as toxic to H. azteca. Metals did not likely cause the toxicity based on low concentrations of metals in the pore water and elevated concentrations of acid volatile sulfide in the sediments. Although individual polycyclic aromatic hydrocarbons (PAHs) frequently exceeded effect-based sediment quality guidelines [probable effect concentrations (PECs)], only four of the samples had a PEC quotient (PEC-Q) for total PAHs over 1.0 and only one of these four samples was identified as toxic. For the mean PEC-Q for organochlorine compounds (chlordane, dieldrin, sum DDEs), 4 of the 12 samples with a mean PEC-Q above 1.0 were toxic and 4 of the 8 samples with a mean PEC-Q above 3.0 were toxic. Additionally, four of eight samples were toxic, with a mean PEC-Q above 1.0 based on metals, PAHs, polychlorinated biphenyls (PCBs), and organochlorine pesticides. The increase in the incidence of toxicity with the increase in the mean PEC-Q based on organochlorine pesticides or based on metals, PAHs, PCBs, and organochlorine pesticides suggests that organochlorine pesticides might have contributed to the observed toxicity and that the use of a mean PEC-Q, rather than PEC-Qs for individual compounds, might be more informative in predicting toxic effects. Our study shows that stream sediments subject to predominant nonpoint sources contamination can be toxic and that many factors, including analysis of a full suite of PAHs and pesticides of both past and present urban applications and the origins of these organic compounds, are important to identify the causes of toxicity.     

Relationships between contaminant levels in marine sediments and their biological effects on embryos of oysters,Crassostrea gigas

Abstract-Surface sediment samples from 10 coastal locations were analyzed with respect to their physical and chemical characteristics as well as their biological quality. The toxicity of the decanted fresh and freeze-dried sediments and of their elutriates was assessed by bioassays with embryos of the oysters Crassostrea gigas. The concentration inhibiting normal embryogenesis in 20% of the larvae (EC20) was used as a measure of toxicity and compared with the physical and chemical properties of the sediments and elutriates by principal components analysis. Decanted whole sediments were one to four orders of magnitude more toxic than their elutriates because the latter have lower contaminant concentrations. The biological effects of decanted whole sediment depended mostly on the levels of heavy metals and polycyclic aromatic hydrocarbons (PAHs), while in the case of the elutriates, the toxicity was mainly correlated with the concentrations of total ammonia and of dissolved organic carbon (DOC). Freeze-dried sediments and their elutriates were up to one order of magnitude more toxic than fresh sediments and elutriates, respectively, presumably because the freeze-drying procedure increases pollutant bioavailability or causes a release of unidentified organic compounds having toxic effects.     

An Evaluation of the Toxicity of Contaminated Sediments from Waukegan Harbor, Illinois, Following Remediation

Waukegan Harbor in Illinois was designated as a Great Lakes Area of Concern due to high concentrations of sediment-associated polychlorinated biphenyls (PCBs). The objective of this study was to evaluate the toxicity of 20 sediment samples collected after remediation (primarily dredging) of Waukegan Harbor for PCBs. A 42-day whole sediment toxicity test with the amphipod Hyalella azteca (28-day sediment exposure followed by a 14-day reproductive phase) and sediment toxicity tests with Microtox(R) were conducted to evaluate sediments from Waukegan Harbor. Endpoints measured were survival, growth, and reproduction (amphipods) and luminescent light emission (bacteria). Survival of amphipods was significantly reduced in 6 of the 20 sediment samples relative to the control. Growth of amphipods (either length or weight) was significantly reduced relative to the control in all samples. However, reproduction of amphipods identified only two samples as toxic relative to the control. The Microtox basic test, conducted with organic extracts of sediments identified only one site as toxic. In contrast, the Microtox solid-phase test identified about 50% of the samples as toxic. A significant negative correlation was observed between reproduction and the concentration of three polynuclear aromatic hydrocarbons (PAHs) normalized to total organic carbon. Sediment chemistry and toxicity data were evaluated using sediment quality guidelines (consensus-based probable effect concentrations, PECs). Results of these analyses indicate that sediment samples from Waukegan Harbor were toxic to H. azteca contaminated at similar contaminant concentrations as sediment samples that were toxic to H. azteca from other areas of the United States. The relationship between PECs and the observed toxicity was not as strong for the Microtox test. The results of this study indicate that the first phase of sediment remediation in Waukegan Harbor successfully lowered concentrations of PCBs at the site. Though the sediments were generally not lethal, there were still sublethal effects of contaminants in sediments at this site observed on amphipods in long-term exposures (associated with elevated concentrations of metals, PCBs, and PAHs).     

Toxicity of saline and organic solvent extracts of sediments from Boston Harbor,Massachusetts and the Hudson River-Raritan Bay estuary,New York using the Microtox® bioassay

The toxic effects of organic and saline extracts of sediment samples collected from 16 sites in Boston Harbor, Massachusetts and from 17 sites in the Hudson River-Raritan Bay estuary, New York were tested with the Microtox^® bioassay. This bioassay measures changes in light production by bioluminescent marine bacteria exposed to sediment extracts. Organic solvent extracts of all 33 sediments showed some degree of toxicity, with sediment samples from sites in the urban areas of the bays being significantly more toxic than those from less urbanized areas of the bays. Saline extracts, however, were less toxic, only seven of 33 saline extracts produced a significant response using the recommended method of data analyses. The proportional decrease in bacterial light production at the highest concentration of saline sediment extract in the reaction mixture compared to the bacterial light production in the controls (saline light change—SLC) appeared to be a better indicator of sediment toxicity than generating a saline EC₅₀ (the amount of sediment required to reduce bioluminescence 50%) value; 16 of 33 saline extracts produced a significant response (?10% reduction in bioluminescence). Organic extracts of sediments previously extracted with saline were also always toxic in the Microtox^® bioassay but were less toxic than sediments not previously extracted. Organic EC₅₀ and SLC were inversely related to concentrations of sediment contaminants, principally low- and high-molecular-weight polycyclic aromatic hydrocarbons (PAHs). This relationship was strongest for the organic solvent extracts of sediments tested in the bioassay. Organic solvent extracts of sediments from Boston Harbor were also significantly more toxic in the Microtox^® bioassay than those from the Hudson-Raritan estuary, even though sediment concentrations of PAHs, a measure of anthropogenic contamination, were similar. The cause for the differential toxicity is unknown at this time, but chemical contaminants other than chlorinated hydrocarbons (CHs) and PAHs may be contributing to the observed toxicity in the Microtox^® bioassay using organic extracts of sediment. Testing sediment toxicity using organic extracts of sediment with the Microtox^® bioassay provides better estimates of toxicity due to sediment contaminants than using saline extracts of 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.     

The use of coarse, separable, condensed-phase organic carbon particles to characterize desorption resistance of polycyclic aromatic hydrocarbons in contaminated sediments

Physical separations were employed to characterize the source of desorption-resistant behavior for polycyclic aromatic hydrocarbons (PAHs) in laboratory- and field-contaminated sediments. Size and density separation of laboratory-contaminated sediments did not effectively separate the amorphous-phase (volatile) and condensed-phase (nonvolatile) organic carbon as measured by thermal oxidation at 375 degrees C. These separations also did not result in sediment fractions with significantly different desorption characteristics as measured by apparent partition coefficients. Coarse particles from a field-contaminated sediment from Utica Harbor (UH; Utica, NY, USA), however, could be directly separated into sandy fractions and organic fractions that were composed of woody organic matter, charcoal or charred vegetative matter, and coal-like and coal-cinder particles. Chemical analysis showed that coal-like (glassy, nonporous) and coal-cinder (porous, sintered) particles exhibited very high PAH concentrations and high apparent partition coefficients. These particles also exhibited significantly higher condensed-phase (nonvolatile) organic carbon contents as defined by thermal oxidation at 375 degrees C. The apparent partition coefficients of PAHs in the coal-cinder particles were a good indication of the apparent partition coefficients in the desorption-resistant fraction of UH sediment, indicating that the coarse particles provided a reasonable characterization of the desorption-resistance phenomena in these sediments even though the coarse fractions represented less than 25% of the organic carbon in the whole sediment.     

Whole-sediment toxicity identification evaluation tools for pyrethroid insecticides: II. Esterase addition

An esterase enzyme capable of catalyzing the hydrolysis of the ester bond common to all pyrethroid insecticides has been proposed as a toxicity identification evaluation procedure for the compounds when present in water samples. It appeared to show promise in previous applications to pore water and in one published application to bulk sediment. The present study was designed to provide the additional validation of the technique when applied to whole sediment, demonstrating its efficacy and specificity to pyrethroids. When added to the overlying water in a standard sediment toxicity test with the amphipod Hyalella azteca, the enzyme reduced toxicity of pyrethroid-spiked laboratory sediments. The technique had no effect on toxicity of DDT or chlorpyrifos, but it dramatically reduced the toxicity of cadmium, presumably by complexation of the cadmium with dissolved organic matter rather than by enzymatic activity. Esterase addition consistently reduced pyrethroid-related toxicity in 12 tests with field-collected sediments. The procedure, however, also results in substantial changes in water quality, provides an undesirable nutritional benefit to the test organisms exposed to the esterase, and achieves a substantial fraction of the protective capability simply by complexation of the pyrethroids with the esterase or the microbial growth that the esterase promotes. The esterase addition technique has potential for whole-sediment application, but further development of procedures and confirmation by independent lines of evidence are needed to reduce the potential for misinterpretation of results.     

The sorption of polycyclic aromatic hydrocarbons in Zegrzyńskie Lake

The sorption of polycyclic aromatic hydrocarbons in aquatic sediments from Zegrzyńskie Lake was examined. Batch experiment was performed in order to determine sorption efficiency in different kinds of sediments from Zegrzyńskie Lake. Five polycyclic aromatic hydrocarbons (phenanthrene, fluoranthene, pyrene, chrysene benzo[a]pyrene) were chosen to this experiment and sorption process was examined on seven sediments of different properties. Chosen hydrocarbons are of different structure of molecule and different chemical and physical properties. Concentrations of polycyclic aromatic hydrocarbons in aquatic sediments and in water phase were measured in the following order: extraction with dichloromethane, concentration on rotary evaporator, silica gel clean up, n-hexane elution, concentration on rotary evaporator and in vials, GC/MS analysis. Chemical composition of aquatic sediments were examined using methods for sewage sludge and soils analysis. In every sediment concentrations of PAHs, organic matter and organic: carbon, phosphorus, nitrogen and sulphur were measured. Also fractional analysis of sediments was made. Isotherms of sorption were measured for these sediments and compounds. Equations of these isotherms were performed and were used in order to find relationships between sorption efficiency and sediments composition. Depending on sediment properties and composition different concentrations of polycyclic aromatic hydrocarbons were found in solid phase. Sediments of high quantities of organic matter and small particles were the best sorbents for PAHs. Fluoranthene, pyrene and chrysene were efficiently sorbed in sediments of high concentration of organic matter. And efficiency of phenanhrene and benzo[a]pyrene sorption were better in sediments with high quantity of organic sulphur.     

Polycyclic aromatic hydrocarbon and petroleum hydrocarbon contamination in sediment from the Newark Bay estuary,New Jersey

The presence of numerous industrial and municipal sources such as former creosote wood preserving facilities, petroleum storage and refinery facilities, paint and chemical manufacturers, combined sewer overflows, and sewage treatment facilities along the shores of Newark Bay, New Jersey and its major tributaries suggests the potential for widespread contamination by polycyclic aromatic hydrocarbons (PAHs) and petroleum hydrocarbons. In this study, the concentrations and distributions of 19 PAHs and total extractable petroleum hydrocarbon (TEPH) were determined in 213 sediment samples obtained from 58 sediment cores collected between November 1991 and March 1993 from the Arthur Kill, Elizabeth River, Hackensack River, Kill Van Kull, Newark Bay, Upper New York Bay, and Rahway River. Chronological profiles of PAH and TEPH deposition from pre-1930 to the present were determined in each sediment core using ¹³⁷Cs and ²¹⁰Pb radioisotope measurements. The concentrations of total PAHs (tPAH) and individual PAHs were compared to National Oceanic and Atmospheric Administration (NOAA) benchmark sediment effects-range median (ER-M) values. The objectives of this study were to: (a) determine the spatial and temporal distributions of PAHs in sediments; (b) identify their possible sources; and (c) assess the potential for sediment toxicity within the estuary. The results indicate elevated concentrations of PAHs and TEPH in surface and buried sediments throughout the estuary, particularly in the Elizabeth River, the Arthur Kill, and in the Passaic River above the Dundee Dam and below the Jackson Street Bridge. Sediments collected from ship berths at Port Newark and Port Elizabeth in Newark Bay were also found to contain elevated levels of PAHs and TEPH. The concentrations of PAHs and TEPH in sediment generally increase with depth throughout the estuary. Comparisons to NOAA ER-M values indicate that the concentrations of many PAHs in surface and buried sediments at several locations in the estuary pose a significant hazard to aquatic organisms. Radiodating of sediment cores reveals that the highest concentrations of PAHs, and the greatest potential hazards to aquatic biota, occur in sediments deposited during the 1950s. Although the major inputs of PAHs are probably combustion sources and urban runoff entering the estuary through combined sewer overflows and storm drains, the unusually high concentrations of PAHs and TEPH found in some sediments may be best explained by point source inputs or catastrophic oil spills.     

Whole-sediment toxicity identification evaluation tools for pyrethroid insecticides: I. Piperonyl butoxide addition

Piperonyl butoxide (PBO) is a synergist used in some pyrethroid and pyrethrin pesticide products and has been used in toxicity identification evaluations (TIEs) of water samples to indicate organophosphate or pyrethroid-related toxicity. Methods were developed and validated for use of PBO as a TIE tool in whole-sediment testing to help establish if pyrethroids are the cause of toxicity observed in field-collected sediments. Pyrethroid toxicity was increased slightly more than twofold in 10-d sediment toxicity tests with Hyalella azteca exposed to 25 microg/L of PBO in the overlying water. This concentration was found to be effective for sediment TIE use, but it is well below that used in previous water and pore-water TIEs with PBO. The effect of PBO on the toxicity of several nonpyrethroids also was tested. Toxicity of the organophosphate chlorpyrifos was reduced by PBO, and the compound had no effect on toxicity of cadmium, DDT, or fluoranthene. Mixtures of the pyrethroid bifenthrin and chlorpyrifos were tested to determine the ability of PBO addition to identify pyrethroid toxicity when organophosphates were present in a sample. The PBO-induced increase in pyrethroid toxicity was not seen when chlorpyrifos was present at or above equitoxic concentrations with the pyrethroid. In the vast majority of field samples, however, the presence of chlorpyrifos does not interfere with use of PBO to identify pyrethroid toxicity. Eleven field sediments or soils containing pyrethroids and/or chlorpyrifos were used to validate the method. Characterization of the causative agent as determined by PBO addition was consistent with confirmation by chemical analysis and comparison to known toxicity thresholds in 10 of the 11 sediments.     

Effects of acid-volatile sulfide on metal bioavailability and toxicity to midge (Chironomus tentans) larvae in black shale sediments

Metal bioavailability and toxicity to aquatic organisms are greatly affected by variables such as pH, hardness, organic matter, and sediment acid-volatile sulfide (AVS). Sediment AVS, which reduces metal bioavailability and toxicity by binding and immobilizing metals as insoluble sulfides, has been studied intensely in recent years. Few studies, however, have determined the spatial variability of AVS and its interaction with simultaneously extracted metals (SEM) in sediments containing elevated concentrations of metals resulting from natural geochemical processes, such as weathering of black shales. We collected four sediment samples from each of four headwater bedrock streams in northcentral Arkansa (USA; three black shale-draining streams and one limestone-draining stream). We conducted 10-d acute whole-sediment toxicity tests using the midge Chironomus tentans and performed analyses for AVS, total metals, SEMs, and organic carbon. Most of the sediments from shale-draining streams had similar total metal and SEM concentrations but considerable differences in organic carbon and AVS. Zinc was the leading contributor to the SEM molar sum, averaging between 68 and 74%, whereas lead and cadmium contributed less than 3%. The AVS concentration was very low in all but two samples from one of the shale streams, and the sum of the SEM concentrations was in molar excess of AVS for all shale stream sediments. No significant differences in mean AVS concentrations between sediments collected from shale-draining or limestone-draining sites were noted (p > 0.05). Midge survival and growth in black shale-derived sediments were significantly less (p < 0.001) than that of limestone-derived sediments. On the whole, either SEM alone or SEM-AVS explained the total variation in midge survival and growth about equally well. However, survival and growth were significantly greater (p < 0.05) in the two sediment samples that contained measurable AVS compared with the two sediments from the same stream that contained negligible AVS.     

Performance and sensitivity of rapid sublethal sediment toxicity tests with the amphipod Melita plumulosa and copepod Nitocra spinipes

Sublethal whole-sediment toxicity tests are an important tool for assessing the potential effects of contaminated sediments. However, the longer duration required for evaluating potential chronic effects may increase endpoint variability and test costs compared to survival endpoints. In the present study we compare the performance and sensitivity to contaminants of 10-d sublethal sediment toxicity tests with the amphipod Melita plumulosa and harpacticoid copepod Nitocra spinipes. For both tests, sublethal effects were consistently observed when sediment contaminant concentrations exceeded sediment quality guideline (SQG) concentrations. The response of these bioassays in metal-contaminated sediments was shown to conform ideally with respect to the mean SQG quotient calculated on the basis of the Australian and New Zealand lower SQG trigger value, with toxicity being observed only in those sediments where the mean quotient exceeded one. Better predictions of nontoxicity were obtained when dilute acid-extractable rather than total metal concentrations were used. Using the upper SQG, toxicity frequently occurred at mean quotients below one. The effects were generally consistent with predictions from the acid-volatile sulfide and simultaneously extracted metal model. Effects on reproduction of M. plumulosa were detected for sediments that did not cause effects on survival and highlighted the environmental relevance and importance of using these sublethal endpoints. When using four replicates for M. plumulosa and five replicates for N. spinipes, the endpoint variability (standard error) was less than 10%. Variations in sediment particle size and organic carbon content did not affect endpoint variability. Both species are relatively easily cultured in the laboratory, and the estimated effort and cost of achieving the sublethal endpoints is 1.5 times that of the acute survival test endpoints.     

Polycyclic Aromatic Hydrocarbons in Superficial Sediments from Ghar El Melh Lagoon, Tunisia

The concentrations of 17 polycyclic aromatic hydrocarbons (PAHs) were determined in 12 superficial sediments collected from the Ghar El Melh lagoon. Sediment samples were extracted by Soxhlet, and analyzed by Gas chromatography with flame ionisation detector (FID). PAH concentrations, ranged from 39.59 to 655.28 ng/g on a dry weight. Total PAH concentrations were not correlated with organic carbon (OC) content or grain size (% <63 μm). Special PAH compound ratios, such as Ft/Py and Ft/Ft + Py were calculated to evaluate different hydrocarbon origins and showed that PAHs are derived from pyrolytic process.