bluuebunny/crossref_metadata_2025 huggingface dataset:
Bioluminescence inhibition assays for toxicity screening of wood extractives and biocides in paper mill process waters
Authors: Rigol Anna , Latorre Anna , Lacorte Silvia , Barceló Damià
Published: November 2004

The risk associated with wood extractives, biocides, and other additives in pulp and paper mill effluents was evaluated by performing a characterization of process waters and effluents in terms of toxicity and chemical analysis. The individual toxicity of 10 resin acids, two unsaturated fatty acids, and three biocides was estimated by measuring the bioluminescence inhibition with a ToxAlert® 100 system. Median effective concentration values (EC50) of 4.3 to 17.9, 1.2 to 1.5, and 0.022 to 0.50 mg/L were obtained, respectively. Mixtures of these three families of compounds showed antagonistic effects. Chemical analysis of process waters was performed by liquid chromatography-and gas chromatography-mass spectrometry. Biocides such as 2-(thiocyanome-thylthio)-benzotiazole (TCMTB) (EC50 = 0.022 mg/L) and 2,2-dibromo-3-nitrilpropionamide (DBNPA) (EC50 = 0.50 mg/L) were the most toxic compounds tested and were detected at concentrations of 16 and 59 μg/L, respectively, in a closed-circuit recycling paper mill. Process waters from kraft pulp mills, printing paper mills, and packing board paper mills showed the highest concentration of resin acids (up to 400 μg/L) and accounted for inhibition percentages up to 100%. Detergent degradation products such as nonylphenol (NP) and octylphenol (OP) and the plasticizer bisphenol A (BPA) were also detected in the waters at levels of 0.6 to 10.6, 0.3 to 1.4, and 0.7 to 187 μg/L, respectively. However, once these waters were biologically treated, the concentration of detected organic compounds diminished and the toxicity decreased in most cases to values of inhibition lower than 20%.
Bioconcentration of inorganic and organic thallium by freshwater phytoplankton
Authors: Twiss Michael R. , Twining Benjamin S. , Fisher Nicholas S.
Published: November 2004

Uptake of inorganic Tl(I) and dimethylthallium, (CH3)2Tl+, by Chlorella spp. (Chlorophyta) and the diatom Stephan-odiscus hantzschii (Heterokontophyta) were measured using radio-tracer techniques in water from Lakes Erie and Superior (North America). Uptake of both Tl(I) and dimethylthallium was bioactive. Uptake of [204Tl]-Tl(I) was greater in Lake Superior water than in Lake Erie water due to the greater K content in Lake Erie that inhibits Tl(I) uptake by phytoplankton but not that of [204Tl]-dimethylthallium. Volume-based bioconcentration factors for Tl(I) after 72 h of exposure were 5 × 104 and 1.1 × 104 for Chlorella sp. and S. hantzschii; for dimethylthallium they were 7.8 × 102 and 8.3 × 103. Both Tl(I) and Tl(III) were concentrated similarly by Chlorella spp. These results suggest that chlorophytes, but not diatoms, accumulate Tl(I) to a greater extent than dimethylthallium. Greater bioaccumulation factors of inorganic Tl are possible in waters containing low amounts of K+; water quality guidelines seeking to protect biota from deleterious effects of Tl should consider the role of K.
Endangered Vancouver Island marmots (Marmota vancouverensis): Sentinels of atmospherically delivered contaminants to British Columbia, Canada
Authors: Lichota Gillian B. , Mcadie Malcolm , Ross Peter S.
Published: November 2004

We characterized legacy and new contaminants in the highly endangered Vancouver Island (British Columbia, Canada) marmot and found generally low blood and fat concentrations of a complex mixture of pesticides, polychlorinated biphenyls (PCBs), -dibenzo-p-dioxins (PCDDs), -dibenzofurans (PCDFs), polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs), and polychlorinated naphthalenes (PCNs) in their tissues. The dominance of the more volatile α-hexachlorocyclohexane (HCH) and hexachlorobenzene (HCB) pesticides and the lesser chlorinated PCB congeners suggests that atmospheric processes largely explain the contamination of this high-altitude herbivore.
Caged midge larvae (Chironomus riparius) for the assessment of metal bioaccumulation from sediments in situ
Authors: Bervoets Lieven , Meregalli Giovanna , De Cooman Ward , Goddeeris Boudewijn , Blust Ronny
Published: November 2004

First-stage larvae of the midge Chironomus riparius were exposed in small enclosures at 19 sites located in three different river basins in Flanders (Belgium). Sediments were sampled and sieved at 200 μm at all exposure sites. A layer of approximately 2 cm of sediment was placed in each cage and 100 midge larvae were added. Cages were placed in watercourses where resident midge larvae were present. Accumulation of Cd, Cr, Cu, Pb, Ni, and Zn was determined after four weeks of exposure when larvae had reached the fourth stage. Comparing metal levels between caged and resident larvae revealed no significant differences. A significant correlation between metal levels in caged and resident larvae was found when all sites were considered. However, such correlation was low (r2 = 0.28) for Pb. The highly significant r2 values found for Cu and Ni probably were due to only one site. Metal levels in tissue were related to levels in water and sediment, taking into account some sediment characteristics (particle size distribution and organic carbon) and oxygen level in the water. To determine the relative importance of these different sediment factors contributing to the variation in metal accumulation by the chironomids, nonlinear regression models were constructed. With the models used, 56.1, 32.2, and 57.4% of the variation for Cd, Pb, and Zn, respectively, could be described. None and 26.9% of the variation could be described for Cu and Ni, respectively. Among the environmental factors, organic carbon and oxygen levels in water were important in describing the accumulation of metals.
Effect of sediment on the fate of metolachlor and atrazine in surface water
Authors: Rice Pamela J. , Anderson Todd A. , Coats Joel R.
Published: November 2004

In aquatic environments, pesticides can partition between the dissolved phase and particulate phase depending on the type of suspended sediment present and the physical and chemical properties of the pesticides and water. Particulate matter and sediment can alter the bioavailability of contaminants to organisms and therefore influence their toxicity and availability for microbial degradation. Experiments were conducted to determine the degradation of atrazine (6-chloro-N-ethyl-N′-(1-methylethyl)-1,3,5-triazine-2,4-diamine) and metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-(methooxyprop-2-yl)acetamide) in surface water, and to evaluate the contribution of sediment to their dissipation. Sediment significantly reduced concentrations of atrazine and metolachlor in the surface water as a result of greater degradation, evident by increased quantities of degradates in the surface water, and the partitioning of the herbicide or herbicide degradates in the sediment. First-order 50% dissipation time (DT50) values for atrazine and metolachlor were 42 and 8 d in the surface water-sediment incubation systems, which were almost four times less than the DT50s calculated for the sediment-free systems. The results of this research illustrate the importance of sediment in the fate of pesticides in surface water. Greater comprehension of the role of sediment to sequester or influence degradation of agrichemicals in aquatic systems will provide a better understanding of the bioavailability and potential toxicity of these contaminants to aquatic organisms.
Comparative effects of pH and Vision® herbicide on two life stages of four anuran amphibian species
Authors: Edginton Andrea N. , Sheridan Patrick M. , Stephenson Gerald R. , Thompson Dean G. , Boermans Herman J.
Published: November 2004

Vision®, a glyphosate-based herbicide containing a 15% (weight:weight) polyethoxylated tallow amine surfactant blend, and the concurrent factor of pH were tested to determine their interactive effects on early life-stage anurans. Ninety-six-hour laboratory static renewal studies, using the embryonic and larval life stages (Gosner 25) of Rana clamitans, R. pipiens, Bufo americanus, and Xenopus laevis, were performed under a central composite rotatable design. Mortality and the prevalence of malformations were modeled using generalized linear models with a profile deviance approach for obtaining confidence intervals. There was a significant (p < 0.05) interaction of pH with Vision concentration in all eight models, such that the toxicity of Vision was amplified by elevated pH. The surfactant is the major toxic component of Vision and is hypothesized, in this study, to be the source of the pH interaction. Larvae of B. americanus and R. clamitans were 1.5 to 3.8 times more sensitive than their corresponding embryos, whereas X. laevis and R. pipiens larvae were 6.8 to 8.9 times more sensitive. At pH values above 7.5, the Vision concentrations expected to kill 50% of the test larvae in 96-h (96-h lethal concentration [LC50]) were predicted to be below the expected environmental concentration (EEC) as calculated by Canadian regulatory authorities. The EEC value represents a worst-case scenario for aerial Vision application and is calculated assuming an application of the maximum label rate (2.1 kg acid equivalents [a.e.]/ha) into a pond 15 cm in depth. The EEC of 1.4 mg a.e./L (4.5 mg/L Vision) was not exceeded by 96-h LC50 values for the embryo test. The larvae of the four species were comparable in sensitivity. Field studies should be completed using the more sensitive larval life stage to test for Vision toxicity at actual environmental concentrations.
Assessing structural and functional plankton responses to carbendazim toxicity
Authors: Slijkerman Diana M.E. , Baird Donald J. , Conrad Anne , Jak Robbert G. , van Straalen Nico M.
Published: November 2004

A model ecosystem experiment was conducted to investigate the ability of an in situ Daphnia magna feeding bioassay to assess impairment of ecosystem function. Animals were deployed in model ecosystems dosed with different concentrations of the fungicide carbendazim, and effects on the postexposure feeding rate of D. magna were compared with effects on zooplankton species richness (ecosystem structure) and development of phytoplankton biomass (ecosystem function). In the medium-dosed systems (21 μg/L), a structural change was observed within the zooplankton community, but no indirect effects on phytoplankton development were detected. It appears that at this treatment level, functional redundancy was sufficient to prevent functional impairment despite species loss. The feeding assay did not show any response at this concentration. In the high-dosed systems (221 μg/L), structural changes in the zooplankton community were accompanied by increased development of phytoplankton biomass. The feeding bioassay also showed a significant response at this concentration. At the high treatment level, species loss resulted in functional impairment, indicating that at this level, functional redundancy could not compensate for loss of individuals. The D. magna feeding bioassay matched well with the functional response (i.e., the indirect effects on phytoplankton) in the dosed systems but not with the more subtle effects on zooplankton community structure. These results lend positive support to the use of in situ feeding bioassays in combination with structural indices, such as species richness, to assess the effects of stress on ecosystem functioning in a direct way.
Development of a coupled metal speciation-fate model for surface aquatic systems
Authors: Bhavsar Satyendra P. , Diamond Miriam L. , Evans Les J. , Gandhi Nilima , Nilsen Joel , Antunes Paula
Published: November 2004

A coupled metal transport and speciation model (TRANSPEC) has been developed for surface aquatic systems that explicitly considers the influence of metal speciation on fate. The TRANSPEC, which is general to most metal and surface aquatic systems, is constructed by sequentially coupling the speciation/complexation module (in this application MINEQL+) with the fugacity/aquivalence approach for the fate calculations. This model formulation increases the mechanistic detail, predictive power, and fidelity to reality of current fugacity-aquivalence fate models for metals by estimating aqueous speciation and complexation, rather than relying on empirically derived partition coefficients. A pseudo-steady state version of TRANSPEC was used to simulate Zn dynamics in Ross Lake (Flin Flon, MB, Canada) that received elevated metal and organic matter inputs for over 50 years. Field studies revealed that ZnS forms soluble ZnL, Zn2+, and ZnSO40 increasing pore water concentrations when surficial sediments turn oxic during fall. The model results for three seasonal scenarios suggest that Zn remobilization is driven by resuspension of insoluble ZnS and the contribution of diffusion is negligible, even during fall when ZnS dissolves to increase the concentration of soluble species under oxic conditions in the sediments. The low diffusive flux is due to the binding of Zn to colloidal dissolved organic matter (DOM) for which sediment-water diffusion is relatively slow, a result that was obtained as a result of considering metal speciation in the fate calculations.
Fate and stability of 14C-labeled 2,4,6-trinitrotoluene in contaminated soil following microbial bioremediation processes
Authors: Weiß Martin , Geyer Roland , Günther Thomas , Kaestner Matthias
Published: November 2004

Biological treatment of 2,4,6-trinitrotoluene (TNT) in soil rarely results in complete mineralization of the parent compound. More often, the largest proportion of the TNT carbon is incorporated into the soil organic matrix. Therefore, we evaluated the stability of nonextractable residues from various bioremediation processes of 14C-TNT in soils. The extractable amounts of the residual radioactivity varied between 7 and 33% and thus the nonextractable amount between 93 and 67% (3–15% in fulvic acids, 26–46% in humic acids, and 27–44% in the humin fraction). The residue-containing soils were analyzed for the release of radioactivity after treatment by physical (freeze and thaw, grinding of soil, and steam extraction), chemical (acid rain and addition of metal complexing agent), and biological methods (addition of compost, white rot fungi, radical-generating enzymes, and germination of plants). Freeze and thaw treatment and grinding of the soil did not alter the partitioning of the label significantly. Steam extraction and acid rain extraction increased the water extractability to 11 to 29% and to 51.6% in the native TNT-contaminated soil. The addition of ethylenediamine-tetraacetate (EDTA) increased the extractability from 7 to 12%. After biological treatment, only slightly increased extractability (<<10%) was observed. No increase of extractable TNT or known metabolites was observed with any of the treatments. Thus, under the treatment conditions applied in this study, the residues formed during microbial transformation of TNT may be biogenic residues with low mobilization potential and low hazardous impact.
Influence of chloride on silver uptake by two green algae, Pseudokirchneriella subcapitata and Chlorella pyrenoidosa
Authors: Lee Dae-Young , Fortin Claude , Campbell Peter G. C.
Published: November 2004

Silver bioavailability in the presence of chloride was estimated from short-term (≤60 min) uptake experiments with two green algae, Pseudokirchneriella subcapitata and Chlorella pyrenoidosa. In the first experiment, silver uptake was monitored under two concentration regimes in which total dissolved silver ([Ag]tot) and [Cl] were manipulated to maintain [Ag+] at a constant value (10 nM). Comparable uptake rates were measured for both treatments despite the dramatic changes in [Cl] and [Ag]tot. In the second experiment, ambient [Ag]tot was held constant (10 or 115 nM), but [Cl] was varied (0.005-50 mM) to explore the whole range of silver chloro-complexes. Intracellular silver varied markedly along the [Cl] gradient and exhibited a clear, positive correlation with ambient [Ag+] for both algae. We conclude that the biotic ligand model reliably describes silver bioavailability in the presence of chloride for the two test algae and that its applicability depends on the relative magnitudes of silver fluxes through the unstirred diffusion layer and across the cell membrane, with the latter being affected by the presence or absence of a Cu(I) transporter. In the presence of chloride, no evidence was found for the internalization of silver via anion transport or passive diffusion of the neutral mono-chloro-complex, AgCl0.
Some fundamental (and often overlooked) considerations underlying the free ion activity and biotic ligand models
Authors: Hassler Christel S. , Slaveykova Vera I. , Wilkinson Kevin J.
Published: November 2004

Trace metal bioavailability is often evaluated on the basis of steady-state models such as the free ion activity model (FIAM) and the biotic ligand model (BLM). Some of the assumptions underlying these models were verified by examining Pb and Zn uptake by the green microalga Chlorella kesslerii. Transporter bound metal ({M-Rcell}) and free ion concentrations ([MZ+]) were related to experimentally determined uptake fluxes (Jint). Although the BLM and FIAM correctly predicted Pb uptake in the absence of competing ions, they failed to predict competitive interactions with Ca2+, likely because of modifications of the algal surface charge and the active nature of Ca2+ transport. Zinc transport is also active; in this case, both the internalization rate constant (kint) and the equilibrium constant for the binding of Zn to the transport sites (KZn-Rcell) varied as a function of [Zn2+] in the bulk solution. For this reason, Zn uptake could not be modeled by the steady-state models either in the presence or absence of competitors (Cd and Ca). Furthermore, the role of Cu on Pb and Zn adsorption and uptake could not be predicted by either model because of secondary effects on the algal physiology and membrane permeability. Finally, a 17°C reduction in temperature resulted in a two-to fivefold decrease in membrane permeability of the metals, an observation that also is unaccounted for by either the FIAM or BLM. This paper emphasizes the limitations of the models in well-controlled laboratory systems with the goal of extrapolating the results to complex environmental systems.
Effects of the antifungal imidazole ketoconazole on CYP1A and CYP3A in rainbow trout and killifish
Authors: Hegelund Tove , Ottosson Karin , Rådinger Madeleine , Tomberg Peter , Celander Malin C.
Published: November 2004

The use of N-substituted imidazoles is widespread, and imidazole and triazole fungicides have been detected in the aquatic environment and shown to bioaccumulate in fish. We have investigated effects of the model imidazole, ketoconazole, on drug-metabolizing cytochrome P450 (CYP) forms. We focused on cytochrome P4501A (CYP1A) and cytochrome P4503A (CYP3A) expression and activities in juvenile rainbow trout and in adult killifish. The CYP1A expression (mRNA, protein) and activity was induced in rainbow trout, whereas in killifish no effect of ketoconazole on CYP1A protein expression was observed. A biphasic dose-response relationship was observed between ketoconazole exposure and hepatic CYP1A-mediated ethoxyresorufin O-deethy-lase (EROD) activity in rainbow trout in vitro and in vivo, implying that higher doses of ketoconazole inhibit CYP1A activities. Slight induction of CYP3A protein levels was observed in rainbow trout exposed in vivo to ketoconazole. However, the CYP3A-mediated benzyloxy-4-[trifluoromethyl]-coumarin (BFC) O-debenzyloxylase activity was reduced in rainbow trout and killifish treated with ketoconazole. In vitro inhibition studies confirmed that ketoconazole was a potent inhibitor of both CYP3A and CYP1A enzyme activities in these species. This study showed that ketoconazole induced CYP1A and CYP3A expression in rainbow trout. However, the most pronounced effect of ketoconazole was a 60 to 90% decrease in CYP3A catalytic activities in rainbow trout and in killifish.
Assessment of mercury in waters, sediments, and biota of New Hampshire and Vermont lakes, USA, sampled using a geographically randomized design
Authors: Kamman Neil C. , Lorey Peter M. , Driscoll Charles T. , Estabrook Robert , Major Andrew , Pientka Bernie , Glassford Ed
Published: November 2004

We report on mercury (Hg) contamination in waters, sediments, and biota of Vermont and New Hmpshire (USA) lakes measured during 1998—2000, using a geographically randomized design. Waters and sediments of 92 lakes were sampled for mercury, methylmercury, and ancillary parameters. Yellow perch (Perca flavescens) muscle tissues were analyzed for mercury on 47 of these lakes. Interannual variation in mercury was limited; only epilimnetic Hg was elevated by approximately 1.5 ng/L in 1998 over remaining years because of wet weather. Aqueous total and methylmercury concentrations were elevated in both dystrophic and eutrophic lakes over other types. Yellow perch tissue concentrations were elevated by 0.218 μg/g in dystrophic lakes over other types and were very low in eutrophic lakes. Fish tissue mercury concentrations showed no relationship to hypolimnetic or sediment mercury or methylmercury. A statistical model indicated that yellow perch tissues in 40.2 ± 13% of lakes were likely to exceed the U.S. Environmental Protection Agency (U.S. EPA) methylmercury criterion of 0.3 μg/g, and yellow perch from New Hampshire were twice as likely to exceed the criterion as those from Vermont. Results of this study provide a regional-scale baseline against which the success of future reductions in mercury emissions can be assessed.
Bioconcentration, biotransformation, and elimination of polycyclic aromatic hydrocarbons in sheepshead minnows (Cyprinodon variegatus) Exposed to Contaminated Seawater
Authors: Jonsson Grete , Bechmann Renee K. , Bamber Shaw D. , Baussant Thierry
Published: November 2004

Sheepshead minnows (Cyprinodon variegatus) were continuously exposed to two concentrations of polycyclic aromatic hydrocarbons (PAHs) dissolved in seawater (Σ PAH = 7.57 and 72.31 μg/L) for 36 d, followed by 8 d of depuration. The PAHs studied were naphthalene (NPH or C0-NPH), phenanthrene (PHE or C0-PHE), pyrene (PYR), 2-methylnaphthalene (C1-NPH), 1,3-dimethylnaphthalene (C2-NPH), 2-isopropylnaphthalene (C3-NPH), 9-methylphenanthrene (C1-PHE), and 9-ethylphenanthrene (C2-PHE). Uptake rate constants (k1) for NPHs increased with increasing degree of alkylation and log value of the octanol/water partition coefficient (Kow), whereas k1 values for three- and four-ring PAHs were lower despite their high log Kow values. Elimination rate constants (k2) for the homologue series of NPHs and PHEs generally increased with decreasing degree of alkylation and log Kow values. However, the depuration time did not directly correlate with the molecular size for nonalkylated PAHs. Bioconcentration factors (BCFs) were estimated from the ratio of k1 to k2 and also directly from PAH concentrations in fish tissue and water samples, and the factors generated by the two methods were very similar. A significant positive correlation was determined between log BCFs and log Kow values for the series of C0- through C3-NPH at both low (r2 = 0.985, p = 0.0077) and high (r2 = 0.956, p = 0.022) exposures, although this correlation was not determined for all the PAHs studied. As a result of increased metabolism and/or reduced bioavailability with increasing lipophilic character, the estimated BCFs for C0- through C2-PHE and PYR were generally lower than those for C0- through C3-NPH. The two exposure levels revealed minor variations in k1 and k2 values for parent PAHs and in the temporal pattern of PAH metabolite concentrations in bile. The present results indicate that the presence and nature of alkyl groups have a significant influence on the kinetics and metabolism of PAHs in fish.
Sulfide as a confounding factor in toxicity tests with the sea urchin Paracentrotus lividus: Comparisons with chemical analysis data
Authors: Losso Chiara , Novelli Alessandra Arizzi , Picone Marco , Ghirardini Annamaria Volpi , Ghetti Pier Francesco , Rudello Danilo , Ugo Paolo
Published: November 2004

Sperm cell and embryo toxicity tests with the sea urchin Paracentrotus lividus were performed to assess the toxicity of sulfide, which is considered a confounding factor in toxicity tests. For improved information on the sensitivity of these methods to sulfide, experiments were performed in the same aerobic conditions used for testing environmental samples, with sulfide concentrations being monitored at the same time by cathodic stripping voltammetry. New toxicity data for sulfide expressed as median effective concentration (EC50) and no-observed-effect concentration (NOEC) are reported. The EC50 value for the embryo toxicity test (total sulfide at 0.43 mg/L) was three times lower than for the sperm cell test (total sulfide at 1.20 mg/L), and the NOEC values were similar (on the order of total sulfide at 10−1 mg/L) for both tests. The decrease in sulfide concentration during the bioassay as a consequence of possible oxidation of sulfide by dissolved oxygen was determined by voltammetric analysis, indicating a half-life of about 50 min in the presence of gametes. To check the influence of sulfide concentrations on toxicity effects in real samples, toxicity (with the sperm cell toxicity test) and chemical analyses also were performed in pore-water samples collected with an in situ sampler in sediments of the Lagoon of Venice (Italy). A highly positive correlation between increased acute toxicity and increased sulfide concentration was found. Examination of data revealed that sulfide is a real confounding factor in toxicity testing in anoxic environmental samples containing concentrations above the sensitivity limit of the method.
Effects of atrazine on fathead minnow in a short-term reproduction assay
Authors: Bringolf Robert B. , Belden Jason B. , Summerfelt Robert C
Published: November 2004

Atrazine is the most extensively used herbicide in the United States. Part-per-million concentrations of atrazine have been reported in agricultural runoff. It is detectable in surface waters and precipitation throughout the year, and it has been found in groundwater sources of drinking water. Recent studies indicate that atrazine may be a potent endocrine-disrupting compound in frogs exposed to part-per-billion (μg/L) concentrations. For these reasons, the effects of atrazine (5 and 50 μg/L) on several endpoints related to reproductive fitness were examined in fathead minnows (Pimephales promelas) in a 21-d static exposure. Estradiol (0.5 μg/L) was included as a positive-control treatment. Endpoints examined in adult fish during and after the exposures included survival, egg production, number of spawns, eggs/spawn, relative gonad weight, gonad histology, number of nuptial tubercles, and plasma vitellogenin concentration. Eggs produced during the exposures were hatched and reared in control water. The percentages of embryos fertilized and hatched as well as larval survival were evaluated. Decreasing trends were observed in relative testis weight, testis maturity, and percentage embryo fertilization. These trends suggest that further investigation is warranted, but the differences in these and other endpoints were not statistically significant in the atrazine-exposed fish. Nearly all endpoints concerning fish exposed to estradiol were significantly different from atrazine-exposed fish and control fish. These results suggest that atrazine did not have strong estrogenic effects in adult fathead minnows and did not cause overt reproductive toxicity at environmentally relevant concentrations.
Effect of dissolved organic matter source on acute copper toxicity to Daphnia magna
Authors: De Schamphelaere Karel A. C. , Vasconcelos Flavio M. , Tack Filip M. G. , Allen Herbert E. , Janssen Colin R.
Published: November 2004

The protective effect of dissolved organic matter (DOM) on metal toxicity to aquatic organisms has been reported by numerous authors. Bioavailability models such as the biotic ligand model (BLM) thus account for this factor to predict metal toxicity to aquatic organisms. Until now, however, few attempts have been made to assess the effect of the DOM source on metal speciation and toxicity and, accordingly, on BLM predictions. The aims of this study were to investigate to what extent DOMs differ in their ability to decrease acute copper toxicity to the cladoceran Daphnia magna and to evaluate if ultraviolet (UV) absorbance measurements may be a simple and effective method to incorporate DOM variability into the acute Cu-BLM for D. magna. Acute toxicity tests were carried out in artificial test water enriched with DOMs isolated from six locations in Europe and North America and in seven natural European surface waters. The acute Cu-BLM for D. magna was then used to estimate the copper complexing capacity of each DOM (expressed as % active fulvic acid, %AFA). A factor of 6 difference was observed between the lowest and the highest copper complexing capacity. A significant linear relationship was observed between the UV-absorbance coefficient at 350 nm (ε350) and the %AFA. Linking this relationship to the acute Cu-BLM resulted in a significant improvement of the predictive capacity of this BLM. Without accounting for this relationship, 90% of the predicted 48-h 50% effective concentrations (EC50) were within a factor of 2 of the observed EC50s; taking this relationship into account, 90% of the EC50s were predicted with an error of less than factor 1.3. The present study and other studies seem to indicate that UV absorbance may be a good measure of biologically and toxicologically relevant differences in copper binding behavior of DOM.
Effects of zinc pyrithione and copper pyrithione on microbial community function and structure in sediments
Authors: Petersen Dorthe Groth , Dahllof Ingela , Nielsen Lars Peter
Published: November 2004

The effects of the new antifouling biocides, zinc pyrithione (ZPT) and copper pyrithione (CPT), onmicrobial communities in estuarine sediments were studied in microcosms. As functional endpoints, fluxes of nutrients (NO−3, NH+4, HPO2−4, Si(OH)4) and protein synthesis ([14C]leucine incorporation) were used, whereas molecular fingerprinting methods (polymerase chain reaction/denaturing gradient gel electrophoresis) were used to describe the bacterial community structure. The lowest-observed-effect concentration (LOEC) for ZPT was 0.001 nmol/g dry sediment for the phosphate flux and total DNA content, whereas the LOEC for CPT was 0.1 nmol/g dry sediment for the nitrate flux and total DNA content. Nitrate fluxes increased significantly following additions of both ZPT and CPT, whereas ammonium fluxes decreased significantly after ZPT addition, suggesting changes in the nitrification and denitrification processes. The total DNA content decreased significantly following addition of both ZPT and CPT, but at the highest addition of ZPT (10 nmol ZPT/g dry sediment), an increase in total DNA content was found. Increased protein synthesis and bacterial diversity were also observed at this concentration of ZPT, suggesting growth of tolerant opportunistic species.
Laboratory and field responses to cadmium: An experimental study in effluent-dominated stream mesocosms
Authors: Brooks Bryan W , Stanley Jacob K. , White Jessica C , Turner Philip K. , Wu K. Benjamin , La Point Thomas W.
Published: November 2004

Although select stream flows in the southwestern United States are dominated by effluent discharges, metal hazards have not been experimentally evaluated in effluent-dominated streams. Lotic mesocosms were designed to assess cadmium effects on multiple levels of biological organization, to determine relevance to regulatory criteria of standard laboratory toxicity tests, and to link laboratory tests to stream responses. Replicate streams were treated with 15 or 143 μg/L Cd during a 10-d study. Streams were sampled on days 0 and 10 for benthic macroinvertebrates, periphyton, and ecosystem metabolism. Concurrent Ceriodaphnia dubia and Pimephales promelas laboratory tests were performed with water from streams. Individual organism, population, and community response variables were affected by 143 μg/L Cd but not by the 15-μg/L treatment level. A biotic ligand model for cadmium predicted a 48-h median effective concentration (EC50) value of 280 μg/L Cd for C. dubia in these effluent-dominated streams; an EC50 value of 38.3 μg/L Cd was estimated for C. dubia in tests performed with reconstituted hard water. Our findings generally support use of the biotic ligand model for establishing site-specific, acute water quality criteria for cadmium. However, future effluent-dominated stream research is required to evaluate relationships between chronic cadmium exposure and organismal and community responses.
An enzyme-linked immunosorbent assay for lipovitellin quantification in copepods: A screening tool for endocrine toxicity
Authors: Volz David C. , Chandler G. Thomas
Published: November 2004

Vitellogenin (VTG) has been widely used as a biomarker of estrogenic exposure in fish, leading to the development of standardized assays for VTG quantification. However, standardized quantitative assays for invertebrate, particularly crustacean, lipovitellin (also known as vitellin [VTN]) are lacking. In this study, a fluorescence-based VTN enzyme-linked immunosorbent assay (ELISA) was developed to quantify microquantities of VTN in the estuarine, sediment-dwelling copepod Amphiascus tenuiremis. This ELISA utilizes a VTN-specific polyclonal antibody developed against amphipod (Leptocheirus plumulosus) embryo VTN and exhibits specificity toward female copepod proteins. In routine assays, the working range of the ELISA was 31.25 to 1,000 ng/ml (75–25% specific binding/maximum antibody binding [B/B0]) with a 50% B/B0 intra- and interassay variation of 3.9% (n = 9) and 12.5% (n = 26), respectively. This ELISA is capable of detecting VTN as low as 2 ng/ml, and can accurately detect VTN in as few as four copepods. The ELISA significantly discriminated positive (gravid female) and negative (male) samples, and was suitable for screening endocrine toxicity in copepods. Stage-I juvenile copepods were individually reared to adults in aqueous microvolumes of the phenylpyrazole insecticide, fipronil, and whole-body homogenate extracts were assayed for VTN levels. Fipronil-exposed virgin adult females, but not males, exhibited significantly higher levels of VTN relative to control males and females. This crustacean VTN ELISA is likely useful for evaluating endocrine activity of environmental toxicants in copepods and other crustacean species.
Effects of chronic waterborne nickel exposure on two successive generations of Daphnia magna
Authors: Pane Eric F. , Mcgeer James C. , Wood Chris M.
Published: November 2004

In a 21-d chronic toxicity test in which an F0 generation of Daphnia magna were exposed to waterborne Ni, the no-observable-effect concentration (for survival, reproduction, and growth) was 42 μg Ni L−1, or 58% of the measured 21-d median lethal concentration (LC50) of 71.9 μg Ni L−1 (95% confidence interval, 56.5–95.0). Chronic exposure to 85 μg Ni L−1 caused marked decreases in survival, reproduction, and growth in F0 animals. In the F1 generation (daphnids born of mothers from the chronically exposed F0 generation), animals chronically exposed to 42 μg Ni L−1 for 11 d weighed significantly less (20%) than controls, indicating increased sensitivity of F1 animals. Additionally, in this successive generation, significant decreases in whole-body levels of metabolites occurred following exposure to both 42 μg Ni L−1 (decreased glycogen and adenosine triphosphate [ATP]) and 21 μg Ni L−1 (decreased ATP). No significant changes were observed in whole-body total lipid, total protein, and lactate levels at any concentration. Whereas F1 neonates with mothers that were exposed to 21 μg Ni L−1 showed increased resistance to acute Ni challenge, as measured by a significant (83%) increase in the acute (48-h) LC50, F1 neonates with mothers that were exposed to 42 μg Ni L−1 were no more tolerant of acute Ni challenge than control animals were. Nickel accumulations in F1 animals chronically exposed to 21 and 42 μg Ni L−1 were 11- and 18-fold, respectively, above control counterparts. The data presented suggest that chronic Ni exposure to two successive generations of D. magna lowered the overall energy state in the second generation. Whereas the quantity of neonates produced was not affected, the quality was; thus, environmentally meaningful criteria for regulating waterborne Ni concentrations in freshwater require consideration of possible multigenerational effects.
Eiders (Somateria mollissima) obtain nodularin, a cyanobacterial hepatotoxin, in baltic sea food web
Authors: Sipiä Vesa O. , Karlsson Krister M. , Meriluoto Jussi A. O. , Kankaanpää Harri T.
Published: November 2004

Nodularin (NODN) is a cyclic pentapeptide hepatotoxin produced by the cyanobacterium Nodularia spumigena, which occurs regularly in the Baltic Sea during the summer season. Nodularia blooms have caused several animal kills in the Baltic Sea area, and NODLN has been found in mussels and fish caught from the northern Baltic Sea in 1996 to 2002. We analyzed liver samples of common eider (Somateria mollissima) for NODLN by enzyme-linked immunosorbent assay (ELISA) and liquid chromatography/mass spectrometry (LC-MS). Eiders feed extensively on mussel and can be exposed to NODLN by contaminated mussels. Fifteen eiders were shot and collected from three different sites in the western Gulf of Finland (northern Baltic Sea) in August and September 2002. Analyses by ELISA and LC-MS showed that eider liver samples contained 3 to 180 μg NODLN/kg dry weight and 0.1 to 5.8 μg NODLN/liver (dry wt). This is the first documentation of NODLN in seabirds and additional evidence for the transfer of NODLN in different parts of the Baltic Sea food web.
Noncovalent interactions between aromatic compounds and dissolved humic acid examined by nuclear magnetic resonance spectroscopy
Authors: Simpson Myrna J. , Simpson André J. , Hatcher Patrick G.
Published: November 2004

We examined the molecular-level interactions of aromatic compounds with a humic acid that was extensively characterized with one- and two-dimensional nuclear magnetic resonance (NMR) spectroscopy. Interactions of target compounds were evaluated by monitoring their NMR relaxation properties. Solid-state NMR revealed that the humic sample contains paraffinic carbon (31%), substituted aliphatic carbon (30%), and aromatic carbon (28%). The liquid-state experiments further identified amino acids, a range of carbohydrates, methoxylated aromatics (likely derived from lignin), and a series of aliphatic chains. The 13C spin-lattice relaxation time (T1) of site-specifically labeled naphthalene, 1-naphthol, and quinoline was found to decrease with increasing additions of humic acid. The 1H T1 values also were measured and demonstrated that the association with the humic acid was not specific because all the protons acquired the T1 value of the humic acid at the same rate. The lack of a chemical shift change and an increase in signal line broadening indicates that the interaction between these compounds and humic acid is noncovalent. These interactions were detected at low humic concentrations (5 mg C/L) and suggest that low concentrations of humic material, which are prevalent in both aquatic and terrestrial systems, will significantly affect the fate and transport of contaminants in the environment.
Estrogenic potential of the Venice, Italy, lagoon waters
Authors: Pojana Giulio , Bonfà Angela , Busetti Francesco , Collarin Anna , Marcomini Antonio
Published: November 2004

The exposure of the Venice lagoon (Italy) to endocrine-disrupting compounds (EDCs) from different sources was investigated. Spatial and time distribution of EDC concentrations were determined in four sampling sessions (December 2001–May 2002) by solid phase extraction followed by high-performance liquid chromatography separation coupled with mass spectrometry detection via electrospray interface (SPE-HPLC-ESI-MS), which allowed identification of natural (estradiol, estrone) and synthetic estrogenic compounds, both steroidal (ethinylestradiol, mestranol) and nonsteroidal (benzophenone, bisphenol-A, nonylphenol, nonylphenol monoethoxylate carboxylate). No significant differences in the EDC distribution were observed between stations located near selected sources (raw sewage from the historical center of Venice, treated municipal and industrial effluents from sewage treatment plants, and areas undergoing the inflow of rivers). While synthetic nonsteroidal analytes were recorded in the 1 to 1,040 ng/L range (average concentration: 34 ng/L), steroidal EDC (estradiol, ethinylestradiol) concentrations were lower (1–125 ng/L; average concentration: 8 ng/L). The estrogenic activity of lagoon waters was estimated in terms of estradiol equivalent concentration (EEQ) by applying the estradiol equivalency factors (EEFs). Steroidal EDCs (estradiol, ethinylestradiol) contributed >97% to the total potential estrogenicity of the waters, which accounted for 4 to 172 ng/L (average: 25 ng/L), as total EEQs. These levels are likely to pose adverse effects on the Venice lagoon aquatic organisms.
Micronucleus induction in gill cells of green-lipped mussels (Perna viridis) exposed to mixtures of polycyclic aromatic hydrocarbons and chlorinated pesticides
Authors: Siu William H. L. , Mak Eva , Cao Jia , De Luca-Abbott Sharon B. , Richardson Bruce J. , Lam Paul K. S.
Published: November 2004

Different groups of green-lipped mussels (Perna viridis) were exposed to the same net amount of a genotoxicant mixture of four polycyclic aromatic hydrocarbons ([PAHs]; anthracene, fluoranthene, pyrene, and benzo[a]pyrene) and four organochlorine pesticides ([OCs]; α-hexachlorocyclohexane (HCH), aldrin, dieldrin, and p,p′-DDT) for four weeks under different regimes that simulated various scenarios of fluctuating toxicant levels in the marine environment. Micronucleus (MN) formation in gill cells was studied at the end of each week. Micronucleus frequencies increased with continual addition of genotoxicants, and did not diminish significantly under conditions of either gradually decreasing concentrations or cessation of exposure for one to two weeks, suggesting that the MN response may persist over relatively long exposure periods. An almost two-fold higher mean MN frequency was recorded in a chronic exposure group than in an acute group that had received the same net nominal dose of genotoxicants, indicating that chronic exposure may lead to a greater genotoxic impact than acute exposure. The results suggested that in field studies, MN response should be monitored at multiple time points in order to elucidate the effects of potentially fluctuating toxicant levels. Finally, MN formation was positively correlated with both nominal contaminant levels and tissue levels of the genotoxicants. These findings suggest that MN responses can be a sensitive indicator of exposure to relatively low levels of genotoxicants and that MN response in mussel gill cells can be a stable biomarker of genotoxicity.
Influence of 4-nonylphenol on the structure of nematode communities in freshwater microcosms
Authors: Höss Sebastian , Traunspurger Walter , Everin Gabriele F. S , Jüttner Ingrid , Pfister Gerd , Schramm Karl-Werner
Published: November 2004

We investigated the effect of 4-nonylphenol (NP) on nematode communities in the sediment of freshwater microcosms. Seven treatments were dosed with various concentrations of NP over a period of six weeks by using a controlled-release method (NP1-NP7; maximum sediment concentrations: 0.29–3.37 mg/kg dry wt). Four microcosms were not exposed to NP and served as controls. Nematode communities were analyzed over a period of 15 weeks, including sampling dates before, within, and after the NP application. Communities were characterized in terms of total nematode abundance and species diversity (Shannon index and evenness), as well as composition of species, feeding types, and different life-history strategists (maturity index [MI]). Species composition was analyzed by using a multivariate method (principal response curves). Total nematode abundance and species diversity were not affected in any of the NP-treated microcosms. However, in the highest dosed treatment, NP-induced changes in the nematode communities occurred. Species and feeding types composition, as well as the MI, were affected in the postapplication period, with species composition being altered most clearly. In the highest dosed treatment, deposit-feeding species, classified as colonizers (Eumonhystera), increased in dominance, whereas epistrate feeders and chewers (Prodesmodora and Tobrilus) decreased in relative abundance compared to the control.
Identification of in vitro estrogen and androgen receptor agonists in North Sea offshore produced water discharges
Authors: Thomas Kevin V. , Balaam Jan , Hurst Mark R. , Thain John E.
Published: November 2004

The estrogen receptor (ER) agonist potency of offshore produced water discharges was examined via bioassay-directed chemical analysis. The in vitro estrogen receptor (ER) and androgen receptor (AR) agonist potency of five produced water samples collected from oil-production platforms in the British and Norwegian sectors of the North Sea was determined by using the yeast estrogen and androgen screens. Produced water samples were extracted in situ on the production platforms by using large-volume solid-phase extraction. All five extracts tested positive for the presence of ER agonists, whereas no AR agonist activity could be detected. By using the yeast estrogen screen assay in association with bioassay-directed fractionation, attempts were made to identify the ER agonist compounds present in the produced water extracts. The fractionation procedure used cyano-amino—bonded silica normal-phase high-performance liquid chromatography to isolate estrogenic compounds from produced water extract followed by full-scan gas chromatography—electron-impact mass spectrometry (GC-(EI)MS) to identify them. Isomeric mixtures of C1 to C5 and C9 alkylphenols contributed to the majority of the ER agonist potency measured in the samples.
Development of multispecies algal bioassays using flow cytometry
Authors: Franklin Natasha M. , Stauber Jennifer L. , Lim Richard P.
Published: November 2004

Multispeciesalgal bioassays, suitable for assessing copper toxicity, were developed with three marine (Micromonas pusilla, Phaeodactylum tricornutum, and Heterocapsa niei) and three freshwater (Microcystis aeruginosa, Pseudokirchneriella subcapitata, and Trachelomonas sp.) microalgae. Flow cytometry was used to separate and count algal signals based on pigment fluorescence and cell size. Species were mixed together on the basis of equivalent surface areas to avoid the confounding effect on toxicity of increased biomass for metal binding. Under control conditions (no added copper), M. pusilla growth was inhibited in the presence of the other marine microalgae compared to single-species tests, while the opposite was true (i.e., growth stimulation) for M. aeruginosa and P. subcapitata in freshwater mixtures. Competition for nutrients, including CO2, and algal exudate production may account for these effects. Interactions between microalgal species also had a significant effect on copper toxicity to some species. In freshwater multispecies bioassays, the toxicity of copper to Trachelomonas sp. was greater in the presence of other species, with copper concentrations required to inhibit growth (cell division) rate by 50% (72-h [IC50]) decreasing from 9.8 to 2.8 μg Cu/L in single- and multispecies bioassays, respectively. In contrast, in marine multispecies bioassays, copper toxicity to the marine diatom P. tricornutum was reduced compared to single-species bioassays, with an increase in the 72-h IC50 value from 13 to 24 μg Cu/L. This reduction in copper toxicity was not explained by differences in the copper complexing capacity in solution (as a result of exudate production) because labile copper, measured by anodic stripping voltammetry, was similar for P. tricornutum alone and in the mixture. These results demonstrate that single-species bioassays may over- or underestimate metal toxicity in natural waters.