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The brominated flame retardant bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH) is used widely in consumer items including polyurethane foam used in furniture. Information on its bioaccumulation in aquatic species is limited and in the current study, sediment bioaccumulation tests with the oligochaete Lumbriculus variegatus were performed on a spiked natural sediment equilibrated for 14.5 months. Analysis showed the TBPH used to spike the sediment contained a small amount (0.046% by mass) of mono-(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBMEHP), a potential biotransformation product of the parent chemical. Steady-state biota-sediment accumulation factors (BSAFs) of 0.254 and 1.50 (kg organic carbon/kg lipid) were derived for TBPH and TBMEHP, respectively. TBPH had biphasic elimination behavior where 94% percent of the body burden was depleted within the first 12 hours of elimination (i.e., half-life of 1.2 hours or less), and the remaining 6% eliminated very slowly thereafter (half-life of 15 days). There was little evidence for biotransformation of either chemical by L. variegatus. This investigation confirms the extremely hydrophobic behavior of TBPH and its impact on its bioavailability.

Mathematical models are presented for the acute median lethal concentrations of major geochemical ions (Na

The results of a series of experiments on the acute toxicity of major geochemical ions (Na

Testicular oocytes in wild adult bass (Micropterus spp.) are considered a potential indication of exposure to estrogenic compounds in municipal, agricultural, or industrial wastewater. However, our ability to interpret links between testicular oocyte occurrence in wild fish species and environmental pollutants is limited by our understanding of normal and abnormal gonadal development. We previously reported low-to-moderate testicular oocyte prevalence (7%-38%) among adult male bass collected from Minnesota waters with no known sources of estrogenic compounds. In the present study, two experiments were conducted in which smallmouth bass (Micropterus dolomieu) fry were exposed to control water or 17-α-ethinylestradiol (EE2) during gonadal differentiation, then reared in clean water for an additional period. Histological samples were evaluated at several time points during the exposure and grow-out periods, and the sequence and timing of gonadal development in the presence of estrogen were compared with that of control fish. Testicular oocytes were not observed in any control or EE2-exposed fish. Among groups exposed to 1.2 or 5.1 ng/L EE2 in Experiment 1 or 3.0 ng/L EE2 in Experiment 2, ovaries were observed in 100% of fish up to 90 days after exposure ceased, and approximately half of those ovaries had abnormal characteristics, suggesting that they likely developed in sex-reversed males. Groups exposed to 0.1, 0.4, or 1.0 ng/L in Experiment 2 developed histologically normal ovaries and testes in proportions not significantly different from 1:1. These findings suggest that, while presumably able to cause sex reversal, juvenile exposure to EE2 may not be a unique cause of testicular oocytes in wild bass, although the long-term outcomes of exposure are unknown. Environ Toxicol Chem 2022;41:1416-1428. © 2022 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Passive sampling to quantify net partitioning of hydrophobic organic contaminants between the porewater and solid phase has advanced risk management for contaminated sediments. Direct porewater (Cfree) measures represent the best way to predict adverse effects to biota. However, when the need arises to convert between solid-phase concentration (Ctotal) and Cfree, a wide variation in observed sediment-porewater partition coefficients (KTOC) is observed due to intractable complexities in binding phases. We propose a stochastic framework in which a given Ctotal is mapped to an estimated range of Cfree through variability in passive sampling-derived KTOC relationships. This mapping can be used to pair estimated Cfree with biological effects data or inversely to translate a measured or assumed Cfree to an estimated Ctotal. We apply the framework to both an effects threshold for polycyclic aromatic hydrocarbon (PAH) toxicity and an aggregate adverse impact on an assemblage of species. The stochastic framework is based on a "bioavailability ratio" (BR), which reflects the extent to which potency-weighted, aggregate PAH partitioning to the solid-phase is greater than that predicted by default, KOW-based KTOC values. Along a continuum of Ctotal, we use the BR to derive an estimate for the probability that Cfree will exceed a threshold. By explicitly describing the variability of KTOC and BR, estimates of risk posed by sediment-associated contaminants can be more transparent and nuanced.

The effects on juvenile rainbow trout survival, growth, food consumption, and food conversion efficiency from dietborne exposures to inorganic arsenic (arsenite, arsenate) and to the organoarsenicals monomethylarsonate (MMA), dimethylarsinate (DMA), and arsenobetaine (AsB) were investigated in two experiments: (1) a 28-d exposure using a live diet of oligochaete worms separately exposed via water to these five arsenic compounds and (2) a 56-d exposure using a pellet diet prepared from commercial fish food to which arsenite, MMA, or DMA were added. In the live diet experiment, the degree to which worms could be contaminated with the organoarsenicals was limited by toxicity to the worms and other experimental constraints, so that their toxicity relative to inorganic arsenic could not be fully established, but AsB was concluded to have low toxicity, consistent with published results for mammals. For the pellet diet experiment, MMA and DMA were found to be at least an order of magnitude less toxic than inorganic As on the basis of concentration in the diet, as well as much less toxic on the basis of accumulation in the fish. The need to consider speciation in aquatic risk assessments for arsenic was further demonstrated by tissue analyses of three macroinvertebrate species from a mining-impacted stream, which showed large variations in both total arsenic and the relative amounts of inorganic and organic arsenic. Additionally, although effects of arsenic on trout appear to be well correlated with inorganic arsenic, worms were found to be more sensitive to waterborne DMA than to inorganic arsenic, showing that low toxicity of organoarsenicals cannot be assumed for all aquatic organisms. Various difficulties in evaluating and applying studies on dietborne exposures and fish growth are also discussed.

Direct measurement of the n-octanol partition coefficients (K(OW)) for highly hydrophobic organic chemicals is extremely difficult because of the extremely low concentrations present in the water phase. n-Butanol/water partition coefficients (K(BW)) are generally much lower than K(OW) due to the increased solubility of solute in the alcohol saturated aqueous phase, and therefore become easier to measure. We measured the K(BW) for 25 neutral organic chemicals having measured log K(OW)s ranging from 2 to 9 and 4 additional highly hydrophobic chemicals, with unmeasured K(OW)s, having estimated log K(OW)s ranging from 6 to 18. The measured log K(BW) and log K(OW) values were linearly related, r(2)= 0.978, and using the regression developed from the data, K(OW)s were predicted for the 4 highly hydrophobic chemicals with unmeasured K(OW)s. The resulting predictions were orders of magnitude lower than those predicted by a variety of computational models and suggests the estimates of K(OW) in the literature for highly hydrophobic chemicals (i.e., log K(OW) greater than 10) are likely incorrect by several orders of magnitude.

An emerging Multi-Ion Toxicity (MIT) model for assessment of environmental salt pollution is based on the premise that major ion toxicity to aquatic organisms is related to a critical disturbance of the trans-epithelial potential across the gills (ΔTEP), which can be predicted by electrochemical theory. However, the model has never been evaluated physiologically. We directly tested key assumptions by examining the individual effects of eight different salts (NaCl, Na2SO4, MgCl2, MgSO4, KCl, K2SO4, CaCl2, and CaSO4) on measured TEP in three different fish species (fathead minnow, Pimephales promelas = FHM; channel catfish, Ictalurus punctatus = CC; bluegill, Lepomis macrochirus = BG). A geometric concentration series based on previously reported 96-h LC50 values for FHM was used. All salts caused concentration-dependent increases in TEP to less negative/more positive values in a pattern well-described by the Michaelis-Menten equation. The ΔTEP responses for different salts were similar to one another within each species when concentrations were expressed as a percentage of the FHM LC50. A plateau was reached at or before 100 % of the LC50 where the ΔTEP values were remarkably consistent, with only 1.4 to 2.2-fold variation. This relative uniformity in the ΔTEP responses contrasts with 28-fold variation in salt concentration (in mmol L−1), 9.6-fold in total dissolved solids, and 7.9-fold in conductivity at the LC50. The Michaelis-Menten Km values (salt concentrations causing 50 % of the ΔTEPmax) were positively related to the 96-h LC50 values. ΔTEP responses were not a direct effect of osmolarity in all species and were related to specific cation rather than specific anion concentrations in FHM. These responses were stable for up to 24 h in CC. The results provide strong physiological support for the assumptions of the MIT model, are coherent with electrochemical theory, and point to areas for future research.

Freshwater mussels (order Unionoida) are one of the most imperiled groups of animals in the world. However, many ambient water quality criteria and other environmental guideline values do not include data for freshwater mussels, in part because mussel toxicity test methods are comparatively new and data may not have been available when criteria and guidelines were derived. The objectives of the present study were to evaluate the acute toxicity of sodium chloride (NaCl) and potassium chloride (KCl) to larvae (glochidia) and/or juveniles of a unionid mussel (fatmucket, Lampsilis siliquoidea) and to determine the potential influences of water hardness (50, 100, 200, and 300 mg/L as CaCO3 ) and other major ions (Ca, K, SO4 , or HCO3 ) on the acute toxicity of NaCl to the mussels. From the KCl test, the 50% effect concentration (EC50) for fatmucket glochidia was 30 mg K/L, similar to or slightly lower than the EC50s for juvenile fatmucket (37-46 mg K/L) tested previously in our laboratory. From the NaCl tests, the EC50s for glochidia increased from 441 to 1597 mg Cl/L and the EC50s for juvenile mussels increased from 911 to 3092 mg Cl/L with increasing water hardness from 50 to 300 mg/L. Increasing K from 0.4 to 1.9 mg/L, SO4 from 13 to 40 mg/L, or HCO3 from 44 to 200 mg/L in the 50 mg/L hardness water did not substantially change the NaCl EC50s for juvenile mussels, whereas increasing Ca from 9.9 to 42 mg/L increased the EC50s by a factor of 2. The overall results indicate that glochidia were equally or more sensitive to NaCl and KCl compared with juvenile mussels and that the increased water hardness ameliorated the acute toxicity of NaCl to glochidia and juveniles. These responses rank fatmucket among the most acutely sensitive freshwater organisms to NaCl and KCl. Environ Toxicol Chem 2018;37:3041-3049. © 2018 SETAC. This article is a US government work and, as such, is in thepublic domain in the United States of America.

Testicular oocytes (TOs) have been found in black bass (Micropterus spp.) from many locations in North America. The presence of TOs is often assumed to imply exposure to estrogenic endocrine disrupting compounds (EDCs); however, a definitive causal relationship has yet to be established, and TO prevalence is not consistently low in fish from areas lacking evident EDC sources. This might indicate any of a number of situations: 1) unknown or unidentified EDCs or EDC sources, 2) induction of TOs by other stressors, or 3) testicular oocytes occurring spontaneously during normal development. In the present study, we analyzed TO occurrence in smallmouth bass (Micropterus dolomieu) from 8 populations in northeastern Minnesota watersheds with differing degrees of human development and, hence, presumed likelihood of exposure to anthropogenic chemicals. Three watersheds were categorized as moderately developed, based on the presence of municipal wastewater discharges and higher human population density (4-81 per km2 ), and 5 watersheds were minimally developed, with very low human population density (0-1 per km2 ) and minimal built environment. Testicular tissues from mature fish were evaluated using a semiquantitative method that estimated TO density, normalized by cross-sectional area. Testicular oocyte prevalence and density among populations from moderately developed watersheds was higher than in populations from minimally developed watersheds. However, TO prevalence was unexpectedly high and variable (7-43%) in some populations from minimally developed watersheds, and only weak evidence was found for a relationship between TO density and watershed development, suggesting alternative or more complex explanations for TO presence in smallmouth bass from this region. Environ Toxicol Chem 2017;36:3424-3435. © 2017 SETAC.

Many metals (aluminum, cadmium, cobalt, copper, nickel, lead, zinc) are widely studied environmental contaminants because of their ubiquity, potential toxicity to aquatic life, and tendency for toxicity to vary widely as a function of water chemistry. The interactions between metal and water chemistry influence metal "bioavailability," an index of the rate and extent to which the metal reaches the site of toxic action. The implications of metal bioavailability for ecological risk assessment are large, with as much as a 100-fold variability across a range of water chemistries in surface waters. Beginning as early as the 1930s, considerable research effort was expended toward documenting and understanding metal bioavailability as a function of total and dissolved metal, water hardness, natural organic matter, pH, and other water characteristics. The understanding of these factors and improvements in both analytical and computational chemistry led to the development of modeling approaches intended to describe and predict the relationship between water chemistry and metal toxicity, including the free ion activity model, the gill surface interaction model, the biotic ligand model, and additional derivatives and regression models that arose from similar knowledge. The arc of these scientific advances can also be traced through the evolution of the US Environmental Protection Agency's ambient water quality criteria over the last 50 yr, from guidance in the "Green Book" (1968) to metal-specific criteria produced in the last decade. Through time, water quality criteria in many jurisdictions have incorporated increasingly sophisticated means of addressing metal bioavailability. The present review discusses the history of scientific understanding of metal bioavailability and the development and application of models to incorporate this knowledge into regulatory practice. Environ Toxicol Chem 2019;39:48-59. (c) 2019 SETAC

Many human activities increase concentrations of major geochemical ions (Na+1 , K+1 , Ca+2 , Mg+2 , Cl-1 , SO4-2 , and HCO3-1 /CO3-2 ) in freshwater systems, and can thereby adversely affect aquatic life. Such effects involve several toxicants, multiple toxicity mechanisms, various ion interactions, and widely varying ion compositions across different water bodies. Previous studies of individual salt toxicities have defined some useful relationships; however, adding single salts to waters results in atypical compositions and does not fully address mixture toxicity. To better understand mechanisms and interactions for major ion toxicity, 29 binary mixture experiments, each consisting of 7 to 8 toxicity tests, were conducted on the acute toxicity of major ion salts and mannitol to Ceriodaphnia dubia. These tests showed multiple mechanisms of toxicity, including: 1) nonspecific ion toxicity, correlated with osmolarity and to which all ions contribute; and 2) cation-dependent toxicities for potassium (K), magnesium (Mg), and calcium (Ca) best related to their chemical activities. These mechanisms primarily operate independently, except for additive toxicity of Mg-dependent and Ca-dependent toxicities. These mixture studies confirmed ameliorative effects of Ca on sodium (Na) and Mg salt toxicities and of Na on K salt toxicity, and further indicated lesser ameliorative effects of Ca on K salt toxicity and Mg on Na salt toxicity. These results provide a stronger basis for assessing risks from the complex mixtures of ions found in surface waters. Environ Toxicol Chem 2017;36:1525-1537. Published 2016 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

The ions Na+ , K+ , Ca2+ , Mg2+ , Cl- , SO42- , and HCO3- /CO32- (referred to in the present study as "major ions") are present in all freshwaters and physiologically required by aquatic organisms but can increase to harmful levels from a variety of anthropogenic activities. It is also known that the toxicities of major ion salts can vary depending on the concentrations of other ions, and understanding these relationships is key to establishing appropriate environmental limits. The authors present a series of experiments with Ceriodaphnia dubia to evaluate the acute toxicity of 12 major ion salts and to determine how toxicity of these salts varies as a function of background water chemistry. All salts except CaSO4 and CaCO3 were acutely toxic below saturation, with the lowest median lethal concentrations found for K salts. All 10 salts that showed toxicity also showed some degree of reduced toxicity as the ionic content of the background water increased. Experiments that independently varied Ca:Mg ratio, Na:K ratio, Cl:SO4 ratio, and alkalinity/pH demonstrated that Ca concentration was the primary factor influencing the toxicities of Na and Mg salts, whereas the toxicities of K salts were primarily influenced by the concentration of Na. These experiments also indicated multiple mechanisms of toxicity and suggested important aspects of dosimetry; the toxicities of K, Mg, and Ca salts were best related to the chemical activity of the cation, whereas the toxicities of Na salts also reflected an influence of the anions and were well correlated with osmolarity. Understanding these relationships between major ion toxicity and background water chemistry should aid in the development of sensible risk-assessments and regulatory standards. Environ Toxicol Chem 2016;35:3039-3057. Published 2016 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Studies have been conducted to refine US Environmental Protection Agency, ASTM International, and Environment Canada standard methods for conducting 42-d reproduction tests with Hyalella azteca in water or in sediment. Modifications to the H. azteca method include better-defined ionic composition requirements for exposure water (i.e., >15 mg/L of chloride and >0.02 mg/L of bromide) and improved survival, growth, and reproduction with alternate diets provided as increased rations over time in water-only or whole-sediment toxicity tests. A total of 24 laboratories volunteered to participate in the present interlaboratory study evaluating the performance of H. azteca in 42-d studies in control sand or control sediment using the refined methods. Improved growth and reproduction of H. azteca was observed with 2 alternate diets of 1) ramped diatoms (Thalassiosira weissflogii) + ramped Tetramin or 2) yeast-cerophyll-trout chow (YCT) + ramped Tetramin, especially when compared with results from the traditional diet of 1.8 mg YCT/d. Laboratories were able to meet proposed test acceptability criteria and in most cases had lower variation in growth or reproduction compared with previous interlaboratory studies using the traditional YCT diet. Laboratory success in conducting 42-d H. azteca exposures benefited from adherence to several key requirements of the detailed testing, culturing, and handling methods. Results from the present interlaboratory study are being used to help revise standard methods for conducting 10-d to 42-d water or sediment toxicity exposures with H. azteca. Environ Toxicol Chem 2016;35:2439-2447. © 2016 SETAC.

At contaminated sediment sites, the bioavailability of contaminants in sediments is assessed using sediment-bioaccumulation tests with Lumbriculus variegates (Lv). The testing protocols recommend that ratio of total organic carbon (TOC) in sediment to L. variegatus (dry weight) (TOC/Lv) should be no less than 50:1. Occasionally, this recommendation is not followed, especially with sediments having low TOC, e.g.

The survival and growth of juvenile fathead minnows were investigated at various combinations of waterborne exposure to arsenate and of dietborne exposure to oligochaete worms which had been exposed to inorganic arsenic. Previous work with rainbow trout established that dietborne arsenic can reduce fish growth at environmentally relevant concentrations and could be more important than waterborne exposures. This was found to be less true for fathead minnows, which were less sensitive to dietborne exposures than rainbow trout, while being as or more sensitive to waterborne exposures. When assessed on the basis of accumulation of total As by the fish, further differences between fathead minnows and rainbow trout were evident. Fathead minnows accumulated relatively more arsenic from water versus diet than trout, and the accumulations at which growth effects occurred in minnows were different for dietborne and waterborne exposure, whereas they were the same for trout. These results suggest complex relationships involving arsenic speciation, toxicokinetics, and toxicodynamics, and underscore a need for care in relating effects information to real-world exposures. The present study also demonstrated the challenges in testing and interpreting growth effects in long-term exposures to fish, because the expression of toxicity can be confounded by the relationship of fish growth to size, the feeding regime, and wet weight versus dry weight relationships.

The toxicity of waters with sufficiently elevated concentrations of major geochemical ions (Na(+), K(+), Ca(2+), Mg(2+), Cl(−), SO(4)(2−), and HCO(3)(−)/CO(3)(2−)) to aquatic life is well documented, though the majority of such studies have focused on acute toxicity. In previous work we intensively studied the acute responses of the cladoceran, Ceriodaphnia dubia, to major ion salts and their mixtures, culminating in the development of models to predict acute toxicity from ionic composition. To quantitatively evaluate whether the toxicological behavior of major ions observed for C. dubia extends to chronic toxicity, we conducted 60 chronic toxicity tests with individual salts and binary mixtures thereof. Chronic responses paralleled those demonstrated previously for acute exposure, specifically: 1) similar relative toxicity of individual salts; 2) different Na salts showing similar potency when exposure is expressed as osmolarity; 3) toxicity of Mg, Ca, and K salts related to cation activity; 4) decreased toxicity of Na and Mg salts when Ca activity is increased at less than toxic concentrations; 5) additive behavior for salt mixtures sharing a common cation; 6) independent behavior for salt mixtures with dissimilar cations, except Mg/Ca mixtures which appeared additive; and 7) expressing exposure on the basis of chemical activity rather than total concentration improved coherence of data across different ion mixtures. Acute-chronic ratios were fairly consistent among salts, with values around 1.8 for acute LC50:chronic EC50, and 2.8 for LC50/EC20 when expressed on an activity basis. Adjusting the previous acute toxicity model for acute-chronic ratios yielded chronic models that predict chronic toxicity within the range of inter-test variability. As these models are informed by a wide range of ion mixtures, they should provide robust assessment tools for waters with a variety of ionic compositions.

Field and laboratory studies have shown that mayflies (Ephemeroptera) tend to be relatively sensitive to elevated major ion concentrations, but little is known about how ionic composition influences these responses. The present study evaluated the acute toxicity of major ion salts to the mayfly Neocloeon triangulifer over a range of background water quality conditions. The mayfly was particularly sensitive to Na2 SO4 , with the median lethal concentration (LC50) of 1338 mg SO4 /L being lower than LC50s reported for 7 other species at that hardness. Increasing hardness of the dilution water from 30 to 150 mg/L (as CaCO3 ) resulted in doubling of LC50s for sodium salts, and an approximately 1.5-fold increase in LC50 for MgSO4 . Potassium salt toxicity was not strongly influenced by hardness, consistent with findings for other species. When hardness was held constant but the Ca to Mg ratio was manipulated, the ameliorative effect on Na2 SO4 and NaCl did not appear as strong as when hardness was varied; but for MgSO4 the amelioration relative to Ca activity was similar between the 2 experiments. The toxicity of K salts to N. triangulifer was similar to Na salts on a millimolar basis, which contrasts with several other species for which K salts have been much more toxic. In addition, the toxicity of KCl to N. triangulifer was not notably affected by Na concentration, as has been shown for Ceriodaphnia dubia. Finally, plotting LC50s in terms of ion activity (Cl, SO4 , Na, Mg, or K) over the range of Ca activities in dilution water resulted in significant positive relationships, with comparable slopes to those previously observed for C. dubia over the same range of Ca activities. Environ Toxicol Chem 2018;37:1330-1339. © 2018 SETAC.

Freshwater mussels (order Unionoida) are one of the most imperiled groups of animals in the world. However, many ambient water quality criteria and other environmental guideline values do not include data for freshwater mussels, in part because mussel toxicity test methods are comparatively new and data may not have been available when criteria and guidelines were derived. The objectives of the present study were to evaluate the acute toxicity of sodium chloride (NaCl) and potassium chloride (KCl) to larvae (glochidia) and/or juveniles of a unionid mussel (fatmucket, Lampsilis siliquoidea), and to determine the potential influences of water hardness (50, 100, 200, and 300 mg/L as CaCO(3)) and other major ions (Ca, K, SO(4), or HCO(3)) on the acute toxicity of NaCl to the mussels. From the KCl test, the 50% effect concentration (EC50) for fatmucket glochidia was 30 mg K/L, similar to or slightly lower than EC50s for juvenile fatmucket (37-46 mg K/L) tested previously in our laboratory. From the NaCl tests, the EC50s for glochidia increased from 441 to 1,597 mg Cl/L and the EC50s for juvenile mussels increased from 911 to 3,092 mg Cl/L with increasing water hardness from 50 to 300 mg/L. Increasing K from 0.4 to 1.9 mg/L, SO(4) from 13 to 40 mg/L, or HCO(3) from 44 to 200 mg/L in the 50 mg/L hardness water did not substantially change the NaCl EC50s for juvenile mussels, whereas increasing Ca from 9.9 to 42 mg/L increased the EC50s by a factor of 2. The overall results indicate that glochidia were equally or more sensitive to NaCl and KCl compared to juvenile mussels, and the increased water hardness ameliorated the acute toxicity of NaCl to glochidia and juveniles. These responses rank fatmucket among the most acutely sensitive freshwater organisms to NaCl and KCl.

Bioaccumulation of highly hydrophobic chemicals (log KOW > 8) from contaminated sediments by Lumbriculus variegatus has been studied for relatively few chemicals, and the measured and model predicted biota-sediment accumulation factors (BSAFs) can differ by orders of magnitude. In the current study, sediment bioaccumulation tests with L. variegatus were performed on sediments dosed with chemicals having a wide range of predicted n-octanol/water partition coefficients (KOW; 106–1018), including some higher than most highly hydrophobic chemicals studied to date. The highly hydrophobic chemicals had biphasic elimination kinetics with compartments A and B having fast and slow elimination kinetics, respectively, and for compartment B, elimination followed first-order kinetics. For compartment A with fast elimination kinetics, the mechanism and its kinetic-order could not be determined. Steady-state BSAFs (kg organic carbon/kg lipid) of 0.015, 0.024, and 0.022 were derived for tetradecachloro-p-terphenyl, tetradecachloro-m-terphenyl, and octadecachloro-p-quaterphenyl, respectively. The high uncertainty in predicted KOWs for highly hydrophobic chemicals limited the comparison and evaluation of predicted BSAFs from the Arnot–Gobas food web model and BSAFs measured in this study. The results of this study point to the need to perform dietary assimilation efficiency studies with highly hydrophobic compounds to resolve uncertainties surrounding the estimation of their KOW and the need to understand mechanism and models for the biphasic elimination kinetics.

The acute and chronic toxicity of sulfate (tested as sodium sulfate) was determined in diluted well water (hardness of 100 mg/L and pH 8.2) with a cladoceran (Ceriodaphnia dubia; 2-d and 7-d exposures), a midge (Chironomus dilutus; 4-d and 41-d exposures), a unionid mussel (pink mucket, Lampsilis abrupta; 4-d and 28-d exposures), and a fish (fathead minnow, Pimephales promelas; 4-d and 34-d exposures). Among the 4 species, the cladoceran and mussel were acutely more sensitive to sulfate than the midge and fathead minnow, whereas the fathead minnow was chronically more sensitive than the other 3 species. Acute-to-chronic ratios ranged from 2.34 to 5.68 for the 3 invertebrates but were as high as 12.69 for the fish. The fathead minnow was highly sensitive to sulfate during the transitional period from embryo development to hatching in the diluted well water, and thus, additional short-term (7- to 14-d) sulfate toxicity tests were conducted starting with embryonic fathead minnow in test waters with different ionic compositions at a water hardness of 100 mg/L. Increasing chloride in test water from 10 mg Cl/L to 25 mg Cl/L did not influence sulfate toxicity to the fish, whereas increasing potassium in test water from 1 mg K/L to 3 mg K/L substantially reduced the toxicity of sulfate. The results indicate that both acute and chronic sulfate toxicity data, and the influence of potassium on sulfate toxicity to fish embryos, need to be considered when environmental guidance values for sulfate are developed or refined. Environ Toxicol Chem 2016;35:115–127. Published 2015 SETAC. This article is a US Government work and is in the public domain in the United States.

The strain of Hyalella azteca (Saussure: Amphipoda) commonly used for aquatic toxicity testing in the United States has been shown to perform poorly in some standardized reconstituted waters frequently used for other test species. In 10-d and 42-d experiments, the growth and reproduction of the US laboratory strain of H. azteca was shown to vary strongly with chloride concentration in the test water, with declining performance observed below 15 mg/L to 20 mg/L. In contrast to the chloride-dependent performance of the US laboratory strain of H. azteca, growth of a genetically distinct strain of H. azteca obtained from an Environment Canada laboratory in Burlington, Ontario, Canada, was not influenced by chloride concentration. In acute toxicity tests with the US laboratory strain of H. azteca, the acute toxicity of sodium nitrate increased with decreasing chloride in a pattern similar not only to that observed for control growth, but also to previous acute toxicity testing with sodium sulfate. Subsequent testing with the Burlington strain showed no significant relationship between chloride concentration and the acute toxicity of sodium nitrate or sodium sulfate. These findings suggest that the chloride-dependent toxicity shown for the US laboratory strain may be an unusual feature of that strain and perhaps not broadly representative of aquatic organisms as a whole.

Based on previous research on the acute toxicity of major ions (Na+ , K+ , Ca2+ , Mg2+ , Cl- , SO42- , and HCO3- /CO32- ) to Ceriodaphnia dubia, a mathematical model was developed for predicting the median lethal concentration (LC50) for any ion mixture, excepting those dominated by K-specific toxicity. One component of the model describes a mechanism of general ion toxicity to which all ions contribute and predicts LC50s as a function of osmolarity and Ca activity. The other component describes Mg/Ca-specific toxicity to apply when such toxicity exceeds the general ion toxicity and predicts LC50s as a function of Mg and Ca activities. This model not only tracks well the observed LC50s from past research used for model development but also successfully predicts LC50s from new toxicity tests on synthetic mixtures of ions emulating chemistries of various ion-enriched effluents and receiving waters. It also performs better than a previously published model for major ion toxicity. Because of the complexities of estimating chemical activities and osmolarity, a simplified model based directly on ion concentrations was also developed and found to provide useful predictions. Environ Toxicol Chem 2018;37:247-259. Published 2017 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Testicular oocytes (TOs) have been found in black basses (Micropterus spp.) from many locations in North America. The presence of TOs is often assumed to imply exposure to estrogenic endocrine disrupting compounds (EDCs), however, a definitive causal relationship has yet to be established, and TO prevalence is not consistently low in fish from areas lacking evident EDC sources. This might indicate any of a number of situations: (a) unknown or unidentified EDCs or EDC sources, (b) induction of TOs by other stressors, or (c) TOs occurring spontaneously during normal development. In the present study we analyzed TO occurrence in smallmouth bass (M. dolomieu) from eight populations in Northeastern Minnesota watersheds with differing degrees of human development and hence, presumed likelihood of exposure to anthropogenic chemicals. Three watersheds were categorized as moderately developed, based on the presence of municipal wastewater discharges and higher human population density (4-81 per km2), and five watersheds were minimally developed, with very low human population density (0-1 per km2) and minimal built environment. Testicular tissues from mature fish were evaluated using a semi-quantitative method that estimated TO density, normalized by cross-sectional area. TO prevalence and density among populations from moderately developed watersheds was higher than in populations from minimally developed watersheds. However, TO prevalence was unexpectedly high and variable (7-43%) in some populations from minimally developed watersheds, and only weak evidence was found for a relationship between TO density and watershed development, suggesting alternative or more complex explanations for TO presence in smallmouth bass from this region.

The ions Na+, K+, Ca2+, Mg2+, Cl−, SO42−, and HCO3−/CO32− (referred to here as “major ions”) are present in all fresh waters and are physiologically required by aquatic organisms, but can increase to harmful levels from a variety of anthropogenic activities. It is also known that the toxicities of major ion salts can vary depending on the concentrations of other ions, and understanding these relationships is key to establishing appropriate environmental limits. In this paper we present a series of experiments with Ceriodaphnia dubia to evaluate the acute toxicity of twelve major ion salts and to determine how toxicity of these salts varies as a function of background water chemistry. All salts except CaSO4 and CaCO3 were acutely toxic below saturation, with the lowest LC50s found for K salts. All ten salts that showed toxicity also showed some degree of reduced toxicity as the ionic content of the background water increased. Experiments that independently varied Ca:Mg ratio, Na:K ratio, Cl:SO4 ratio, and alkalinity/pH demonstrated that Ca concentration was the primary factor influencing the toxicities of Na and Mg salts, while the toxicities of K salts were primarily influenced by the concentration of Na. These experiments also indicated multiple mechanisms of toxicity and suggested important aspects of dosimetry: the toxicities of K, Mg, and Ca salts were best related to the chemical activity of the cation, while the toxicities of Na salts also reflected an influence of the anions and were well correlated with osmolarity. Understanding these relationships between major ion toxicity and background water chemistry should aid in the development of sensible risk assessment and regulatory standards.

Globally, estimated costs to manage (i.e., remediate and monitor) contaminated sediments are in the billions of U.S. dollars. Biologically based approaches for assessing the contaminated sediments which pose the greatest ecological risk range from toxicity testing to benthic community analysis. In addition, chemically based sediment quality guidelines (SQGs) provide a relatively inexpensive line of evidence for supporting these assessments. The present study summarizes a mechanistic SQG based on equilibrium partitioning (EqP), which uses the dissolved concentrations of contaminants in sediment interstitial waters as a surrogate for bioavailable contaminant concentrations. The EqP-based mechanistic SQGs are called equilibrium partitioning sediment benchmarks (ESBs). Sediment concentrations less than or equal to the ESB values are not expected to result in adverse effects and benthic organisms should be protected, while sediment concentrations above the ESB values may result in adverse effects to benthic organisms. In the present study, ESB values are reported for 34 polycyclic aromatic hydrocarbon, 32 other organic contaminants, and seven metals (cadmium, chromium, copper, nickel, lead, silver, zinc). Also included is an overview of EqP theory, ESB derivation, examples of applying ESB values, and considerations when using ESBs. The ESBs are intended as a complement to existing sediment-assessment tools, to assist in determining the extent of sediment contamination, to help identify chemicals causing toxicity, and to serve as targets for pollutant loading control measures. Environ. Toxicol. Chem. 2013;32:102–114. © 2012 SETAC

The increasing use of nanosilver in consumer products and the likelihood of environmental exposure warrant investigation into the toxicity of nanosilver to aquatic organisms. A series of studies were conducted comparing the potency of nanosilver to ionic silver (Ag+) at acute and sublethal levels using two test organisms (Daphnia magna and Pimephales promelas). The 48-h D. magna median lethal concentration (LC50) of multiple sizes (10, 20, 30, and 50 nm) of commercially prepared nanosilver (nanoComposix) ranged from 4.31 to 30.36 µg total Ag L−1 with increasing toxicity associated with decreasing particle size. A strong relationship between estimated specific particle surface area and acute toxicity was observed. Nanosilver suspensions (10 nm) treated with cation exchange resin to reduce the concentration of Ag+ associated with it were approximately equally toxic to D. magna compared to untreated nanosilver (48-h LC50s were 2.15 and 2.79 µg total Ag L−1, respectively). The 96-h LC50 and 7-d sublethal 20% effective concentrations (EC20s) for P. promelas were 89.4 and 46.1 µg total Ag L−1, respectively, for 10 nm nanosilver and 4.70 and 1.37 µg total Ag L−1, respectively, for Ag+; the resulting ratios of 96-h LC50 to 7-d EC20 were not significantly different for nanosilver and ionic silver. Overall, these studies did not provide strong evidence that nanosilver either acts by a different mechanism of toxicity than ionic silver, or is likely to cause acute or lethal toxicity beyond that which would be predicted by mass concentration of total silver. This in turn suggests that regulatory approaches based on the toxicity of ionic silver to aquatic life would not be underprotective for environmental releases of nanosilver. Environ. Toxicol. Chem. 2012; 31: 2557–2563. © 2012 SETAC

Previous work demonstrated reduced growth of rainbow trout receiving diets containing environmentally relevant concentrations of arsenic, but did not address the relative and combined potency of waterborne and dietborne exposures. In the current study, juvenile rainbow trout were exposed for 28 d to a range of arsenic concentrations in water and in a live oligochaete diet, separately and in combination. In clean water, fish fed worms previously exposed to arsenate at 4 or 8 mg As/L showed pronounced reductions in growth, but fish exposed to these same water concentrations and a clean diet experienced less or no effect. Increasing waterborne arsenate to 16 or 32 mg As/L had substantial effects on both growth and survival, and simultaneous exposure via both routes intensified growth effects, but not mortality. Growth reduction was strongly correlated to total arsenic accumulation in the fish tissue, regardless of the route of exposure, but mortality was better correlated to waterborne arsenic concentration. The relative concentration of total arsenic in fish viscera and in the remaining carcass was not a useful indicator of exposure route. Speciation analysis showed that most arsenate was converted to arsenite within the worms, but organoarsenic species were not found. The greater toxicity of dietborne exposure when fish and prey were exposed to the same waterborne arsenate concentration emphasizes the need to address dietborne exposure when assessing the aquatic risks of arsenic contamination. This is of particular concern because risk from dietary exposure may occur at even lower water concentrations than used here when prey organisms are exposed for longer periods and via multiple routes.

The effects of diet-borne copper, cadmium, lead, and arsenic on juvenile fish were evaluated using a live diet consisting of the oligochaete Lumbriculus variegatus . In 30 d exposures, no effects were observed on the growth and survival of rainbow trout ( Oncorhynchus mykiss ), fathead minnow ( Pimephales promelas ), and channel catfish ( Ictalurus punctatus ) fed diets contaminated with copper [130–310 µg Cu·(g dm)−1], cadmium [90–540 µg Cd·(g dm)−1], and lead [850–1000 µg Pb·(g dm)−1]. However, rainbow trout growth was reduced in a dose-dependent manner for diets contaminated with arsenic [26–77 µg As·(g dm)−1]. These effects of arsenic on fish growth were accompanied by slower feeding rate, reduced food conversion efficiency, liver cell abnormalities, and fecal matter changes suggestive of digestive effects, and occurred to a similar extent whether the diet was exposed to arsenate or arsenite. Effects from these dietary levels of arsenic, and the absence of effects from these dietary levels of metals, were generally consistent with literature reports using laboratory diets amended with toxicant salts. These results also indicated that reported growth effects on rainbow trout fed diets of invertebrates collected from mining-contaminated areas of the Clark Fork River (Montana, USA) or exposed in the laboratory to Clark Fork River sediments are likely more attributable to the arsenic than the metals in those diets.

The acute and chronic toxicity of sulfate (tested as sodium sulfate) was determined in diluted well water (hardness of 100 mg/L and pH 8.2) with a cladoceran (Ceriodaphnia dubia; 2-d and 7-d exposures), a midge (Chironomus dilutus; 4-d and 41-d exposures), a unionid mussel (pink mucket, Lampsilis abrupta; 4-d and 28-d exposures), and a fish (fathead minnow, Pimephales promelas; 4-d and 34-d exposures). Among the 4 species, the cladoceran and mussel were acutely more sensitive to sulfate than the midge and fathead minnow, whereas the fathead minnow was chronically more sensitive than the other 3 species. Acute-to-chronic ratios ranged from 2.34 to 5.68 for the 3 invertebrates but were as high as 12.69 for the fish. The fathead minnow was highly sensitive to sulfate during the transitional period from embryo development to hatching in the diluted well water, and thus, additional short-term (7- to 14-d) sulfate toxicity tests were conducted starting with embryonic fathead minnow in test waters with different ionic compositions at a water hardness of 100 mg/L. Increasing chloride in test water from 10 mg Cl/L to 25 mg Cl/L did not influence sulfate toxicity to the fish, whereas increasing potassium in test water from 1 mg K/L to 3 mg K/L substantially reduced the toxicity of sulfate. The results indicate that both acute and chronic sulfate toxicity data, and the influence of potassium on sulfate toxicity to fish embryos, need to be considered when environmental guidance values for sulfate are developed or refined.

Toxicity tests using standard effluent test procedures described by the U.S. Environmental Protection Agency were conducted with Ceriodaphnia dubia, fathead minnows (Pimephales promelas), and seven threatened and endangered (listed) fish species from four families: (1) Acipenseridae: shortnose sturgeon (Acipenser brevirostrum); (2) Catostomidae; razorback sucker (Xyrauchen texanus); (3) Cyprinidae: bonytail chub (Gila elegans), Cape Fear shiner (Notropis mekistocholas) Colorado pikeminnow (Ptychocheilus lucius), and spotfin chub (Cyprinella monacha); and (4) Poecillidae: Gila topminnow (Poeciliopsis occidentalis). We conducted 7-day survival and growth studies with embryo-larval fathead minnows and analogous exposures using the listed species. Survival and reproduction were also determined with C. dubia. Tests were conducted with carbaryl, ammonia--or a simulated effluent complex mixture of carbaryl, copper, 4-nonylphenol, pentachlorophenol and permethrin at equitoxic proportions. In addition, Cape Fear shiners and spotfin chub were tested using diazinon, copper, and chlorine. Toxicity tests were also conducted with field-collected effluents from domestic or industrial facilities. Bonytail chub and razorback suckers were tested with effluents collected in Arizona whereas effluent samples collected from North Carolina were tested with Cape Fear shiner, spotfin chub, and shortnose sturgeon. The fathead minnow 7-day effluent test was often a reliable estimator of toxic effects to the listed fishes. However, in 21 % of the tests, a listed species was more sensitive than fathead minnows. More sensitive species results varied by test so that usually no species was always more or less sensitive than fathead minnows. Only the Gila topminnow was consistently less sensitive than the fathead minnow. Listed fish species were protected 96% of the time when results for both fathead minnows and C. dubia were considered, thus reinforcing the value of standard whole-effluent toxicity tests using those two species. If the responses of specific listed species are important for management decisions, our study supports the value in developing culture and testing procedures for those species.

Biologically directed fractionation techniques are a fundamental tool for identifying the cause of toxicity in environmental samples, but few are available for studying mixtures of organic chemicals in aquatic sediments. This paper describes a method for extracting organic chemicals from sediments and then re-introducing them into water column toxicity tests in a way that mimics, at least in part, the partitioning processes that govern bioavailability in sediment. This involves transferring solvent extracts of sediment into triolein and then placing the mixture inside low-density polyethylene dialysis tubing in a configuration similar to semipermeable membrane devices (SPMDs) used for environmental monitoring. For four model compounds, SPMDs were shown to effectively maintain water column exposure in static systems for 10-14 d, with partition coefficients similar to K(OW). Toxicity tests indicated that the SPMDs were compatible with four of five freshwater organisms tested and could be used to measure both lethal and sublethal end points. An example application showed good correspondence between organism responses in intactsediment and extracts in SPMDsfor both field-collected and spiked sediments. The SPMD-based method offers a simple, flexible test design, amenable to several different test organisms, and the ability to work with complex mixtures of contaminants while maintaining partitioning behavior similar to that within intact sediments.

After exposure for 21 d to sediment spiked with Cd, Pb, Cu, or Zn, oligochaetes (Lumbriculus variegatus) held in clean water depurated metal rapidly over the first few hours but much more slowly from 8 h up to 32 h. Results are consistent with previous work suggesting a 6-h depuration period as generally appropriate for sediment bioaccumulation studies with L. variegatus.

Uptake of sediment-associated contaminants by the oligochaete Lumbriculus variegatus was evaluated after 1, 3, 7, 14, 28, and 56 d of exposure to a field-collected sediment contaminated with DDT and its metabolites, dichlorodiphenyldichloroethane (DDD) and dichlorodiphenyldichloroethylene (DDE), or to a field-collected sediment contaminated with polycyclic aromatic hydrocarbons (PAHs). Depuration of contaminants by oligochaetes in a control sediment or in water was also evaluated over a 7-d period after 28 d of exposure to the field-collected sediments. Accumulation of PAHs with a log octanol-water partitioning coefficient (log Kow) 5.6 or DDD and DDE typically exhibited a steady increase from day 1 to about day 14 or 28, followed by a plateau. Therefore, exposures conducted for a minimum of 14 to 28 d better reflected steady-state concentrations for DDT and its metabolites and for PAHs. Depuration rates for DDT and its metabolites and high-Kow PAHs were much higher in organisms held in clean sediment relative to both water-only depuration and model predictions. This suggests that depuration in clean sediment may artificially accelerate depuration of hydrophobic compounds. Comparisons between laboratory-exposed L. variegatus and oligochaetes collected in the field from these sediments indicate that results of laboratory tests can be extrapolated to the field with a reasonable degree of certainty.

The strain of Hyalella azteca (Saussure: Amphipoda) commonly used for aquatic toxicity testing in the United States has been shown to perform poorly in some standardized reconstituted waters frequently used for other test species. In 10-d and 42-d experiments, the growth and reproduction of the US laboratory strain of H. azteca was shown to vary strongly with chloride concentration in the test water, with declining performance observed below 15 mg/L to 20 mg/L. In contrast to the chloride-dependent performance of the US laboratory strain of H. azteca, growth of a genetically distinct strain of H. azteca obtained from an Environment Canada laboratory in Burlington, Ontario, Canada, was not influenced by chloride concentration. In acute toxicity tests with the US laboratory strain of H. azteca, the acute toxicity of sodium nitrate increased with decreasing chloride in a pattern similar not only to that observed for control growth, but also to previous acute toxicity testing with sodium sulfate. Subsequent testing with the Burlington strain showed no significant relationship between chloride concentration and the acute toxicity of sodium nitrate or sodium sulfate. These findings suggest that the chloride-dependent toxicity shown for the US laboratory strain may be an unusual feature of that strain and perhaps not broadly representative of aquatic organisms as a whole.

Standard sediment-bioaccumulation test methods specify that Lumbriculus variegatus should not be fed during the 28-day exposure. This lack of feeding can lead to decreases in L. variegatus weight and lipid content during the 28-day exposure period. Differences in intrinsic nutritional content of sediments could lead to additional variability in organism performance and/or contaminant uptake. To evaluate the potential benefits of feeding, sediment-bioaccumulation tests were performed comparing treatments with and without supplemental feeding with tropical fish food and also comparing performance food introduced as blended slurry versus fine flakes. The ration of food provided had to be limited to 6 mg/300-mL beaker with 250 mg of L. variegatus (ww) receiving three feedings per week to maintain acceptable dissolved oxygen (DO) in the test chambers. Relative weight change during exposure varied across sediments in the absence of food from very little change to as much as a 40 % decrease from starting weight. Feeding slurry and flake foods increased the total weight of recovered organisms by 32 and 48 %, respectively, but they did not decrease variability in weight changes across sediments. Lipid contents of the organisms decreased similarly across all feeding treatments during the test. At test termination, lipid contents of L. variegatus across unfed, slurry-fed, and flake-fed treatments were not significantly different per Tukey’s honest significant difference test with 95 % family-wise confidence. Feeding resulted in polychlorinated biphenyl residues in L. variegatus being generally slightly less (median 78 %) and slightly greater (median 135 %) than the unfed treatments with slurry and flake formulated foods, respectively.

The objective of the present study was to evaluate the relative sensitivity of test organisms in exposures to dilutions of a highly toxic sediment contaminated with metals and organic compounds. One dilution series was prepared using control sand (low total organic carbon [TOC

Seven phthalate esters were evaluated for their 10-d toxicity to the freshwater invertebrates Hyalella azteca and Chironomus tentans in sediment. The esters were diethyl phthalate (DEP), di-n-butyl phthalate (DBP), di-n-hexyl phthalate (DHP), di-(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and a commercial mixture of C7, C9, and C11 isophthalate esters (711P). All seven esters were tested in a sediment containing 4.80% total organic carbon (TOC), and DBP alone was tested in two additional sediments with 2.45 and 14.1% TOC. Sediment spiking concentrations for DEP and DBP were based on LC50 (lethal concentration for 50% of the population) values from water-only toxicity tests, sediment organic carbon concentration, and equilibrium partitioning (EqP) theory. The five higher molecular weight phthalate esters (DHP, DEHP, DINP, DIDP, 711P), two of which were tested and found to be nontoxic in water-only tests (i.e., DHP and DEHP), were tested at single concentrations between 2,100 and 3,200 mg/kg dry weight. Preliminary spiking studies were performed to assess phthalate ester stability under test conditions. The five higher molecular weight phthalate esters in sediment had no effect on survival or growth of either C. tentans or H. azteca, consistent with predictions based on water-only tests and EqP theory. The 10-d LC50 values for DBP and H. azteca were >17,400, >29,500, and >71,900 mg/kg dry weight for the low, medium, and high TOC sediments, respectively. These values are more than 30x greater than predicted by EqP theory and may reflect the fact that H. azteca is an epibenthic species and not an obligative burrower. The 10-d LC50 values for DBP and C. tentans were 826, 1,664, and 4.730 mg/kg dry weight for the low, medium, and high TOC sediments, respectively. These values are within a factor of two of the values predicted by EqP theory. Pore-water 10-d LC50 values for DBP (dissolved fraction) and C. tentans in the three sediments were 0.65, 0.89, and 0.66 of the water-only LC50 value of 2.64 mg/L, thereby agreeing with EqP theory predictions to within a factor of 1.5. The LC50 value for DEP and C. tentans was >3,100 mg/kg dry weight, which is approximately 10x that predicted by EqP theory. It is postulated that test chemical loss and reduced organism exposure to pore water may have accounted for the observed discrepancies with EqP calculations for DEP

We evaluated the effectiveness of Amersorbb®, a carbonaceous resin, in reducing bioavailability of polycyclic aromatic hydrocarbons (PAHs) in contaminated sediments collected from the field. In laboratory studies, sediment pore-water concentrations of eight unsubstituted PAHs were significantly decreased after resin addition. Reduced PAH concentrations in oligochaete tissues from a laboratory bioaccumulation test, along with increased survival/reproduction and reduced photo-enhanced toxicity and sediment avoidance, also resulted from sediment treatment with Ambersorb. Resin amendment also decreased pore-water PAH concentrations in field deployed sediments but did not improve benthic invertebrate colonization. Prediction of partitioning of PAHs between solid and aqueous phases in the test sediments was complicated by the presence of coal and soot. However, accurate predictions of bioavailability were achieved based on pore-water chemistry. Overall, these studies show that the addition of high affinity sorbents effectively reduces pore-water PAH concentrations and bioavailability and suggests that sorbent addition may serve as an option for in situ remediation of some contaminated sediments.

A toxicity identification evaluation (TIE) was conducted on effluent from a major industrial discharger. Although initial monitoring typically showed only slight, intermittent, chronic toxicity to Ceriodaphnia dubia, a later sample showed substantial acute toxicity to C. dubia (48-h lc 50=9%). Acute phase I toxicity characterization tests were conducted on this acutely toxic sample; none of the phase I manipulations reduced sample toxicity. The toxic effluent sample was then treated with activated carbon, and cation, anion, and mixed-bed ion exchange. Acute toxicity was not reduced by treatment with activated carbon or cation exchange, but was completely removed by anion and mixed-bed ion exchange. Based on these data, we concluded that the causative toxicant(s) was likely an inorganic anion(s); chemical analysis detected hexavalent chromium (Cr[VI]) at concentrations sufficient to account for the observed acute toxicity. Although Cr[VI] could clearly explain the presence of acute toxicity, subsequent confirmation testing was designed to determine whether Cr[IV] was responsible for the low-level chronic toxicity more typical of the effluent. Concurrent chronic tests conducted on unaltered and anion-exchanged effluent showed that the presence of chronic toxicity was associated with chronically toxic concentrations of Cr[VI]. The source of Cr[VI] in the effluent was traced to a malfunctioning heat exchanger; after this malfunction was corrected, neither chronic toxicity nor appreciable Cr[VI] was observed in the effluent again.

Acid volatile sulfide (AVS) is a component of sediments that complexes some cationic metals and thereby influences the toxicity of these metals to benthic organisms. Experimental manipulation of AVS in metal-contaminated sediments may provide a means to neutralize toxicity due to metals and thereby help assess the cause of sediment toxicity. This study evaluated the effect of spiking FeS, Na 2 S, and Na 2 S/FeSO 4 combined on the concentration of AVS, simultaneously extracted metals (SEM), and pore-water metals in uncontaminated and metal-enriched sediments. Experiments with solid FeS showed comparatively low effectiveness in increasing AVS. Spiking with either Na 2 S or Na 2 S/FeSO 4 combined increased AVS and/or reduced SEM metal in Cd-, Zn-, and Ni-spiked sediments and in a Cu-contaminated sediment collected from the field. Spiking with Na 2 S/FeSO 4 caused marked reductions in dissolved metal concentrations in the pore waters of these sediments; spiking with Na 2 S alone caused an apparent elevation in pore-water (Cu) metal that we believe is an artifact of metal sulfide formation in the filtered pore water. When the Na 2 S/FeSO 4 treatment was evaluated under conditions simulating those in sediment toxicity tests, alterations of AVS/SEM were nearly quantitative, except for Ni-spiked sediment, which showed lower efficiency than the Cd, Zn, or Cu sediments. It appears that AVS spiking holds promise for the experimental manipulation of metal toxicity in sediments.

The objective of this study was to evaluate the effectiveness of Ambersorb{reg_sign} 1500, a carbonaceous resin, for reducing the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in sediment. Initial studies were conducted with a model PAH, fluoranthene, to determine how effective the resin would be at reducing fluoranthene concentrations in water and sediment pore water. Fluoranthene concentrations were reduced by more than 70% within 24 h when 0.1 g of unconditioned resin was added to 500-ml solutions containing 160 {micro}g/L fluoranthene. Within 48 h, concentrations decreased by more than 92%. Addition of Ambersorb to fluoranthene-spiked sediment showed similar reductions of fluoranthene concentrations in pore water. Based on these initial results, a 10-d bioaccumulation/toxicity experiment was conducted in which the oligochaete Lumbriculus variegatus was exposed to fluoranthene-spiked sediment with and without resin. Chemical analyses showed that sediment amended with resin had greatly diminished pore-water fluoranthene concentrations compared with sediment without resin. Proportional reductions in whole-body fluoranthene concentrations were observed in oligochaetes exposed to resin-amended sediments. As would be expected from enhancement of fluoranthene toxicity by ultraviolet light, organisms exposed to fluoranthene-spiked sediment exhibited significant mortality upon subsequent exposure to ultraviolet light. Consistent with their lower body burdens, organisms from resin-treated sediment lackedmore » this sensitivity (100% survival). These experiments demonstrate that Ambersorb 1500 effectively reduces the bioavailability of fluoranthene in spiked sediment. Additional studies are needed to define the boundaries of the resin`s effectiveness in influencing the bioavailability of other PAHs and nonpolar organic chemicals in spiked and field-contaminated sediments.« less

Techniques for reducing ammonia toxicity in freshwater sediments were investigated as part of a project to develop toxicity identification and evaluation (TIE) procedures for whole sediments. Although ammonia is a natural constituent of freshwater sediments, pollution can lead to ammonia concentrations that are toxic to benthic invertebrates, and ammonia can also contribute to the toxicity of sediments that contain more persistent contaminants. We investigated the use of amendments of a natural zeolite mineral, clinoptilolite, to reduce concentrations of ammonia in sediment pore water. Zeolites have been widely used for removal of ammonia in water treatment and in aqueous TIE procedures. The addition of granulated zeolite to ammonia-spiked sediments reduced pore-water ammonia concentrations and reduced ammonia toxicity to invertebrates. Amendments of 20% zeolite (v/v) reduced ammonia concentrations in pore water by ≥70% in spiked sediments with ammonia concentrations typical of contaminated freshwater sediments. Zeolite amendments reduced toxicity of ammonia-spiked sediments to three taxa of benthic invertebrates (Hyalella azteca, Lumbriculus variegatus, and Chironomus tentans), despite their widely differing sensitivity to ammonia toxicity. In contrast, zeolite amendments did not reduce acute toxicity of sediments containing high concentrations of cadmium or copper or reduce concentrations of these metals in pore waters. These studies suggest that zeolite amendments, used in conjunction with toxicity tests with sensitive taxa such as H. azteca, may be an effective technique for selective reduction of ammonia toxicity in freshwater sediments.

Toxicity of fresh waters with high total dissolved solids has been shown to be dependent on the specific ionic composition of the water. To provide a predictive tool to assess toxicity attributable to major ions, the authors tested the toxicity of over 2,900 ion solutions using the daphnids, Ceriodaphnia dubia and Daphnia magna, and fathead minnows (Pimephales promelas). Multiple logistic regression was used to relate ion composition to survival for each of the three test species. In general, relative ion toxicity was K{sup +} > HCO{sub 3}{sup {minus}} {approx} Mg{sup 2+} > Cl{sup {minus}} > SO{sub 4}{sup 2{minus}}; Na{sup +} and Ca{sup 2+} were not significant variables in the regressions, suggesting that the toxicity of Na{sup +} and Ca{sup 2+} salts was primarily attributable to the corresponding anion. For C. dubia and D. magna, toxicity of Cl{sup {minus}}, SO{sub 4}{sup 2{minus}}, and K{sup +} was reduced in solutions enriched with more than one cation. Final regression models showed a good quality of fit to the data (R{sup 2} = 0.767--0.861). Preliminary applications of these models to field-collected samples indicated a high degree of accuracy for the C. dubia model, while the D. magna and fathead minnow models tended to overpredictmore » ion toxicity. Studies of oil and gas produced waters, irrigation drain waters, shale oil leachates, sediment pore waters, and industrial process waters have shown toxicity caused by elevated concentrations of common ions.« less

Review of data from several contaminated sediment sites suggested that biota-sediment accumulation factors (BSAFs) declined with increasing contaminant concentrations in the sediment. To evaluate the consistency and possible causes of this behavior, polychlorinated biphenyl (PCB)-contaminated sediment samples from the Hudson, Grasse, and Fox River Superfund sites were used in sediment bioaccumulation tests with the freshwater oligochaete, Lumbriculus variegatus, with PCB concentrations in interstitial water (IW) quantified using polyoxymethylene passive samplers. Measured BSAFs tended to decrease with increasing PCB concentration in sediment, especially for the more highly chlorinated congeners. Measures of partitioning between sediment, IW, and oligochaetes showed that measured sediment-IW partition coefficients (KTOC ) tended to increase slightly with increasing sediment contamination, whereas the ratio of tissue PCB to IW PCB tended to decrease with increasing concentration in IW. Variation in accumulation among sediments was clearly influenced by bioavailability, as reflected by IW measurements, although the specific cause of varying KTOC was not clear. Calculated partitioning between IW and organism lipid (Klipid ) indicated that accumulation was generally 5 to 10-fold higher than would be predicted if Klipid was approximately equal to the n-octanol-water partition coefficient (KOW ). While affirming previous observations of decreasing BSAFs with increasing PCB contamination, the relatively shallow slope of the observed relationship in the current data may suggest that this concentration dependence is not a major uncertainty in sediment risk assessment, particularly if measurements of PCBs in IW are incorporated.

Metals are common toxicants found in effluents and other environmental samples. Within Toxicity Identification Evaluation methods proposed by the US Environmental Protection Agency and others, addition of ethylenediaminetetraacetic acid (EDTA) is used as an indicator of metal toxicity. Previous experiments showed that addition of sodium thiosulfate, originally included to detect toxicity due to oxidants, was also effective at reducing toxicity from some common metals. in the present study, the authors characterized the effectiveness of both EDTA and thiosulfate in removing the toxicity of 16 different metal ions to Ceriodaphnia dubia. Ethylenediaminetetraacetic acid addition removed toxicity associated with all cationic metals tested except for Cr{sup 3+}, Fe{sup 2+}, Al{sup 3+}, and Ag{sup +}. Thiosulfate addition was less effective than EDTA for Zn{sup 2+}, Mn{sup 2+}, Pb{sup 2+}, and Ni{sup 2+}, but reduced toxicity of both Ag{sup +} and selenite (Se[VI]), which EDTA did not. Results of this research can be used to categorize metal toxicity in unknown samples based on the response to additions of EDTA and thiosulfate.

(1996). Retrospective analysis of the ecological risk of contaminant mixtures in aquatic sediments. Human and Ecological Risk Assessment: An International Journal: Vol. 2, New developments in modeling wildlife exposure to toxic chemicals, pp. 434-440.

The toxicity of certain polycyclic aromatic hydrocarbons (PAHs) can be greatly increased by simultaneous exposure of test organisms to ultraviolet (UV) wavelengths present in sunlight. This phenomenon, commonly termed photoinduced toxicity, had been evaluated extensively in laboratory settings where only one chemical of concern was present. However, more recent studies have demonstrated that complex mixtures of PAHs present, for example in sediments, also can cause phototoxicity to a variety of aquatic species when the samples are tested in simulated sunlight. Unfortunately, because these types of samples can contain thousands of substituted and unsubstituted PAHs it is difficult, if not impossible, to use conventional analytical techniques to identify those responsible for photoinduced toxicity. The objective of the present study was to link two powerful ecotoxicology tools, toxicity-based fractionation techniques and QSAR models, to identify phototoxic chemicals in a sediment contaminated with ...

Procedures are described for calculating and evaluating sediment effect concentrations (SECs) using laboratory data on the toxicity of contaminants associated with field-collected sediment to the amphipod Hyalella azteca and the midge Chironomus riparius . SECs are defined as the concentrations of individual contaminants in sediment below which toxicity is rarely observed and above which toxicity is frequently observed. The objective of the present study was to develop SECs to classify toxicity data for Great Lake sediment samples tested with Hyalella azteca and Chironomus riparius . This SEC database included samples from additional sites across the United States in order to make the database as robust as possible. Three types of SECs were calculated from these data: (1) Effect Range Low (ERL) and Effect Range Median (ERM), (2) Threshold Effect Level (TEL) and Probable Effect Level (PEL), and (3) No Effect Concentration (NEC). We were able to calculate SECs primarily for total metals, simultaneously extracted metals, polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). The ranges of concentrations in sediment were too narrow in our database to adequately evaluate SECs for butyltins, methyl mercury, polychlorinated dioxins and furans, or chlorinated pesticides. About 60 to 80% of the sediment samples in the database are correctly classified as toxic or not toxic depending on type of SEC evaluated. ERMs and ERLs are generally as reliable as paired PELs and TELs at classifying both toxic and non-toxic samples in our database. Reliability of the SECs in terms of correctly classifying sediment samples is similar between ERMs and NECs; however, ERMs minimize Type I error (false positives) relative to ERLs and minimize Type II error (false negatives) relative to NECs. Correct classification of samples can be improved by using only the most reliable individual SECs for chemicals (i.e., those with a higher percentage of correct classification). SECs calculated using sediment concentrations normalized to total organic carbon (TOC) concentrations did not improve the reliability compared to SECs calculated using dry-weight concentrations. The range of TOC concentrations in our database was relatively narrow compared to the ranges of contaminant concentrations. Therefore, normalizing dry-weight concentrations to a relatively narrow range of TOC concentrations had little influence on relative concentra of contaminants among samples. When SECs are used to conduct a preliminary screening to predict the potential for toxicity in the absence of actual toxicity testing, a low number of SEC exceedances should be used to minimize the potential for false negatives; however, the risk of accepting higher false positives is increased.