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The primary goal of the present study is to provide a broad view of best practices for evaluating bioavailability models for metals for use in the protection of aquatic life. We describe the state of the science regarding 1) the evaluation and selection of ecotoxicity data, 2) the selection of bioavailability models for use in normalization, and 3) subsequent application of bioavailability models. Although many examples of normalization steps exist worldwide, a scheme is proposed to evaluate and select a model that takes account of its representativeness (water chemistry and taxonomic coverage of the ecotoxicity data set) and validation performance. Important considerations for a suitable model are the quantity of inputs needed, accuracy, and ease of use, all of which are needed to set protective values for aquatic life and to use these values to evaluate potential risks to organisms in receiving waters. Although the end results of different model application approaches may be broadly similar, the differences in these application frameworks ultimately come down to a series of trade-offs between who needs to collect the data and use the bioavailability model, the different requirements of spatial scales involved (e.g., regional vs site-specific values), and model predictiveness and protectiveness. Ultimately, understanding the limits and consequences of these trade-offs allows for selection of the most appropriate model and application framework to best provide the intended levels of aquatic life protection. Environ Toxicol Chem 2019;39:118-130. © 2019 SETAC.

Acceptance of the biotic ligand model (BLM) to derive aquatic life criteria, for metals in general and copper (Cu) in particular, is growing among regulatory agencies worldwide. Thus, it is important to ensure that water quality data are used appropriately and consistently in deriving such criteria. Here we present a suggested BLM implementation framework (hereafter referred to as "the Framework") to help guide the decision-making process when designing sampling and analysis programs for use of the BLM to derive water quality criteria applied on a site-specific basis. Such a framework will help inform stakeholders on the requirements needed to derive BLM-based criteria, and thus ensure that the appropriate types and amount of data are being collected and interpreted. The Framework was developed for calculating BLM-based criteria when data are available from multiple sampling locations on a stream. The Framework aspires to promote consistency when applying the BLM across data sets of disparate water quality, data quantity, and spatial and temporal representativeness and is meant to be flexible to maximize applicability over a wide range of scenarios. Therefore, the Framework allows for a certain level of interpretation and adjustment to address the issues unique to each data set. Integr Environ Assess Manag 2018;14:736-749. © 2018 SETAC.

There is concern over whether regulatory criteria for copper (Cu) are protective against chemosensory and behavioral impairment in aquatic organisms. We compiled Cu toxicity data for these and other sublethal endpoints in 35 tests with saltwater organisms and compared the Cu toxicity thresholds with biotic ligand model (BLM)-based estimated chronic limits (ECL values, which are 20% effect concentrations [EC20s] for the embryo-larval life stage of the blue mussel [Mytilus edulis], a saltwater species sensitive to Cu that has historically been used to derive saltwater Cu criteria). Only 8 of the 35 tests had sufficient toxicity and chemistry data to support unequivocal conclusions (i.e., a Cu EC20 or no-observed-effect concentration could be derived, and Cu and dissolved organic carbon [DOC] concentrations were measured [or DOC concentrations could be inferred from the test-water source]). The BLM-based ECL values would have been protective (i.e., the ECL was lower than the toxicity threshold) in 7 of those 8 tests. In the remaining 27 tests, this meta-analysis was limited by several factors, including 1) the Cu toxicity threshold was a "less than" value in 19 tests because only a lowest-observed-effect concentration could be calculated and 2) Cu and/or DOC concentrations often were not measured. In 2 of those 27 tests, the ECL would not have been protective if based only on a conservatively high upper-bound DOC estimate. To facilitate future evaluations of the protectiveness of aquatic life criteria for metals, we urge researchers to measure and report exposure-water chemistry and test-metal concentrations that bracket regulatory criteria. Environ Toxicol Chem 2018;37:1515-1522. © 2018 SETAC.

The chemistry, bioavailability, and toxicity of aluminum (Al) in the aquatic environment are complex and affected by a wide range of water quality characteristics (including pH, hardness, and dissolved organic carbon). Data gaps in Al ecotoxicology exist for pH ranges representative of natural surface waters (pH 6-8). To address these gaps, a series of chronic toxicity tests were performed at pH 6 with 8 freshwater species, including 2 fish (Pimephales promelas and Danio rerio), an oligochaete (Aeolosoma sp.), a rotifer (Brachionus calyciflorus), a snail (Lymnaea stagnalis), an amphipod (Hyalella azteca), a midge (Chironomus riparius), and an aquatic plant (Lemna minor). The 10% effect concentrations (EC10s) ranged from 98 μg total Al/L for D. rerio to 2175 μg total Al/L for L. minor. From these data and additional published data, species-sensitivity distributions (SSDs) were developed to derive concentrations protective of 95% of tested species (i.e., 50% lower confidence limit of a 5th percentile hazard concentration [HC5-50]). A generic HC5-50 (not adjusted for bioavailability) of 74.4 μg total Al/L was estimated using the SSD. An Al-specific biotic ligand model (BLM) was used to develop SSDs normalized for bioavailability based on site-specific water quality characteristics. Normalized HC5-50s ranged from 93.7 to 534 μg total Al/L for waters representing a range of European ecoregions, whereas a chronic HC5 calculated using US Environmental Protection Agency aquatic life criteria methods (i.e., a continuous criterion concentration [CCC]) was 125 μg total Al/L when normalized to Lake Superior water in the United States. The HC5-50 and CCC values for site-specific waters other than those in the present study can be obtained using the Al BLM. Environ Toxicol Chem 2018;37:36-48. © 2017 SETAC.

Acceptance of the biotic ligand model (BLM) to derive aquatic life criteria, for metals in general and copper (Cu) in particular, is growing among regulatory agencies worldwide. Thus, it is important to ensure that water quality data are used appropriately and consistently in deriving such criteria. Here we present a suggested BLM implementation framework (hereafter referred to as "the Framework") to help guide the decision-making process when designing sampling and analysis programs for use of the BLM to derive water quality criteria applied on a site-specific basis. Such a framework will help inform stakeholders on the requirements needed to derive BLM-based criteria, and thus ensure that the appropriate types and amount of data are being collected and interpreted. The Framework was developed for calculating BLM-based criteria when data are available from multiple sampling locations on a stream. The Framework aspires to promote consistency when applying the BLM across data sets of disparate water quality, data quantity, and spatial and temporal representativeness and is meant to be flexible to maximize applicability over a wide range of scenarios. Therefore, the Framework allows for a certain level of interpretation and adjustment to address the issues unique to each data set. Integr Environ Assess Manag 2018;14:736-749. © 2018 SETAC.

Copper (Cu) can impair olfaction in juvenile Pacific salmon (as well as other fishes), thus potentially inhibiting the ability of juveniles to avoid predators or to find food. Because Cu is commonly elevated in stormwater runoff in urban environments, storm events may result in elevated Cu concentrations in salmon-bearing streams. Accordingly, there is concern that existing Cu criteria, which were not derived using data for olfactory-related endpoints, may not be adequately protective of juvenile salmon. However, a modification of the US Environmental Protection Agency (USEPA) biotic ligand model (BLM) for deriving site-specific Cu criteria was recently proposed, which accounted for the sensitivity of olfactory endpoints. The modification was based on olfactory inhibition in juvenile coho salmon (Oncorhynchus kisutch) exposed to Cu in various combinations of pH, hardness, alkalinity, and dissolved organic carbon (DOC) concentrations. We used that olfactory-based BLM to derive 20% inhibition concentrations (IC20) values for Cu for 133 stream locations in the western United States. The olfactory BLM-based IC20 values were compared to the existing hardness-based Cu criteria and the USEPA's BLM-based Cu criteria for these representative natural waters of the western United States. Of the 133 sampling locations, mean hardness-dependent acute and chronic Cu criteria were below the mean olfactory-based BLM IC20 value in 122 (92%) and 129 (97%) of the waters, respectively (i.e.

The goal of this study was to evaluate the reliability of the Biotic Ligand Model to predict Cu toxicity in very hard surface water (>200 mg/L as CaCO3), relative to current copper criteria methodologies (hardness-based equation and the water-effect ratio; WER). To test these methods, we conducted acute Cu toxicity tests with three aquatic test species (Ceriodaphnia dubia, Daphnia pulex and Pimephales promelas) in seven surface waters. The sites were representative of effluent-dependent or effluent-dominated streams common to the arid western United States of America (arid West) and a wide range of water quality variables were tested. In addition, concurrent Cu toxicity tests were conducted in laboratory waters that were matched to hardness and alkalinity of the sites to facilitate calculation of WER values. Results were used to characterize empirical relationships between water quality characteristics and Cu toxicity, and to compare measured Cu toxicity with Biotic Ligand Model (BLM) predictions. Acute toxicity tests were also conducted with C. dubia and P. promelas in a range of Ca or Mg-dominated hardness concentrations to determine the independent effects of Ca or Mg on Cu toxicity at high hardness levels. Conclusions from this study suggest that the BLM generates appropriate criteria for the waters tested in this study when compared to the hardness-based equation or WER approach. Although the historical site-specific methods are useful for surface waters with hardness ≤250 mg/L as CaCO3, the unique conditions of arid West streams require site-specific methods that account for the influences of critical water quality variables (i.e., pH, dissolved organic carbon, alkalinity, Ca, Mg and Na). Therefore, the BLM offers an improved alternative to the hardness-based and WER approaches, particularly for situations where the current methods would be under-protective of sensitive aquatic life.

Worldwide transfer and introduction of non-indigenous species in ballast water causes significant environmental and economic impact. One way to address this problem is to remove or inactivate organisms that are found in ballast water. In this study, 3 experiments were conducted in Puget Sound, Washington, USA, using a prototype ozone treatment system installed on a commercial oil tanker, the S/T Tonsina. Treatment consisted of ozone gas diffused into a ballast tank for 5 and 10 h. Treatment and control tanks were sampled during the ozonation period for chemistry, cultur- able bacteria, phytoplankton and zooplankton. Selected fish and invertebrates were placed in cages deployed in the treatment and control tanks. Ozone introduced into seawater rapidly converts bro- mide (Br - ) to bromines (HOBr/OBr - ), compounds that are disinfectants. These were measured as total residual oxidant (TRO). Ozone treatment inactivated large portions of culturable bacteria, phyto- plankton and zooplankton. The highest reductions observed were 99.99% for the culturable bacteria, >99% for dinoflagellates and 96% for zooplankton. Caged animal results varied among taxa and locations in the ballast tank. Sheepshead minnows and mysid shrimp were most susceptible, shore crabs and amphipods the least. Distribution of ozone in the treatment tank was not homogenous during experiments, as suggested by the observed TRO concentrations and lower efficacies for inactivating the different taxa in selected ballast tank locations. Low concentrations of bromoform, a disinfection byproduct, were found in treated ballast water.

The U.S. Environmental Protection Agency’s (USEPA) current ambient water quality criteria (AWQC) for cyanide were developed in 1984. Since this time, additional research on cyanide toxicity and analytical chemistry has suggested that cyanide AWQC values need to be updated to reflect the current state-of-the-science and to ensure that the methods for implementing the cyanide AWQC reflect the bioavailable and toxic forms of cyanide. Therefore, the Water Environment Research Foundation (WERF) sponsored a reassessment of the AWQC for cyanide by initiating a thorough review of the current scientific literature on cyanide and conducting additional laboratory studies to further understand cyanide chemistry and toxicity. Consistent with the USEPA’s draft strategy for developing AWQC, this evaluation also considered whether the cyanide AWQC are protective of benthos, threatened and endangered (T&E) species, and aquatic-dependent wildlife. This reassessment of AWQC for cyanide resulted in proposed freshwater acute and chronic criteria of 23 and 4.8 µg CN/L, respectively, which are comparable to the current freshwater acute and chronic criteria of 22 and 5.2 µg CN/L (free cyanide). For saltwater organisms, the reassessment resulted in proposed acute and chronic criteria of 20 and 4.1 µg CN/L (free cyanide), respectively, compared to the current saltwater acute and chronic criteria which are both 1.0 µg CN/L. The difference in the current and proposed saltwater criteria values is attributed to recent cyanide toxicity testing with several crab species in the genus Cancer and the copepod Acartia tonsa, which suggests this genus is not as sensitive to cyanide as previous cyanide toxicity testing indicated. A sediment-based cyanide criterion does not appear warranted if it is assumed that benthic organisms are not inordinately more sensitive to cyanide than the water column organisms that drive the basis for the proposed freshwater and saltwater criteria (the available cyanide toxicity data do not suggest that they would be), and given that bioavailable forms of cyanide are not expected to accumulate appreciably in sediment. Cyanide should thus be effectively regulated based on water column-based criteria and concentrations. Based on a combination of available empirical and estimated cyanide toxicity values for T&E species, the proposed freshwater criteria appear to be protective

To assess photosynthesis as a bioindicator of toxicity from polycyclic aromatic hydrocarbons (PAHs), the response of chlorophyll-a fluorescence to creosote exposure was compared with effects on population-level plant growth. Large, outdoor, freshwater microcosms containing Eurasian watermilfoil (Myriophyllum spicatum) received either a single application or multiple applications of liquid creosote at nominal concentrations from 0.109 to 32.7 mg L(-1). For several weeks following treatment, photosynthetic electron transport was measured using pulse amplitude-modulated chlorophyll-a fluorescence. The maximum efficiency of photosystem II electron transport (Fv/Fm) and the quantum yield of photochemistry (deltaF/F'm) were diminished in plants shortly after the addition of creosote. In microcosms that received a single treatment of creosote only, the 50% effective concentrations (EC50s), expressed as the aqueous concentration of 15 of the most abundant PAHs, were 0.28 mg L(-1) for Fv/Fm and 0.30 mg L(-1) for deltaF/F'm. Chlorophyll-a fluorescence was diminished to a greater extent in microcosms that received multiple treatments of creosote, with EC50s of 0.13 mg L(-1) for Fv/Fm and 0.10 mg L(-1) for deltaF/F'm. Plant biomass accumulation was inhibited in a concentration-dependent manner in all microcosms treated with creosote, but this inhibition occurred to a greater degree in microcosms treated with multiple creosote applications. The response of chlorophyll-a fluorescence, measured only 8 d after creosote treatment, was similar to plant growth over the entire growing season, indicating that this technique can be used to estimate potential effects of contaminants before detrimental impacts on populations.

During recent years, the biotic ligand model (BLM) has been proposed as a tool to evaluate quantitatively the manner in which water chemistry affects the speciation and biological availability of metals in aquatic systems. This is an important consideration because it is the bioavailability and bioreactivity of metals that control their potential to cause adverse effects. The BLM approach has gained widespread interest amongst the scientific, regulated and regulatory communities because of its potential for use in developing water quality criteria (WQC) and in performing aquatic risk assessments for metals. Specifically, the BLM does this in a way that considers the important influences of site-specific water quality. This journal issue includes papers that describe recent advances with regard to the development of the BLM approach. Here, the current status of the BLM development effort is described in the context of the longer-term history of advances in the understanding of metal interactions in the environment upon which the BLM is based. Early developments in the aquatic chemistry of metals, the physiology of aquatic organisms and aquatic toxicology are reviewed first, and the degree to which each of these disciplines influenced the development of water quality regulations is discussed. The early scientific advances that took place in each of these fields were not well coordinated, making it difficult for regulatory authorities to take full advantage of the potential utility of what had been learned. However, this has now changed, with the BLM serving as a useful interface amongst these scientific disciplines, and within the regulatory arena as well. The more recent events that have led to the present situation are reviewed, and consideration is given to some of the future needs and developments related to the BLM that are envisioned. The research results that are described in the papers found in this journal issue represent a distinct milestone in the ongoing evolution of the BLM approach and, more generally, of approaches to performing ecological assessments for metals in aquatic systems. These papers also establish a benchmark to which future scientific and regulatory developments can be compared. Finally, they demonstrate the importance and usefulness of the concept of bioavailability and of evaluative tools such as the BLM.

We assessed the response of phytoplankton communities in aquatic microcosms to single applications of liquid creosote. The creosote was applied to 14 microcosms at concentrations ranging from 0.06 to 109 mg/L. Two microcosms served as controls. Phytoplankton samples were collected from each microcosm one week and 1 d before treatment and at 7 and 21 d after treatment. Temporal changes (response-recovery) in phytoplankton community composition were assessed with principal response curves. Creosote had no direct toxic effect on the phytoplankton community based on total abundance and number of taxa. Population levels declined in all treatments between day -1 and day 7, but this trend mirrored a similar decline in the control microcosms. At both 7 and 21 d after treatment, population densities and number of taxa in most treatments exceeded those in the controls and exhibited a parabolic relationship relative to creosote concentration. This relationship was most pronounced at 21 d, at which time population densities and number of taxa at intermediate concentrations were up to twice those at low and high concentrations. This response pattern seems to represent an indirect response to impacts on zooplankton and a corresponding reduction in grazing pressure. In contrast, total algal biomass declined 52 to 97% relative to the controls at all but the lowest creosote concentration at 7 d. This apparent decline was due to a significant proliferation of the alga Closterium moniliforme in the controls and low creosote concentration. At 21 d, no difference was found in total biomass between treated and control microcosms. The results of this study suggest that creosote does not pose a significant direct risk to phytoplankton at concentrations likely to be encountered in most contaminated aquatic environments; however, stimulation of algal populations could occur in situations of long-term chronic exposure or spill events that remove predatory zooplankton populations.

In this article we review the biological effects of Al, primarily with respect to the chemical factors controlling Al bioavailability and toxicity, and how its biological effects are best predicted. Our intent is not to duplicate recent reviews on Al chemistry or toxicity, but rather to update the literature since these reviews were published, and to focus on Al speciation and other external chemical influences on Al bioavailability to freshwater biota. Briefly, we first review Al chemistry, with a specific focus on understanding, as well as measuring, Al chemical species of importance to aquatic biota. Next we more comprehensively review Al toxicity and bioavailability to freshwater algae, with a thorough analysis of the relationships between speciation and toxicity, the role of important chemical complexing agents such as P, Si, and organic carbon, as well as the potential for Al to impact algal community structure. A third section reviews the more sparse literature on aquatic higher plants; the fourth ...

The influence of a commercial humic acid (Aldrich; AHA) on the development of anthracene photoinduced toxicity to the duckweed Lemna gibba was examined using both room- and low-temperature (77°K) chlorophyll fluorescence assays. Plants were exposed to 2 mg liter -1 anthracene both with and without 6.2 mg liter -1 of AHA and grown under either visible light or simulated solar radiation that mimics the natural abundance of UV radiation. Exposure periods ranged from 1 to 48 h to examine temporal changes in chlorophyll degradation and chlorophyll a fluorescence induction in response to these light and HA treatments. The onset of anthracene photoinduced toxicity followed a definite sequence; chlorophyll a fluorescence induction parameters (F v /F m , and t 1 /2) responded earliest to anthracene exposure, with observable chlorophyll degradation requiring up to 24 to 48 h. Of these, t 1 /2 was the most sensitive, with significant inhibition apparent within I h of exposure. Throughout the entire 48-h exposure, 6.2 mg liter 1 AHA ameliorated the photoinduced toxicity of anthracene, in terms of both chlorophyll degradation and F v / F m inhibition. In contrast, AHA delayed the complete inhibition of t 1 /2 by only I to 24 h rather than permanently protecting the plants from anthracene damage to PS2. This suggests that AHA may slow, but not prevent, the entrance of either intact anthracene or its photooxidized byproducts under these exposure conditions.

We examined whether the sensitivity of Ceriodaphnia dubia to copper toxicity was influenced by the hardness of the water in which they were reared or in which they were exposed. Organisms cultured in very hard water were 1.5-fold less sensitive to copper than those in moderately hard water. However, the hardness of the exposure water had a greater (2.5-fold) effect on copper median effective concentration (EC50s).

The acidophilic diatom Asterionella ralfsii cf. var. americana Korn. was grown in continuous culture to examine the influences of both pH and Al on Si-limited growth and uptake kinetics. In contrast to nutrient-replete cultures of A. ralfsii, lowering pH from approximately 6 to 5 reduced algal cell density, chlorophyll a concentration, and intensity of in vivo fluorescence (IVF) at steady state. The lower pH treatments were also characterized by lower Si cell quotas and higher residual dissolved Si concentrations in chemostats with similar nutrient supply rates. Physiological responses to Al stress differed from those to pH reduction when cultures were Si-limited. Nominal Al additions of 20 μmol·L−1 reduced chlorophyll a concentration and IVF values at higher pH, but all other biomass and chemical parameters remained constant at steady state. The combined efects of Al and reduced pH were more severe than either stress alone, inducing culture washout at pH 4.8. Short-term Si uptake experiments performed at pH 6 showed that Al influenced Michaelis-Menten parameter estimates. Half-saturation (Ks and maximum uptake rate (Vm) constants increased approximately 8- and 2-fold in the presence of Al, respectively, but this difference was only significant for Vm. Similar to previously observed effects of Al on cell morphology in A. ralfsii, Si uptake kinetics were more sensitive to Al additions than to Silimited growth per se.

Water pH in the gill micro-environment of adult fathead minnows (Pimephales promelas Rafinesque) was measured by means of opercular catheters and latex masks. Synthetic soft water of pH 5.7 was made more acidic, so that pH of the gill micro-environment stayed at approximately 5.4 to 5.9 over the inspired pH range 4.8 to 6.3. Copper would therefore be >99% Cu2+ at the gills. To measure Cu accumulation on gills, the target organ for Cu toxicity, adult fathead minnows were exposed for 2 to 3 h to 16 μg/L Cu in synthetic soft water (Ca2+ and Na+ approximately 50 μeq/L) at pH 4.8 and 6.3. Gill Cu concentrations were about 1.7 μg Cu/g wet tissue for the inspired pH 4.8 and 6.3 exposures. Added Ca2+ of 2,100 or 4,000 μeq/L reduced gill Cu accumulation during exposures at pH 4.8 but not at pH 6.3. EDTA eliminated Cu deposition at both pH 4.8 and pH 6.3 when equimolar with Cu, but reduced Cu deposition (by 50%) when half equimolar only in the pH 4.8 exposures. These results can be explained by Ca2+ and H+ competition with Cu for gill binding sites and by complexation of Cu by EDTA. Added CaCO3 did not reduce gill Cu, although both competition by Ca2+ and complexation by CO2−3 were expected. Water chemistry calculations suggested that because little CO2−3 is available at pH < 7, CO2−3 from CaCO3 is less likely to affect Cu deposition on fish gills than is Ca2+ from CaCO3.

Legislation introduced by the United Nations International Maritime Organization (IMO) has focused primarily on standards defining successful treatments designed to remove invasive species entrained in ballast water. An earlier shipboard study found that ozone introduced into salt water ballast resulted in the formation of bromine compounds, measured as total residual oxidants (TRO) that were toxic to both bacteria and plankton. However, the diffuser system employed to deliver ozone to the ballast water tanks resulted in patchiness in TRO distribution and toxicity to entrained organisms. In this follow-up study, the shipboard diffuser system was replaced by a single Venturi-type injection system designed to deliver a more homogeneous biocide distribution. Within-tank variability in TRO levels and associated toxicity to zooplankton, phytoplankton and marine bacteria was measured via a matrix of tubes deployed to sample different locations in treated and untreated (control) tanks. Three trials were conducted aboard the oil tanker S/T Prince William Sound in the Strait of Juan de Fuca off Port Angeles, Washington State, USA, between June and December 2007. Mortalities of plankton and bacteria and oxidant concentrations were recorded for treated and untreated ballast water up to 3 days following treatment, and residual toxicity beyond this period was measured by bioassay of standard test organisms. Results indicated uniform compliance with current IMO standards, but only partial compliance with other existing and pending ballast water legislation.

Light, especially UV radiation, greatly elevates the toxicity of PAHs to plants. We have previously shown that chlorosis is an excellent indicator of PAH toxicity. Usually when chlorophyll (Chl) content is diminished, photosynthesis is also inhibited. Therefore, we tested if photosynthesis was indeed inhibited by PAHs in the presence of Simulated Solar Radiation. A Commonly used measure of in vivo photosynthetic activity in plants is chlorophyll a (Chl a) fluorescence, an assay of electron transport in photosystem II (PS II). This assay can be performed in situ on intact plants within 24 h of application of the chemical. In this study, two methods of collecting Chl a fluorescence data are described. Fluorescence induction was used to measure maximal PS II efficiency and photosynthesis downstream from PS II, with the finding that both were predictive of growth inhibition. Pulse amplitude modulated (PAM) fluorometry which measures steady state PS II efficiency was also used. This technique also detected negative impacts of photomodified anthracene on the plants.

The growth rates of two diatoms, acidophilic Asterionella ralfsii and circumneutral A. formosa, were differentially affected by varying pH, Al, and EDTA in chemically defined media. Free Al ion concentration increased as pH and EDTA concentration decreased. Free trace metal ion concentration decreased as EDTA levels increased but increased by orders of magnitude upon addition of Al. pH had an overriding species specific effect on growth rate; at low pH A. ralfsii had higher growth rates than A. formosa and vice versa at high pH. For both species higher EDTA levels depressed growth rates. Moderate additions of Al generally resulted in growth stimulation. The growth rate stimulations, especially at 200 and 400 μg L−1 Al additions, correlate to increases in free trace metal ion concentrations. The EDTA-AI interaction effects on growth rate were both pH and concentration dependent: at pH 7 both species were stimulated by addition of Al at all EDTA levels (except A. ralfsii at 5.0 mM EDTA and A. formosa at 0.5 mNM EDTA); at pH 6 Al addition either stimulated or had no effect on the growth rates of both species (except at low EDTA and high Al levels); at pH 5 A. formosa did not grow and additions of 200 μg L−1 Al stimulated growth of A. ralfsii. It is likely that the effect of pH, Al, and EDTA on speciation of essential or toxic trace metals affects growth rates of these diatoms in a species specific manner.

The effects of pH and Al on the acidophilic diatom Asterionella ra[fsii var. americana K6m. were examined in axenic batch cultures. Experiments were performed under conditions of both high (pH 5) and low (pH 6) Al solubility over a range of concentrations from 0 to 30 firno liter-’ total Al. Growth rates were analyzed with respect to analytically determined Al concentrations and to predicted changes in dissolved metal ion speciation in response to Al additions. Growth rates of A. rufiii were significantly reduced above 15 pmol liter-’ total Al at both pH 5 and 6. Al additions increased estimated free ion activities of Al 3+, Fe3+, and Cu*+ through indirect chelator interactions at pH 5 and 6; therefore, all three were significantly correlated with growth rate reductions, Independent manipulations of total Fe and Cu, however, suggested that Al was not indirectly increasing either Fe’+ or Cu2+ free ion activities to toxic levels. Relationships of growth rates to both inorganic monomeric Al (A13 and to estimates of pA1 were strongly pHdependent with toxicity being greater per unit of dissolved Al concentration at pH 6 than at pH 5. These results are consistent qualitatively with predictions that H.’ ions can ameliorate dissolved metal toxicity by competitively excluding AP+ ions from binding to cell-surface ligands. The impact of Al on natural phytoplankton populations therefore is likely to depend on a combination of pHdependent Al solubility, the protonation of cell-surface ligands, and chelator-mediated metal speciation.

Changes in cell size and silica content were examined in response to aluminum additions in cultures of the acidophilic diatom Asterionella ralfsii var. americana Korn at pH 6.0. The effect of Al were examined over a range of steady-state growth rates using silica-limited semicontinuous cultures (Si:P=8.0). Addittions of ≥2.8 μmol.L -1 total Al decreased mean cell length, total surface area, and biovolume up to 40-50%. The effets of Al were dependent on growth rate with the magnitude of size reduction increasing at higher growth rates. The effects of Al were dependent on growth rate with the magnitude of size reduction increasing at higher growth rates. The proportion of small (approximately 15-20 μm) cell length classes increased relative to large (approximately 50 μm length) cell length classes when total Al exceeded 2.8 μmol.L -1 , particularly at higher growth rates (...)

Mysis relicta were sampled at a 100-m reference staton in southeastern Lake Michigan (43°N 86°40′W) from 1985 to 1989, to quantify nighttime water column abundances and to compare vertical distributions with those of Daphnia. Diel vertical migration produced maximum concentrations in the thermocline at night of 1 to 10 mysids∙m−3. Variation among replicates averaged 28% with a 3-net Tucker trawl and 19% with Puget Sound vertical closing nets. Mean areal abundances over 5 yr averaged 110 mysids∙m−2 (SE = 20; n = 30; range = 25 to 645) based on nighttime vertical and oblique net tows at 1–3-wk intervals during summers at the reference station. Synoptic cruises from 43°N to 45°N during August indicated that densities were considerably greater offshore than inshore, and greater in the north than in the south. Hypothesized long-term changes in mysid abundances were not detected. Although Mysis is potentially an important predator on Daphnia, differences in nighttime vertical distributions reduce encounters between Mysis and Daphnia during summer in Lake Michigan, such that Mysis exert mortality rates on Daphnia of

Creosote has been used extensively as an industrial wood preservative for the protection of marine pilings, railway ties, and utility poles and is a common source of polycyclic aromatic hydrocarbons (PAHs) into aquatic environments. At present, there is little information by which to judge the potential for creosote leached from impregnated pilings to cause toxicity to biota in aquatic environments. The objective of the current study was to assess the effects of creosote on zooplankton and phytoplankton populations in freshwater microcosms in relation to changes in the concentration and composition of PAHs leached from creosote-impregnated Douglas fir pilings during an 83-day exposure period. The study consisted of single microcosms containing one half, one, two, three, four, and six treated pilings. Two microcosms that received untreated pilings were used as controls. The total surface area of pilings in each microcosm was normalized by adding the appropriate number of untreated pilings. Samples were collected periodically between -14 and 83 days pre- and postexposure to determine aqueous concentrations of 15 priority PAHs and to assess the response of zooplankton and phytoplankton communities. Plankton community response to creosote was analyzed using principle responses curves. Peak aqueous concentrations of sigmaPAH occurred at day 7, ranging from 7.3 to 97.3 microg/L. Zooplankton abundance decreased in all microcosms after introduction of the impregnated pilings, with the magnitude of response varying as a function of aqueous creosote concentration. Using inverse regression, a no-observed-effect concentration for the zooplankton community of 11.1 microg/L was estimated. In contrast, algal abundance and diversity increased in all treatments between 7 and 21 days and attained levels up to twice that in control microcosms. This trend most likely reflected decreased grazing pressure because of the decrease in zooplankton populations, but it may also have reflected growth stimulation resulting from exposure to various constituents within the creosote mixture. Our results indicate that creosote leached from impregnated pilings deployed under typical conditions (e.g., wharves) may cause transient toxicity to benthic or limnetic communities shortly after deployment, but this likely poses few long-term risks to aquatic freshwater plankton communities.

We examined whether the sensitivity of Ceriodaphnia dubia to copper toxicity was influenced by the hardness of the water in which they were reared or in which they were exposed. Organisms cultured in very hard water were 1.5-fold less sensitive to copper than those in moderately hard water. However, the hardness of the exposure water had a greater (2.5-fold) effect on copper median effective concentration (EC50s).

To assess photosynthesis as a bioindicator of toxicity from polycyclic aromatic hydrocarbons (PAHs), the response of chlorophyll-a fluorescence to creosote exposure was compared with effects on population-level plant growth. Large, outdoor, freshwater microcosms containing Eurasian watermilfoil (Myriophyllum spicatum) received either a single application or multiple applications of liquid creosote at nominal concentrations from 0.109 to 32.7 mg L(-1). For several weeks following treatment, photosynthetic electron transport was measured using pulse amplitude-modulated chlorophyll-a fluorescence. The maximum efficiency of photosystem II electron transport (Fv/Fm) and the quantum yield of photochemistry (deltaF/F'm) were diminished in plants shortly after the addition of creosote. In microcosms that received a single treatment of creosote only, the 50% effective concentrations (EC50s), expressed as the aqueous concentration of 15 of the most abundant PAHs, were 0.28 mg L(-1) for Fv/Fm and 0.30 mg L(-1) for deltaF/F'm. Chlorophyll-a fluorescence was diminished to a greater extent in microcosms that received multiple treatments of creosote, with EC50s of 0.13 mg L(-1) for Fv/Fm and 0.10 mg L(-1) for deltaF/F'm. Plant biomass accumulation was inhibited in a concentration-dependent manner in all microcosms treated with creosote, but this inhibition occurred to a greater degree in microcosms treated with multiple creosote applications. The response of chlorophyll-a fluorescence, measured only 8 d after creosote treatment, was similar to plant growth over the entire growing season, indicating that this technique can be used to estimate potential effects of contaminants before detrimental impacts on populations.

The mitigating effect of increasing hardness on metal toxicity is reflected in water quality criteria in the United States over the range of 25–400 mg l −1 (as CaCO 3 ). However, waters in the arid west of the US frequently exceed 400 mg l −1 hardness, and the applicability of hardness–toxicity relationships in these waters is unknown. Acute toxicity tests with Ceriodaphnia dubia were conducted at hardness levels ranging from approximately 300 to 1200 mg l −1 using reconstituted waters that mimic two natural waters with elevated hardness: (1) alkaline desert southwest streams (Las Vegas Wash, NV), and (2) low alkalinity waters from a CaSO 4 -treated mining effluent in Colorado. The moderately-alkaline EPA synthetic hard water was also included for comparison. Copper toxicity did not consistently vary as a function of hardness, but likely as a function of other water quality characteristics (e.g., alkalinity or other correlated factors). The hardness equations used in regulatory criteria, therefore, may not provide an accurate level of protection against copper toxicity in all types of very hard waters. However, the mechanistic Biotic ligand model generally predicted copper toxicity within ±2 X of observed EC 50 values, and thus may be more useful than hardness for modifying water quality criteria.

The ability of a commercial (Aldrich Chemical Co.) humic acid (AHA) to ameliorate the photo-induced toxicity of polycyclic aromatic hydrocarbons (PAHs) was examined using Lemna gibba L. (G3). Plants were exposed to anthracene and benzo(a)pyrene both with and without AHA and grown under visible light as well as lighting that simulates relative abundances of UV-A and UV-B in natural sunlight (SSR). Modest additions of 1.6 mg.L-1 AHA were sufficient to ameliorate the photo-induced toxicity of 2 mg.L-1 anthracene by improving growth rates to nearly 50% of controls and inducing minor recovery from complete chlorosis in the most highly affected plants. Benzo(a)pyrene induced minor, but significant, chlorosis under SSR, and AHA additions always increased growth rate and chlorophyll content, although to less of a degree than anthracene toxicity under SSR. The protective effects of AHA on anthracene toxicity increased linearly with increases in AHA concentrations up to 6.2 mg.L-1. Slopes of these relationships changed in the presence of UV light relative to visible light treatments; thus UV changed the extent to which AHA mediates PAH toxicity. However, the net effect was still for AHA to ameliorate PAH photo-induced toxicity even though UV has the potential to photooxidize AHA and enhance the production of potentially toxic reactive oxygen species from AHA photosensitization.

Ballast water transport of nonindigenous species (NIS) is recognized as a significant contributor to biological invasions and a threat to coastal ecosystems. Recently, the use of ozone as an oxidant to eliminate NIS from ballast while ships are in transit has been considered. We determined the toxicity of ozone in artificial seawater (ASW) for five species of marine organisms in short-term (< or = 5 h) batch exposures. Larval topsmelt (Atherinops affinis) and juvenile sheepshead minnows (Cyprinodon variegatus) were the most sensitive to oxidant exposure, and the mysid shrimp (Americamysis bahia) was the most sensitive invertebrate. Conversely, benthic amphipods (Leptocheirus plumulosus and Rhepoxinius abronius) were the least sensitive of all species tested. Mortality from ozone exposure occurred quickly, with median lethal times ranging from 1 to 3 h for the most sensitive species, although additional mortality was observed 1 to 2 d following ozone exposure. Because ozone does not persist in seawater, toxicity likely resulted from bromide ion oxidation to bromine species (HOBr and OBr-), which persist as residual toxicants after at least 2 d of storage. Total residual oxidant (TRO; as Br2) formation resulting from ozone treatment was measured in ASW and four site-specific natural seawaters. The rate of TRO formation correlated with salinity, but dissolved organic carbon and total dissolved nitrogen did not affect TRO concentrations. Acute toxicity tests with each water over 48 h using mysid shrimp, topsmelt, and sheepshead minnows yielded results similar to those of batch exposure. Addition of sodium thiosulfate (Na2S2O3) to ozonated waters resulted in TRO elimination and survival of all organisms. Our results provide necessary information for the optimization of an efficacious ozone ballast water treatment system.

Growth rates for five freshwater algae, Asterionella formosa, Stephanodiscus hantzschii, Scenedesmus sp., Cryptomonas ozolini, and Anabaena flos-aquae, in media ranging in pH from 5.0 to 7.5 using three zwitterionic buffers, MES, PIPES, and TES, were determined. These buffers supported similar growth rates when compared with each other in treatment groups of similar pH. For pH values below 6.0 no growth occurred or growth rates were significantly reduced in some treatment groups for all species except Cryptomonas. In some cases, these lowered growth rates were partially or completely restored by reducing trace metals in the media by one or two orders of magnitude. We suggest that these buffers could provide a useful technique for investigating the physiological responses of phytoplankton in lakes undergoing acidification.