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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 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.

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.

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.

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

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.