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Archives of Environmental Contamination and Toxicology (v.43, #2)
Assessment of Injury to Fish and Wildlife Resources in the Grand Calumet River and Indiana Harbor Area of Concern, USA by D. D. MacDonald; C. G. Ingersoll; D. E. Smorong; R. A. Lindskoog; D. W. Sparks; J. R. Smith; T. P. Simon; M. A. Hanacek (pp. 130-140).
This article is the second in a series of three that describes the results of a Natural Resource Damage Assessment (NRDA) conducted in the Grand Calumet River and Indiana Harbor Area of Concern (IHAOC). The assessment area is located in northwest Indiana and was divided into nine reaches to facilitate the assessment. This component of the NRDA was undertaken to determine if fish and wildlife resources have been injured due to exposure to contaminants that are associated with discharges of oil or releases of other hazardous substances. To support this assessment, information was compiled on the chemical composition of sediment and tissues; on the toxicity of whole sediments, pore water, and elutriates to fish; on the status of fish communities; and on fish health. The data on each of these indicators were compared to regionally relevant benchmarks to assess the presence and extent of injury to fish and wildlife resources. The results of this assessment indicate that injury to fish and wildlife resources has occurred throughout the assessment area, with up to five distinct lines of evidence demonstrating injury within the various reaches. Based on the frequency of exceedance of the benchmarks for assessing sediment and tissue chemistry data, total polychlorinated biphenyls is the primary bioaccumulative contaminant of concern in the assessment area. It is important to note, however, that this assessment was restricted by the availability of published bioaccumulation-based sediment quality guidelines, tissue residue guidelines, and other benchmarks of sediment quality conditions. The availability of chemistry data for tissues also restricted this assessment in certain reaches of the assessment area. Furthermore, insufficient information was located to facilitate identification of the substances that are causing or substantially contributing to effects on fish (i.e., sediment toxicity, impaired fish health, or impaired fish community structure). Therefore, substances not included on the list of COCs cannot necessarily be considered to be of low priority with respect to sediment injury (e.g., metals, polycyclic aromatic hydrocarbons, alkanes, alkenes, organochlorine pesticides, phthalates, dioxins, and furans, etc.).
An Assessment of Injury to Sediments and Sediment-Dwelling Organisms in the Grand Calumet River and Indiana Harbor Area of Concern, USA by D. D. MacDonald; C. G. Ingersoll; D. E. Smorong; R. A. Lindskoog; D. W. Sparks; J. R. Smith; T. P. Simon; M. A. Hanacek (pp. 141-155).
This article is the first in a series of three that describe the results of a Natural Resource Damage Assessment (NRDA) conducted in the Grand Calumet River and Indiana Harbor Area of Concern (IHAOC). The assessment area is located in northwest Indiana and was divided into nine reaches to facilitate the assessment. This component of the NRDA was undertaken to determine if sediments and sediment-dwelling organisms have been injured due to exposure to contaminants that have accumulated in sediments as a result of discharges of oil or releases of other hazardous substances from industrial, municipal, and nonpoint sources. To support this assessment, information was compiled on the chemical composition of sediment and pore water; on the toxicity of whole sediments, pore water, and elutriates; and on the status of benthic invertebrate communities. The data on each of these indicators were compared to regionally relevant benchmarks to assess the presence and extent of injury to surface water resources (i.e., sediments) or biological resources (i.e., sediment-dwelling organisms). The results of this assessment indicate that sediment injury has occurred throughout the assessment area, with up to four distinct lines of evidence demonstrating injury within the various reaches. The primary contaminants of concern (i.e., those substances that are present at concentrations that are sufficient to cause or substantially contribute to sediment injury) include metals, polycyclic aromatic hydrocarbons, and total polychlorinated biphenyls.
Toxicity Assessment of Sediments from the Grand Calumet River and Indiana Harbor Canal in Northwestern Indiana, USA by C. G. Ingersoll; D. D. MacDonald; W. G. Brumbaugh; B. T. Johnson; N. E. Kemble; J. L. Kunz; T. W. May; N. Wang; J. R. Smith; D. W. Sparks; D. S. Ireland (pp. 156-167).
The objective of this study was to evaluate the toxicity of sediments from the Grand Calumet River and Indiana Harbor Canal located in northwestern Indiana, USA. Toxicity tests used in this assessment included 10-day sediment exposures with the amphipod Hyalella azteca, 31-day sediment exposures with the oligochaete Lumbriculus variegatus, and the Microtox® Solid-Phase Sediment Toxicity Test. A total of 30 sampling stations were selected in locations that had limited historic matching toxicity and chemistry data. Toxic effects on amphipod survival were observed in 60% of the samples from the assessment area. Results of a toxicity test with oligochaetes indicated that sediments from the assessment area were too toxic to be used in proposed bioaccumulation testing. Measurement of amphipod length after the 10-day exposures did not provide useful information beyond that provided by the survival endpoint. Seven of the 15 samples that were identified as toxic in the amphipod tests were not identified as toxic in the Microtox test, indicating that the 10-day H. azteca test was more sensitive than the Microtox test. Samples that were toxic tended to have the highest concentrations of metals, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs). The toxic samples often had an excess of simultaneously extracted metals (SEM) relative to acid volatile sulfide (AVS) and had multiple exceedances of probable effect concentrations (PECs). Metals may have contributed to the toxicity of samples that had both an excess molar concentration of SEM relative to AVS and elevated concentrations of metals in pore water. However, of the samples that had an excess of SEM relative to AVS, only 38% of these samples had elevated concentration of metals in pore water. The lack of correspondence between SEM-AVS and pore water metals indicates that there are variables in addition to AVS controlling the concentrations of metals in pore water. A mean PEC quotient of 3.4 (based on concentrations of metals, PAHs, and PCBs) was exceeded in 33% of the sediment samples and a mean quotient of 0.63 was exceeded in 70% of the thirty sediment samples from the assessment area. A 50% incidence of toxicity has been previously reported in a database for sediment tests with H. azteca at a mean quotient of 3.4 in 10-day exposures and at a mean quotient of 0.63 in 28-day exposures. Among the Indiana Harbor samples, most of the samples with a mean PEC quotient above 0.63 (i.e., 15 of 21; 71%) and above 3.4 (i.e., 10 of 10; 100%) were toxic to amphipods. Results of this study and previous studies demonstrate that sediments from this assessment area are among the most contaminated and toxic that have ever been reported.
Suppression of Pyrite Oxidation by Iron 8-Hydroxyquinoline by Y. Lan; X. Huang; B. Deng (pp. 168-174).
One of the important approaches to prevent pyrite (FeS2) oxidation and subsequent formation of acid mine drainage (AMD) is to create a surface coating on pyrite. In this study, a coating of iron 8-hydroxyquinoline was formed by leaching pyrite with a 0.10 M H2O2/0.0034 M 8-hydroxyquinoline solution; stability of the coated pyrite was tested under various pH and temperature conditions. The results showed that iron 8-hydroxyquinoline coating could significantly suppress further pyrite oxidation by both chemical (H2O2) and biological (e.g., Thiobacillus ferrooxidans) processes. At pH from 3.0 to 5.0 and temperature from 10–40°C, the amount of SO4 2− leached out by 0.10 M H2O2 from the coated pyrite samples was 54.8–70.1% less than that from the uncoated controls. The oxidation of pyrite followed a pseudo–zero-order kinetics under the constant concentration of H2O2. In the presence of microorganisms, sulfate leached out of the uncoated pyrite in 1 year accounted for 5.32% of the total pyrite in the system, with a concurrent pH drop to 2.35 under the ambient room temperatures. In contrast, the amount leached out from the coated samples was only 0.15% of the total pyrite and the final pH was 5.48. Thus, the coating decreased the leachability of pyrite by 97% in the inoculated systems. In comparison to the more widely studied iron phosphate coating, the advantage of iron 8-hydroxyquinoline coating was that it inhibited both chemical and biological pyrite oxidation, whereas iron phosphate coating could only inhibit chemical pyrite oxidation.
Characterization of Estrogenic Activity of Riverine Sediments from the Czech Republic by K. Hilscherova; K. Kannan; I. Holoubek; J. P. Giesy (pp. 175-185).
Extracts of sediments from rivers in an industrialized area in the Czech Republic were used to evaluate suitability of a simple in vitro bioassay system to detect estrogen receptor (ER)-mediated activity in the complex mixture. Total estrogenic activity was detected by measuring luciferase activity in a stably transfected cell line containing an estrogen-responsive element linked to a luciferase reporter gene. For appropriate interpretation of ER-mediated activity, the effect of sediment extracts on the cell cytotoxicity was assessed at the same time. All sediment samples elicited considerable estrogenic activity. Fractionation of the extracts along with bioassay testing and subsequent instrumental analysis allowed the estrogenic fractions to be identified. The Florisil fraction, which was intermediate in polarity, was the most estrogenic. Instrumental analysis documented that the concentration of the degradation products of alkylphenol ethoxylates did not occur at sufficient concentrations to account for the estrogenic activity. Mass-balance calculations and testing of fractions confirmed that certain polycyclic aromatic hydrocarbons (PAHs) or their metabolites were the most likely compounds contributing to estrogenicity. Some other compounds, such as PCNs and PAH derivatives, that were present in the first and second fraction were tested for their potential estrogenic activity. Their ER-mediated activity and contribution to the overall responses of the complex extracts were very low. The concentrations of 17β-estradiol present in the bioassay media was an important factor for the evaluation of (anti)estrogenicity of single compound(s) or complex mixtures.
Incorporation of Toxicity Tests into the Turkish Industrial Discharge Monitoring Systems by D. T. Sponza (pp. 186-197).
A toxicity evaluation is an important parameter in wastewater quality and in the monitoring of discharged effluents. Some organic and inorganic compounds at toxic levels have been detected in industrial discharges, resulting in plant upsets and discharge permit violations. In some cases, even though the effluent does not exceed the chemical-specific discharge limits, the results of toxicity tests show potential toxicity. Knowledge of the toxicity of effluents can benefit treatment plant operators in optimizing plant operation, protecting receiving water quality, and establishing sewer discharge permits. In the Turkish regulations only toxicity dilution factor with fish is part of the toxicity monitoring program of permissible wastewater discharge.This study investigated the acute toxicity of pulp-paper, leather, and petrochemical industry wastewaters by traditional and enrichment toxicity tests and emphasized the importance of toxicity tests in wastewater discharge regulations. The enrichment toxicity tests are novel applications indicating whether there is potential toxicity or stimulation conditions. Different organisms were used, including bacteria (Floc and Coliform bacteria) algae (Chlorella sp.), fish (Lepistes sp.), and protozoan species (Vorticella sp.) to represent four trophic levels. The toxicity test results were compared with chemical analyses to identify the pollutants responsible for the toxicity in the effluent wastewater samples. Toxicity of the effluents could not be explained by using physicochemical analyses in five cases for the leather and four cases for the pulp-paper and petrochemical industries. The results clearly showed that the use of bioassay tests produce additional information about the toxicity potential of industrial discharges and effluents.
Fate and Effects of the Triazinone Herbicide Metribuzin in Experimental Pond Mesocosms by J. F. Fairchild; L. C. Sappington (pp. 198-202).
Metribuzin is a triazinone herbicide that is widely used for the control of grasses and broad-leaved weeds in soybeans, sugarcane, and numerous other crops. Metribuzin is highly toxic to freshwater macrophytes and algae under laboratory conditions (median plant EC50 = 31 μg/L; n = 11 species) but has not been studied under controlled outdoor conditions. We conducted a 6-week study to examine the aquatic fate and effects of metribuzin in 0.1-ha outdoor aquatic mesocosms. Mesocosms (n = 2 per treatment) were treated with metribuzin at one of five concentrations: 0, 9, 19, 38, or 75 μg/L. Concentrations were selected to bracket known laboratory effect concentrations and to reflect calculated edge-of-field concentrations. The dissipation half-life of metribuzin in water was 5 days. Metribuzin had no statistically significant effects on water quality, periphyton biomass, macrophyte biomass, macrophyte species composition, fish survival, or fish growth at treatment levels ranging up to and including 75 μg/L. Although metribuzin is highly toxic to freshwater macrophytes and algae under laboratory conditions, it poses little risk to nontarget aquatic plants due to the short aqueous dissipation half-life. The findings also demonstrate that current herbicide risk assessment procedures used in the registration process could benefit from empirical assessments of the fate of chemicals under realistic environmental conditions.
Effects of Metals on Seed Germination, Root Elongation, and Coleoptile and Hypocotyl Growth in Triticum aestivum and Cucumis sativus by O. Munzuroglu; H. Geckil (pp. 203-213).
A simple, fast, and easy-to-perform method was carried out for the quantification of the inhibitory effects of metals on wheat and cucumber. The method uses seed germination, root elongation, and hypocotyl and coleoptile growth in these plants as parameters in the presence of varying concentrations of metals. Metals selected for this study were Hg, Cd, Co, Cu, Pb, and Zn. Although effective concentrations of these metals for a certain degree of inhibition were different, both plants had a reduced seed germination rate, root, and hypocotyl or coleoptile length with increasing concentrations. Mercury was determined to be the most inhibitory metal on these parameters. This metal caused a complete inhibition of germination in wheat and cucumber seeds at certain concentrations—≥1.5 mM in cucumber and at 1.7 mM in wheat. No other metal caused this kind of inhibition even at the highest concentration (8.0 mM) applied. Though this metal possessed a higher inhibition of germination in cucumber than in wheat seeds, the inhibitory effects of other metals used were the reverse, being higher in wheat. With some exceptions, all metals in selected concentrations caused a significant (p < 0.01 or p < 0.05) decrease in germination rate of both plants compared to control group seeds.
Lethal Body Residue of Chlorophenols and Mixtures of Chlorophenols in Benthic Organisms by J. V. K. Kukkonen (pp. 214-220).
The lethal body residue (LBR) of a few chlorophenol congeners were measured in the oligochaete worm Lumbriculus variegatus, and the LBR of pentachlorophenol was measured also in a midge, Chironomus riparius larvae. LBR is defined as the concentration of the compound in the organism, on molar basis, to cause death, and the LBR50 is defined as the calculated LBR value to cause a 50% mortality in population after a given time. Groups of 30 or 40 organisms were exposed to different chlorophenol concentrations in artificial soft fresh water to achieve differential mortality. Exposure times were either 24 h or 48 h. In addition to exposures with individual congeners, mixtures of chlorophenols were also tested. After each exposure, the surviving organisms were collected and the body burden of chlorophenols was measured by gas chromatography with electron capture detection. The measured body burden was related to the percent mortality in the group. The trichlorophenols and pentachlorophenol have a 48-h LBR50 of 0.45–0.66 μmol/g wet weight in L. variegatus. The 48-h LBR50 of pentachlorophenol for C. riparius was 0.15 μmol/g wet weight, indicating a slight difference in the sensitivity of these two species. The 48-h LBR50 of 2,3,4,6-tetrachlorophenol is 0.91 μmol/g wet weight, and the value for 2,6-dichlorophenol is 1.2 μmol/g wet weight in L. variegatus. The 48-h LBR50s of the chlorophenol mixtures ranged from 0.50 to 0.83 μmol/g wet weight, demonstrating an additive toxicity.
Bioavailability and Toxicokinetics of 14C-Lindane (γ-HCH) in the Enchytraeid Enchytraeus albidus in Two Soil Types: The Aging Effect by M. J. Amorim; J. P. Sousa; A. J. A. Nogueira; A. M. V. M. Soares (pp. 221-228).
Enchytraeids are important members of the soil fauna living in the true soil layer instead of the humus like most earthworms, resulting in a different interaction with chemicals in soil. It is well known that the detectable concentration of contaminants in the soil cannot fully predict a biological effect; therefore bioaccumulation studies are of great importance. In this study the bioaccumulation pattern of the pesticide lindane ([14C]γ-HCH) in Enchytraeus albidus was analyzed in two different soil types, an artificial Organisation for Economic Co-operation and Development (OECD) soil and a natural agricultural soil. The effect of aging on bioaccumulation and bioavailability was also analyzed. Aging experiments consisted of having the same procedures at different times after soil contamination: Immediately after contamination and 1, 2, 4, 6, and 10 months after that. Major differences occurred within the first month. Considering the overall data (10 months), it is possible to observe that in OECD soil there is a correlation between concentration in soil and in the organisms, but that was not observed for the natural soil. The decrease patterns for concentration in soil and in watery soil extracts were different: monophasic behavior occurred in OECD soil, and a biphasic pattern was measured in natural soil. It was observed that the bioavailable (i.e., water-extractable) fraction of lindane in the natural soil decreased faster than the total soil concentration. In natural soil the decrease of concentration appeared faster than in OECD soil; this may be related to the lower amount of organic matter content.
Toxicity of Select Beta Adrenergic Receptor-Blocking Pharmaceuticals (B-Blockers) on Aquatic Organisms by D. B. Huggett; B. W. Brooks; B. Peterson; C. M. Foran; D. Schlenk (pp. 229-235).
One class of pharmaceutical compounds identified in U.S. and European waters are the B-adrenergic receptor blocking compounds (B-blockers). However, little information is available on the potential aquatic toxicity of these compounds. Therefore, Hyalella azteca, Daphnia magna, Ceriodaphnia dubia, and Oryias latipes (Japanese medaka) were exposed to metoprolol, nadolol, and propranolol to determine potential toxicity. Average 48-h LC50 for propranolol to H. azteca was 29.8 mg/L. The no-observed-effects concentration (NOEC) and lowest-observed-effects concentration (LOEC) for propranolol affecting reproduction of H. azteca were 0.001 and 0.1 mg/L, respectively. The average propranolol and metoprolol 48-h LC50s for D. magna were 1.6 and 63.9 mg/L, respectively. C. dubia 48-h LC50s were 0.85 and 8.8 mg/L for propranolol and metoprolol, respectively. The NOEC and LOEC of propranolol affecting reproduction in C. dubia were 0.125 and 0.25 mg/L, respectively. In O. latipes, the propranolol 48-h LC50 was 24.3 mg/L. Medaka growth was decreased at 0.5 mg/L propranolol. A 2-week medaka reproductive study indicated significant changes in plasma steroid levels; however, no changes in the average number of eggs produced or number of viable eggs which hatched was observed. In a 4-week follow-up propranolol exposure, the total number of eggs produced by medaka and the number of viable eggs that hatched were decreased at concentrations as low as 0.5 μg/L. Based on this study and the expected aqueous environmental exposure levels, adverse effects of propranolol to invertebrate populations is unlikely; however, further reproductive studies are need to elucidate the risk to teleosts.
Relation Between Growth and the Heavy Metal Concentration in Organs of Bream Abramis brama L. Populating Lake Balaton by A. Farkas; J. Salánki; A. Specziár (pp. 236-243).
The effect of growth and physical condition on the level of heavy metals accumulated in the organs of common bream (Abramis brama L.) populating Lake Balaton was investigated on samples collected in October 1999 and May 2000 from two well-separable sites regarding their trophic state and pollution impact (western and eastern basins). The average metal concentrations in the organs of fish varied in the following ranges: Cd, 0.39–1.98; Cu, 1.73–57.3; Hg, 0.02–0.13; Pb, 0.39–3.15; and Zn, 12.7–159.3 μg/g dry weight. The highest Cd, Cu, Pb and Zn concentrations were detected in the gill and liver of fish, whereas the highest Hg concentrations were measured in the muscle. The maximum metal concentrations in the muscle of bream were on average below the maximum permissible levels for human consumption. Significant positive correlation was found among the heavy metal load of bream and their instantaneous growth rate; hardly any connection was observed related to the physical condition of samples. The relatively low metal concentrations of the ambient water and their poor correlation with the heavy metal load of bream, indicates that for the mature stages of this fish species the metal uptake from food is predominant, and thus the heavy metal load of fish reflect more the pollution state of the sediment and its biota, rather than that of the ambient water.
Global Distribution of Halogenated Dimethyl Bipyrroles in Marine Mammal Blubber by S. Tittlemier; A. Borrell; J. Duffe; P. J. Duignan; P. Fair; A. Hall; P. Hoekstra; K. M. Kovacs; M. M. Krahn; M. Lebeuf; C. Lydersen; D. Muir; T. O'Hara; M. Olsson; J. Pranschke; P. Ross; U. Siebert; G. Stern; S. Tanabe; R. Norstrom (pp. 244-255).
Four halogenated dimethyl bipyrroles (HDBPs), hypothesized to be naturally produced, were quantitated in marine mammal blubber from a number of species obtained from various locations worldwide. HDBPs were found in samples from all locations studied. Concentrations of total HDBPs (ΣHDBPs) ranged from 0.4 ng/g lipid weight in ringed seals (Phoca hispida) from the White Sea to 2,540 ng/g lipid weight in Dall's porpoise (Phocoenoides dalli) from the northwestern North Pacific Ocean. At their highest levels, ΣHDBPs made up 11% of the total quantitated organohalogen body burden of adult male Dall's porpoises. In two beluga (Delphinapterus leucas) data subsets, it was found that males contained significantly higher concentrations of ΣHDBPs than females. No significant effects of age or sex on ΣHDBPs were observed in harbor seal (Phoca vitulina) and bowhead whale (Balaena mysticetus) data subsets. The geographical distribution of concentrations did not resemble that of the ubiquitous anthropogenic organohalogen, polychlorinated biphenyl congener CB-153. Higher concentrations of HDBPs and different patterns of congeners were observed in samples from Pacific as opposed to non–Pacific Ocean influenced environments. Concentrations of HDBPs in beluga from the Arctic and St. Lawrence River were similar. Their high abundance in north Pacific Ocean biota and widespread occurrence suggest that HDBPs undergo extensive transport from a source located primarily in the Pacific Ocean. Evidence from HDBP congener patterns indicates that both ocean currents and atmospheric transport likely play a role in the movement of HDBPs. These results imply that HDBPs and anthropogenic organohalogens have different sources and support the natural production hypothesis.
