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Contaminants in stream sediments from seven United States metropolitan areas: part II—sediment toxicity to the amphipod Hyalella azteca and the midge Chironomus dilutus

Relationships between sediment toxicity and sediment chemistry were evaluated for 98 samples collected from seven metropolitan study areas across the United States. Sediment-toxicity tests were conducted with the amphipod Hyalella azteca (28 day exposures) and with the midge Chironomus dilutus (10 day exposures). Overall, 33 % of the samples were toxic to amphipods and 12 % of the samples were toxic to midge based on comparisons with reference conditions within each study area. Significant correlations were observed between toxicity end points and sediment concentrations of trace elements, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), or organochlorine (OC) pesticides; however, these correlations were typically weak, and contaminant concentrations were usually below sediment-toxicity thresholds. Concentrations of the pyrethroid bifenthrin exceeded an estimated threshold of 0.49 ng/g (at 1 % total organic carbon) in 14 % of the samples. Of the samples that exceeded this bifenthrin toxicity threshold, 79 % were toxic to amphipods compared with 25 % toxicity for the samples below this threshold. Application of mean probable effect concentration quotients (PECQs) based on measures of groups of contaminants (trace elements, total PAHs, total PCBs,OCpesticides, and pyrethroid pesticides [bifenthrin in particular]) improved the correct classification of samples as toxic or not toxic to amphipods compared with measures of individual groups of contaminants. Sediments are a repository for many contaminants released into surface waters. Because of this, organisms inhabiting sediments may be exposed to a wide range of contaminants (United States Environmental Protection Agency (USEPA) United States Environmental Protection Agency 2000; American Society for Testing and Materials [ASTM] American Society for Testing and Materials International 2012). Contaminants of potential concern in sediments typically include trace elements (metals), organochlorine (OC) pesticides, polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs; Ingersoll et al. 2001). In 2000, the USEPA began to restrict the use of organophosphate pesticides, such as diazinon and chlorpyrifos (Spurlock and Lee 2008). These restrictions have led to increased use of pyrethroid pesticides, which have widespread applications in both agricultural and urban environments (Kuivila et al. 2012). Pyrethroids are hydrophobic compounds that have been observed to accumulate in sediments (Laskowski 2002). Toxicity of pyrethroids in field-collected sediment from small urban streams (Weston et al. 2005; Holmes et al. 2008; Ding et al. 2010; Domagalski et al. 2010) or with pyrethroids spiked into sediment (Amweg et al. 2006; Hintzen et al. 2009) have been evaluated primarily in 10 day lethality tests conducted with the amphipod Hyalella azteca . However, the sublethal effects in long-term exposures to pyrethroids in sediment have not been evaluated, and the distribution of pyrethroids sediments has not typically been evaluated in wadeable streams (Gilliom et al. 2006). This article is the second in a series that describe the results of a study of the distribution and toxicity of pyrethroids and other co-occurring trace elements and organic contaminants (PCBs, PAHs, OC pesticides) in stream sediments from 7 metropolitan areas across the United States (Moran et al. 2012). The study evaluated 98 sediment samples collected from streams ranging from undeveloped to highly urban and differs from previous studies by sampling larger wadeable streams and avoiding point sources (such as storm drains) and other inflows (Gilliom et al. 2006). Part 1 of the series characterizes sediment contaminants in relation to urbanization and other factors in the 7 metropolitan study areas (Nowell et al. 2012). Part 2 (this article) evaluates relationships between sediment chemistry and sediment toxicity in 28 day whole-sediment exposures conducted with the amphipod H. azteca and in 10 day whole-sediment exposure conducted with the midge Chironomus dilutus (USEPA United States Environmental Protection Agency 2000; ASTM American Society for Testing and Materials International 2012). Toxicity end points evaluated in the amphipod and midge exposures included the effects of these field-collected sediments on survival, weight, or biomass of the test organisms.

Georgia;Massachusetts;Texas;Colorado;Wisconsin;Uta

Toxicity of alkalinity to Hyalella azteca

Toxicity testing and chemical analyses of sediment pore water have been suggested for use in sediment quality assessments and sediment toxicity identification evaluations. However, caution should be exercised in interpreting pore-water chemistry and toxicity due to inherent chemical characteristics and confounding relationships. High concentrations of alkalinity, which are typical of sediment pore waters from many regions, have been shown to be toxic to test animals. A series of tests were conducted to assess the significance of elevated alkalinity concentrations to Hyalella azteca, an amphipod commonly used for sediment and pore-water toxicity testing. Toxicity tests with 14-d old and 7-d old animals were conducted in serial dilutions of sodium bicarbonate (NaHCO3) solutions producing alkalinities ranging between 250 to 2000 mg/L as CaCO3. A sodium chloride (NaCl) toxicity test was also conducted to verify that toxicity was due to bicarbonate and not sodium. Alkalinity was toxic at concentrations frequently encountered in sediment pore water. There was also a significant difference in the toxicity of alkalinity between 14-d old and 7-d old animals. The average 96-h LC50 for alkalinity was 1212 mg/L (as CaCO3) for 14-d old animals and 662 mg/L for the younger animals. Sodium was not toxic at levels present in the NaHCO3 toxicity tests. Alkalinity should be routinely measured in pore-water toxicity tests, and interpretation of toxicity should consider alkalinity concentration and test-organism tolerance.

Bulletin of Environmental Contamination and Toxico

Effects of contaminants on toxicity of the lampricides TFM and Bayer 73 to three species of fish

Waters in the Great Lakes basin contain more than 400 contaminant chemicals that potentially affect fishery resources, commerce, and human inhabitants. We determined in the laboratory the effects of selected contaminants on the toxicity of the widely used lampricides TFM (3-trifluoromethyl-4-nitrophenol) and Bayer 73 (2′,5-dichloro-4′-nitrosalicylanilide) to three species of fish—rainbow trout ( Salmo gairdneri ), white sucker ( Catostomus commersoni ), and fathead minnow ( Pimephales promelas ). The fish were exposed to paired mixtures of lampricides and selected contaminants in standardized, acute static toxicity tests to determine the resulting type of response—less than additive, additive, or greater than additive (synergistic). As expected, the toxicities of combinations of lampricides with organic pesticides, metal, industrial or municipal pollutants, and tannic acid were mostly additive. However, the toxicity of a combination of TFM, Delnav, and malathion was synergistic, and extremely small quantities of each chemical became lethal when mixed. The concentration that produced 50% mortality was 1.64 mg/L for TFM alone but only 0.041 mg/L for TFM with the pesticides. Toxicities of the pesticides in the combination also increased commensurately. The triple combination of chemicals produced extraordinary synergism and effectively demonstrated the hazards that may result if certain chemical combinations occur in the aquatic environment. However, synergism is not the only kind of toxic action that produces hazards to aquatic organisms. All three types of toxic action are of concern because toxic units produced by contaminant chemicals add to the toxic units of applied management chemicals. Since the toxicity of the majority of chemical combinations is simply additive, this cumulative toxic action contributes more total units to aquatic environments than the extreme actions of less than additive and synergism. The toxicity of the lampricide TFM, as well as other management chemicals, is reinforced by the presence of any contaminant that contributes additional units of toxicity. Therefore, all types of cumulative toxic action should be of concern to people and agencies involved with protecting the environment.

Journal of Great Lakes Research

Evaluation of the toxicity of sediments from the Anniston PCB Site to the mussel Lampsilis siliquoidea

The Anniston Polychlorinated Biphenyl (PCB) Site is located in the vicinity of the municipality of Anniston in Calhoun County, in the north-eastern portion of Alabama. Although there are a variety of land-use activities within the Choccolocco Creek watershed, environmental concerns in the area have focused mainly on releases of PCBs to aquatic and riparian habitats. PCBs were manufactured by Monsanto, Inc. at the Anniston facility from 1935 to 1971. The chemicals of potential concern (COPCs) in sediments at the Anniston PCB Site include: PCBs, mercury, metals, polycyclic aromatic hydrocarbons (PAHs), organochlorine and organophosphorous pesticides, volatile organic compounds (VOCs), semivolatile organic compounds (SVOCs), and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs). The purpose of this study was to evaluate the toxicity of PCB-contaminated sediments to the juvenile fatmucket mussel (Lampsilis siliquoidea) and to characterize relationships between sediment chemistry and the toxicity of sediment samples collected from the Anniston PCB Site using laboratory sediment testing. Samples were collected in August 2010 from OU-4 of the Anniston PCB Site, as well as from selected reference locations. A total of 32 samples were initially collected from six test sites and one reference site within the watershed. A total of 23 of these 32 samples were evaluated in 28-day whole-sediment toxicity tests conducted with juvenile mussels (L. siliquoidea). Physical and chemical characterization of whole sediment included grain size, total organic carbon (TOC), nutrients, PCBs, parent and alkylated PAHs, organochlorine pesticides, PCDD/PCDFs, total metals, simultaneously extracted metals (SEM), and acid volatile sulfide (AVS). Sediment collected from Snow Creek and Choccolocco Creek contained a variety of COPCs. Organic contaminants detected in sediment included PCBs, organochlorine pesticides, PCDDs/PCDFs, and PAHs. In general, the highest concentrations of PCBs were associated with the highest concentrations of PAHs, PCDDs/PCDFs, and organochlorine pesticides. Specifically, sediments 08, 18, and 19 exceeded probable effect concentration quotients (PEC-Qs) of 1.0 for all organic classes of contaminants. These three sediment samples also had high concentrations of mercury and lead, which were the only metals found at elevated concentrations (i.e., above the probable effect concentration [PEC]) in the samples collected. Many sediment samples were highly contaminated with mercury, based on comparisons to samples collected from reference locations. The whole-sediment laboratory toxicity tests conducted with L. siliquoidea met the test acceptability criteria (e.g., control survival was greater than or equal to 80%). Survival of mussels was high in most samples, with 4 of 23 samples (17%) classified as toxic based on the survival endpoint. Biomass and weight were more sensitive endpoints for the L. siliquoidea toxicity tests, with both endpoints classifying 52% of the samples as toxic. Samples 19 and 30 were most toxic to L. siliquoidea, as they were classified as toxic according to all four endpoints (survival, biomass, weight, and length). Mussels were less sensitive in toxicity tests conducted with sediments from the Anniston PCB Site than Hyalella azteca and Chironomus dilutus. Biomass of L. siliquoidea was less sensitive compared to biomass of H. azteca or biomass of larval C. dilutus. Based on the most sensitive endpoint for each species, 52% of the samples were toxic to L. siliquoidea, whereas 67% of sediments were toxic to H. azteca (based on reproduction) and 65% were toxic to C. dilutus (based on adult biomass). The low-risk toxicity threshold (TTLR) was higher for L. siliquoidea biomass (e.g., 20,400 µg/kg dry weight [DW]) compared to that for H. azteca reproduction (e.g., 499 µg/kg DW) or C. dilutus adult biomass (e.g., 1,140 µg/kg DW; MacDonald et al. 2014). While mussels such as L. sili

Alabama

Effects of water temperature and pH on toxicity of terbufos, trichlorfon, 4-nitrophenol and 2,4-dinitrophenol to the amphipod Gammarus pseudolimnaeus and rainbow trout (Oncorhynchus mykiss)

Acute toxicity tests were conducted to determine (a) the individual and interactive effects of water temperature (7, 12, 17°C), pH (6 5, 7 5, 8 5, 9 5), and time on the toxicity of terbufos, trichlorfon, 4 nitrophenol, and 2,4-dinitrophenol to rainbow trout ( Oncorhynchus mykiss ) and the amphipod Gammarus pseudohmnaeus , and (b) the individual and interactive effects of water temperature and pH on chemical bioconcentration during acute tests with rainbow trout and Gammarus exposed to terbufos, 4 nitrophenol, and 2,4 dinitrophenol The toxicity of all four chemicals was significantly affected by pH in all tests, except for Gammarus exposed to terbufos The toxicity of terbufos to rainbow trout and Gammarus was less at pH 7 5 than at higher or lower pH The toxicity of both nitrophenols decreased as pH increased, whereas the toxicity of trichlorfon increased with pH The effect of pH on trichlorfon toxicity decreased with temperature Temperature significantly affected the toxicity of all four chemicals to both species Toxicity increased with temperature in all tests, except for rainbow trout exposed to nitrophenols, toxicity decreased as temperature increased for rainbow trout Chemical bioconcentration was also significantly af fected by temperature and pH and was directly related to toxicity in most tests Significant interactive effects between toxicity modifying factors were also frequently observed Temperature and pH effects on chemical toxicity need to be consid ered in chemical hazard assessment to ensure adequate protection of aquatic organisms

Environmental Toxicology and Chemistry

Estimating aquatic toxicity as determined through laboratory tests of great lakes sediments containing complex mixtures of environmental contaminants

We developed and evaluated a total toxic units modeling approach for predicting mean toxicity as measured in laboratory tests for Great Lakes sediments containing complex mixtures of environmental contaminants (e.g., polychlorinated biphenyls, polycyclic aromatic hydrocarbons, pesticides, chlorinated dioxins, and metals). The approach incorporates equilibrium partitioning and organic carbon control of bioavailability for organic contaminants and acid volatile sulfide (AVS) control for metals, and includes toxic equivalency for planar organic chemicals. A toxic unit is defined as the ratio of the estimated pore-water concentration of a contaminant to the chronic toxicity of that contaminant, as estimated by U.S. Environmental Protection Agency Ambient Water Quality Criteria (AWQC). The toxic unit models we developed assume complete additivity of contaminant effects, are completely mechanistic in form, and were evaluated without any a posteriori modification of either the models or the data from which the models were developed and against which they were tested. A linear relationship between total toxic units, which included toxicity attributable to both iron and un-ionized ammonia, accounted for about 88% of observed variability in mean toxicity; a quadratic relationship accounted for almost 94%. Exclusion of either bioavailability components (i.e., equilibrium partitioning control of organic contaminants and AVS control of metals) or iron from the model substantially decreased its ability to predict mean toxicity. A model based solely on un-ionized ammonia accounted for about 47% of the variability in mean toxicity. We found the toxic unit approach to be a viable method for assessing and ranking the relative potential toxicity of contaminated sediments.

Great Lakes region

Acute toxicity of the herbicide bromoxynil to Daphnia magna

The acute toxicities of technical-grade bromoxynil octanoate (BO) and two commercial formulations, Buctril® and Bronate®, to < 24-h-old neonate Daphnia magna (Straus) were determined in soft, hard, and oligosaline water. In addition, effects of life stage, feeding, aging the herbicide, and exposure duration on BO toxicity to daphnids were investigated. Regardless of formulation, life stage, and water quality, BO was found to be extremely to highly toxic to daphnids in standard tests; 48-h EC50 values ranged from 41 to 161 m̈g/L. Bromoxynil octanoate was the most toxic to neonates in soft water and the least toxic in hard water. The acute toxicities of the three bromoxynil herbicides to a given age group of daphnids were similar within the same water type. Overall, neonates and 7-d-old adults were more sensitive than 14- or 15-d-old adults to each herbicide. Feeding daphnids during the toxicity test significantly decreased BO toxicity compared to not feeding them. Aging BO (as Buctril) in hard water decreased its toxicity, and the rate of deactivation was rapid, with an estimated half-life of biological activity of 13 h. Daphnids immobilized by exposures to toxic BO concentrations for ≤ 6 h recovered their mobility, whereas exposures of 18 and 24 h to BO produced toxic effects in daphnids similar to those exposed for 48 h. These results indicated that standard continuous exposure tests may not adequately predict the acute toxicity of BO to freshwater animals in the field.

Environmental Toxicology and Chemistry

Predicting toxic effects of copper on aquatic biota in mineralized areas by using the Biotic Ligand Model

The chemical speciation of metals influences their biological effects. The Biotic Ligand Model (BLM) is a computational approach to predict chemical speciation and acute toxicological effects of metals on aquatic biota. Recently, the U.S. Environmental Protection Agency incorporated the BLM into their regulatory water-quality criteria for copper. Results from three different laboratory copper toxicity tests were compared with BLM predictions for simulated test-waters. This was done to evaluate the ability of the BLM to accurately predict the effects of hardness and concentrations of dissolved organic carbon (DOC) and iron on aquatic toxicity. In addition, we evaluated whether the BLM and the three toxicity tests provide consistent results. Comparison of BLM predictions with two types of Ceriodaphnia dubia toxicity tests shows that there is fairly good agreement between predicted LC50 values computed by the BLM and LC50 values determined from the two toxicity tests. Specifically, the effect of increasing calcium concentration (and hardness) on copper toxicity appears to be minimal. Also, there is fairly good agreement between the BLM and the two toxicity tests for test solutions containing elevated DOC, for which the LC50 is 3-to-5 times greater (less toxic) than the LC50 for the lower-DOC test water. This illustrates the protective effects of DOC on copper toxicity and demonstrates the ability of the BLM to predict these protective effects. In contrast, for test solutions with added iron there is a decrease in LC50 values (increase in toxicity) in results from the two C. dubia toxicity tests, and the agreement between BLM LC50 predictions and results from these toxicity tests is poor. The inability of the BLM to account for competitive iron binding to DOC or DOC fractionation may be a significant shortcoming of the BLM for predicting site- specific water-quality criteria in streams affected by iron-rich acidic drainage in mined and mineralized areas.

Conference Paper

Pesticide mixtures show potential toxicity to aquatic life in U.S. streams, water years 2013-2017

During water years (WY) 2013–2017, the U.S. Geological Survey, National Water-Quality Assessment (NAWQA) Project, sampled the National Water Quality Network – Rivers and Streams (NWQN) year-round and reported on 221 pesticides at 72 sites across the United States in agricultural, developed, and mixed land use watersheds. The Pesticide Toxicity Index (PTI) was used to estimate the potential chronic and acute toxicity to three taxonomic groups – fish, cladocerans, and benthic invertebrates. For invertebrates (either cladocerans, benthic invertebrates, or both), the maximum PTI score exceeded the predicted acute toxicity screening level at 18 of the 72 sites (25%) at some point during WY 2013–2017. The predicted toxicity of a single pesticide compound was found to overwhelm the toxicity of other pesticides in the mixtures after concentrations were toxicity weighted. For this study, about 71%, 72%, and 92% of the Fish-, Cladoceran-, and Benthic Invertebrate-PTI scores, respectively, had one pesticide compound primarily contributing to sample potential toxicity (>50%). There were 17 (13 insecticides, 2 herbicides, 1 fungicide, and 1 synergist) of the 221 pesticide compounds analyzed that were the primary drivers of potential toxicity in each water sample in which the PTI and TUmax (toxic unit score for the pesticide that makes the single largest contribution to the PTI) scores were above predicted chronic (>0.1) or acute (>1) toxicity levels for one of the three taxa. For cladocerans and benthic invertebrates, the drivers of predicted chronic (>0.1) and acute (>1) PTIs were mostly insecticides. For cladocerans, the pesticide compounds driving the PTI scores were bifenthrin, carbaryl, chlorpyrifos, diazinon, dichlorvos, dicrotophos, diflubenzuron, flubendiamide, and tebupirimfos. For benthic invertebrates, atrazine (an herbicide), as well as the insecticides – bifenthrin, carbaryl, carbofuran, chlorpyrifos, diazinon, dichlorvos, fipronil, imidacloprid, and methamidophos – were the drivers of predicted toxicity. For fish, there were three pesticide types that contributed the most to predicted chronic (>0.1) PTIs – acetochlor, an herbicide; carbendazim, a fungicide degradate; and piperonylbutoxide, a synergist.

Science of the Total Environment

Indices of benthic community tolerance in contaminated Great Lakes sediments: Relations with sediment contaminant concentrations, sediment toxicity, and the sediment quality triad

We evaluated the toxic-units model developed by Wildhaber and Schmitt (1996) as a predictor of indices of mean tolerance to pollution (i.e., Lenat, 1993; Hilsenhoff, 1987) and other benthic community indices from Great Lakes sediments containing complex mixtures of environmental contaminants (e.g., polychlorinated biphenyls – PCBs, polycyclic aromatic hydrocarbons – PAHs, pesticides, chlorinated dioxins, and metals). Sediment toxic units were defined as the ratio of the estimated pore-water concentration of a contaminant to its chronic toxicity as estimated by U.S. Environmental Protection Agency Ambient Water Quality Criteria (AWQC) or other applicable standard. The total hazard of a sediment to aquatic life was assessed by summing toxic units for all contaminants quantified. Among the benthic community metrics evaluated, total toxic units were most closely correlated with Lenat's (1993) and Hilsenhoff's (1987) indices of community tolerance ( T L and T H , respectively); toxic units accounted for 42% T L and 53% T H of variability in community tolerance as measured by Ponar grabs. In contrast, taxonomic richness and Shannon-Wiener diversity were not correlated (P > 0.05) with toxic units. Substitution of order- or family-level identifications for lowest possible (mostly genus- or species-) level identifications in the calculation of T L and T H indices weakened the relationships with toxic units. Tolerance values based on order- and family-level identifications of benthos for artificial substrate samples were more strongly correlated with toxic units than tolerance values for benthos from Ponar grabs. The ability of the toxic-units model to predict the other two components (i.e., laboratory-measured sediment toxicity and benthic community composition) of the Sediment Quality Triad (SQT) may obviate the need for the SQT in some situations.

Environmental Monitoring and Assessment

Characterizing toxicity of metal‐contaminated sediments from the Upper Columbia River, Washington, USA, to benthic invertebrates

Sediments from the Upper Columbia River, Washington, USA, are contaminated with metals from smelting operations. We conducted short‐term and long‐term tests with the midge Chironomus dilutus and the amphipod Hyalella azteca and short‐term tests with the freshwater mussel Lampsilis siliquoidea with 54 sediments from the Upper Columbia River to characterize thresholds for toxicity of metals to benthic invertebrates. Test sediments were screened for toxicity by comparisons with low‐metal reference sediments. Toxic effects on amphipods occurred primarily in sediments from the upstream (riverine) reach, and toxic effects on midges occurred in sediments from both the upstream reach and the downstream (reservoir) reach. Little toxicity was observed in mussel tests. Toxicity thresholds (20% effect concentrations [EC20s]) for metals in sediment and porewater were estimated from logistic concentration–response models. Copper (Cu) concentrations in the simultaneously extracted metal fraction of sediments and bioavailable Cu in porewater, as characterized by biotic ligand models, had consistent associations with toxicity endpoints. Concentration–response models for sediment Cu produced EC20s for 6 endpoints, with long‐term amphipod survival and reproduction being the most sensitive. A logistic regression model fitted to an endpoint sensitivity distribution for sediment Cu predicted that approximately one‐half of the sediments tested would be toxic to at least one endpoint and that approximately 20% of test sediments would be toxic to more than half of the endpoints. These results indicate that sediments from the upstream reach of the Upper Columbia River, which contain high concentrations of metals associated with slags, cause a wide range of toxic effects in laboratory tests and are likely to have adverse effects on benthic invertebrate communities.

Washington

Development and application of freshwater sediment-toxicity benchmarks for currently used pesticides

Sediment-toxicity benchmarks are needed to interpret the biological significance of currently used pesticides detected in whole sediments. Two types of freshwater sediment benchmarks for pesticides were developed using spiked-sediment bioassay (SSB) data from the literature. These benchmarks can be used to interpret sediment-toxicity data or to assess the potential toxicity of pesticides in whole sediment. The Likely Effect Benchmark (LEB) defines a pesticide concentration in whole sediment above which there is a high probability of adverse effects on benthic invertebrates, and the Threshold Effect Benchmark (TEB) defines a concentration below which adverse effects are unlikely. For compounds without available SSBs, benchmarks were estimated using equilibrium partitioning (EqP). When a sediment sample contains a pesticide mixture, benchmark quotients can be summed for all detected pesticides to produce an indicator of potential toxicity for that mixture. Benchmarks were developed for 48 pesticide compounds using SSB data and 81 compounds using the EqP approach. In an example application, data for pesticides measured in sediment from 197 streams across the United States were evaluated using these benchmarks, and compared to measured toxicity from whole-sediment toxicity tests conducted with the amphipod Hyalella azteca (28-d exposures) and the midge Chironomus dilutus (10-d exposures). Amphipod survival, weight, and biomass were significantly and inversely related to summed benchmark quotients, whereas midge survival, weight, and biomass showed no relationship to benchmarks. Samples with LEB exceedances were rare (n = 3), but all were toxic to amphipods (i.e., significantly different from control). Significant toxicity to amphipods was observed for 72% of samples exceeding one or more TEBs, compared to 18% of samples below all TEBs. Factors affecting toxicity below TEBs may include the presence of contaminants other than pesticides, physical/chemical characteristics of sediment, and uncertainty in TEB values. Additional evaluations of benchmarks in relation to sediment chemistry and toxicity are ongoing.

Science of the Total Environment

Using organic compounds and salt mixtures to investigate potential mechanisms of major ion toxicity to the mayfly Neocloeon triangulifer

Field assessments and laboratory studies have demonstrated that mayflies (Ephemeroptera) are relatively sensitive to increased concentrations of major geochemical ions (Na + , Ca 2+ , Mg 2+ , K + , Cl − , SO 4 2− , HCO 3 − /CO 3 2- ), but much remains to be learned about potential mechanisms of toxicity. In the present study, we sought to determine whether solution osmolarity is sufficient to predict the toxic effects of major ions to a mayfly, Neocloeon triangulifer . We further investigated whether binary mixtures of major ion salts with common cations or common anions provide evidence of concentration addition or independent action, potentially illuminating toxicity drivers for this species. Finally, we sought to determine if there are mechanisms for major ion toxicity to mayflies that are comparable to those for other species. The toxicity of single salts showed a Ca-dependent correlation with the total component concentration (the sum of individual ion concentrations, a close correlate of osmolarity), but the effect concentrations were well below those causing toxicity from mannitol (presumed to have only an osmotic effect), suggesting that a general osmotic effect is not responsible for major ion toxicity in this species. The mixture experiments consistently indicated additive toxicity and consistency with the relationship to total component concentration, which supports a single toxic mechanism and thus no evidence for ion-specific mechanisms, as reported for other species. Given the lack of evidence of ion-specific toxicity, the total component metric is likely useful for a broad range of ionic compositions.

Environmental Toxicology and Chemistry

Characterization of toxic conditions above Wilson's Creek National Battlefield Park, Missouri

ABSTRACT: Wilson's Creek has an extensive history of toxicity from both point and nonpoint sources. Seven-day chronic daphnid ( Ceriodaphnia dubia ) bioassays identified one toxic site in the Wilson's Creek watershed. Procedures for the characterization phase of a Toxicity Identification Evaluation (TIE) were modified for chronic assessment and performed on four water samples from the toxic site. The characterization involved chemical/physical alterations of samples, combined with bioassays, to help in identification of the class(es) of toxicants; followed by chemical analyses. To help understand the additivity of mixtures, toxic units were derived. Successive samples contained concentrations of copper, cadmium, nickel and zinc that literature values describe as being chronically toxic to daphnids. Summed chronic toxic units for these values greatly exceeded ambient toxic units, and more than accounted for observed toxicity.

Journal of the American Water Resources Associatio

Evaluation of ability of reference toxicity tests to identify stress in laboratory populations of the amphipod Hyalella azteca

Standard methods for conducting toxicity tests imply that the condition of test organisms can be established using reference toxicity tests. However, only a limited number of studies have evaluated whether reference toxicity tests can actually be used to determine if organisms are in good condition at the start of a test. We evaluated the ability of reference toxicants to identify stress associated with starvation in laboratory populations of the amphipod Hyalella azteca using acute toxicity tests and four reference toxicants: KCl, CdCl2, sodium pentachlorophenate (NaPCP), and carbaryl. Stress associated with severe starvation was observed with exposure of amphipods to carbaryl or NaPCP but not with exposure to KCl or CdCl2 (i.e., lower LC50 with severe starvation). Although the LC50s for NaPCP and carbaryl were statistically different between starved and fed amphipods, this difference may not be biologically significant given the variability expected in acute lethality tests. Stress associated with sieving, heat shock, or cold shock of amphipods before the start of a test was not evident with exposure to carbaryl or KCl as reference toxicants. The chemicals evaluated in this study provided minimal information about the condition of the organisms used to start a toxicity test. Laboratories should periodically perform reference toxicity tests to assess the sensitivity of life stages or strains of test organisms. However, use of other test acceptability criteria required in standard methods such as minimum survival, growth, or reproduction of organisms in the control treatment at the end of a test, provides more useful information about the condition of organisms used to start a test compared to data generated from reference toxicity tests.

Environmental Toxicology and Chemistry

Effects of organic amendments on the toxicity and bioavailability of cadmium and copper in spiked formulated sediments

We evaluated the partitioning and toxicity of cadmium (Cd) and copper (Cu) spiked into formulated sediments containing two types of organic matter (OM), i.e., cellulose and humus. Amendments of cellulose up to 12.5% total organic carbon (TOC) did not affect partitioning of Cd or Cu between sediment and pore water and did not significantly affect the toxicity of spiked sediments in acute toxicity tests with the amphipod Hyalella azteca. In contrast, amendments of natural humus shifted the partitioning of both Cd and Cu toward greater concentrations in sediment and lesser concentrations in pore water and significantly reduced toxic effects of both metals. Thresholds for toxicity, based on measured metal concentrations in whole sediment, were greater for both Cd and Cu in sediments amended with a low level of humus (2.9% TOC) than in sediments without added OM. Amendments with a high level of humus (8.9% TOC) eliminated toxicity at the highest spike concentrations of both metals (sediment concentrations of 12.4 ??g Cd/g and 493 ??g Cu/g). Concentrations of Cd in pore water associated with acute toxicity were similar between sediments with and without humus amendments, suggesting that toxicity of Cd was reduced primarily by sorption to sediment OM. However, toxic effects of Cu in humus treatments were associated with greater pore-water concentrations than in controls, suggesting that toxicity of Cu was reduced both by sorption and by complexation with soluble ligands. Both sorption and complexation by OM tend to make proposed sediment quality guidelines (SQGs) based on total metal concentrations more protective for high-OM sediments. Our results suggest that the predictive ability of SQGs could be improved by models of metal interactions with natural OM in sediment and pore water.

Conference Paper

Linear solvation energy relationships for toxicity of selected organic chemicals to Daphnia pulex and Daphnia magna

In the Laurentian Great Lakes, more than 300 contaminants have been identified in fish, other biota, water, and sediment. Current hazard assessment of these chemicals by the National Fisheries Research Center-Great Lakes is based on their toxicity, occurrence in the environment, and source. Although scientists at the Center have tested over 70 chemicals with the crustacean Daphnia pulex , the number of experimental data needed to screen the huge array of chemicals in the Great Lakes exceeds the practical capabilities of conducting bioassays. This limitation can be partly circumvented, however, by using mathematical models based on quantitative structure-activity relationships (QSAR) to provide rapid, inexpensive estimates of toxicity. Many properties of chemicals, including toxicity, bioaccumulation and water solubility are well correlated and can be predicted by equations of the generalized linear solvation energy relationships (LSER). The equation we used to model solute toxicity is Toxicity = constant + m VI/100 + s (π* + dδ) + b βm + a αm where VI = intrinsic (Van der Waals) molar volume; π* = molecular dipolarity/polarizability; δ = polarizability 'correction term'; βm = solute hydrogen bond acceptor basicity; and αm = solute hydrogen bond donor acidity. The subscript m designates solute monomer values for α and β. We applied the LSER model to 48-h acute toxicity data (measured as immobilization) for six classes of chemicals detected in Great Lakes fish. The following regression was obtained for Daphnia pulex (concentration = μM): log EC50 = 4.86 - 4.35 VI/100; N = 38, r2 = 0.867, sd = 0.403 We also used the LSER modeling approach to analyze to a large published data set of 24-h acute toxicity for Daphnia magna ; the following regression resulted, for eight classes of compounds (concentration = mM): log EC50 = 3.88 - 4.52 VI/100 - 1.62 π* + 1.66 βm - 0.916 αm; N = 62, r2 = 0.859, sd = 0.375 In addition we developed computer software that identifies chemical structures, estimates the LSER parameters, and predicts toxicity. The LSER models promise to be effective in differentiating between reactive and nonreactive toxicity behavior where other models have failed. Contaminants with reactive behavior are generally the most toxic and rank highest in hazard assessment of environmental chemicals.

Proceedings of the QSAR

Fish egg injection as an alternative exposure route for early life stage toxicity studies: Description of two unique methods: Chapter 4

In the environment, lipophilic contaminants such as halogenated aromatic hydrocarbons (HAHs, e.g., polychlorinated biphenyls, PCBs) and polycyclic aromatic hydrocarbons (PAHs, e.g., benzo[a]pyrene) readily bioaccumulate in fish, and the bioaccumulation of these lipophilic chemicals by adult fish may have significant consequences on the development and survival of their offspring. Halogenated and polycyclic aromatic hydrocarbons translocate from adult female body stores into eggs during oocyte maturation, and early life stages of fish are often more sensitive than adults to the toxicity of these chemicals. Thus, the presence of persistent, bioaccumulative contaminants in the environment may pose a risk to fish early life stage survival and ultimately reduce recruitment into the adult population. Typically, standard early life stage toxicity studies exposed embryos, larvae, and juveniles to graded concentrations of waterborne toxicants, and dose-response relationships are based on the concentrations of chemicals in the water. However, use of waterborne exposure to assess the toxicity of persistent, bioaccumulative contaminants, such as HAHs and PAHs, has two significant drawbacks. First, uptake of hydrophobic chemicals, such as HAHs and PAHs, into the developing embryo from water is not a significant route of exposure in the environment since concentrations of these chemicals freely dissolved in water are extremely low. Rather, maternal deposition into developing oocytes is the most significant source of these chemicals to the embryo. Second, the dose received by the target tissue, in this case the developing embryo, is the most accurate predictor of the toxic response, and since extrapolation from water concentrations of the chemical to egg concentrations is required, the exact dose received by the embryo can only be estimated, often with large uncertainty. Due to these drawbacks, it is important to develop an alternative exposure method that will directly expose the developing embryo without the need to chronically expose adult fish with subsequent natural deposition of hydrophobic chemicals into the oocytes. Fish egg injection provides this exposure route. Embryos are exposed directly after fertilization with known doses of contaminants, the dose is delivered prior to critical developmental events, and extrapolation of the dose received by the embryo is not needed. We have developed two unique fish egg injection methods as alternative routes of exposure for fish early life stage toxicity studies of lipophilic environmental contaminants. With either method, individual fish eggs are injected with a known dose of chemical. The first approach, a microinjection method, originally developed to assess the developmental toxicity of HAH congeners to early life stages of salmonids, utilizes micro-syringes, 30- gauge stainless steel injection needles, and micro- to nanoliter injection volume. The second approach, a nano-injection method, utilizes glass capillary micropipettes with 2 to 10 µm tips as injection needles, and nano- to picoliter injection volume, allowing injection of nearly any size of fish egg. Both of these egg injection methods allow an investigator to assess the toxicity of lipophilic environmental contaminants to early life stages of fish in a manner that realistically reflects environmental exposure and allows accurate quantitation of the dose to the developing embryo. These injection techniques, however, are not limited to use with only lipophilic chemicals. Since the developmental toxicity of many environmental contaminants ultimately depends on the dose received by the embryo, these egg injection methods could serve as a realistic exposure route in many fish early life stage toxicity studies.

Book chapter