bluuebunny/crossref_metadata_2025 huggingface dataset:
Toxicity of oil sands to early life stages of fathead minnows (Pimephales promelas)
Authors: Colavecchia Maria V. , Backus Sean M. , Hodson Peter V. , Parrott Joanne L.
Published: November 2004

The present study examines the effects of exposure to oil sands on the early life stages (ELS) off fathead minnows (Pimephales promelas). Sediments within and outside natural oil sand deposits were collected from sites along the Athabasca River (AB, Canada). The ELS toxicity tests were conducted with control water, natural oil sands, reference sediments, and oil-refining wastewater pond sediments. Eggs and larvae were exposed to 0.05 to 25.0 g sediment/L and observed for mortality, hatching, malformations, growth, and cytochrome P4501A induction as measured by immunohistochemistry. Natural bitumen and wastewater pond sediments caused significant hatching alterations and exposure-related increases in ELS mortality, malformations, and reduced size. Larval deformities included edemas, hemorrhages, and spinal malformations. Exposure to reference sediments and controls showed negligible embryo mortality and malformations and excellent larval survival. Sediment analyses using gas chromatography–mass spectrometry revealed high concentrations of alkyl-substituted polyaromatic hydrocarbons (PAHs) compared to unsubstituted PAHs in natural oil sands (220–360 μg/g) and oil-mining wastewater pond sediments (1,300 μg/g). The ELS sediment toxicity tests are rapid and sensitive bioassays that are useful in the assessment of petroleum toxicity to aquatic organisms.
Fate and metabolism of [15N]2,4,6-trinitrotoluene in soil
Authors: Weiß Martin , Geyer Roland , Russow Rolf , Richnow Hans H. , Kästner Matthias
Published: November 2004

The fates of the labels from [14C] and [15N] trinitrotoluene were analyzed in bioreactors under aerobic conditions in soil treated by a fungal bioremediation process with Stropharia rugosoannulata and in control soil. Up to 17.5% of the 15N label had a different fate than the 14C label. Three N-mineralization processes were identified in detailed experiments with [15N]TNT. About 2% of the 15N label was found as NO3− and NH4−, showing simultaneous processes of direct TNT denitration (I) and reduction with cleavage of the amino groups (II). The enrichment of NO2−/NO3− (up to 7.5 atom% 15N abundance) indicates the formation of Meisenheimer complexes with a denitration of [15N]TNT. A 1.4% of the label was found distributed between N2O and N2. However, the 15N enrichment of the N2O (up to 38 atom%) demonstrated that both N atoms were generated from the labeled TNT and clearly indicates a novel formation process (III). We propose, as an explanation, the generation of N2O by cleavage from condensed azoxy metabolites. In addition, 1.7% of the 15N label was detected as biogenic amino acids in the wheat straw containing the fungus. Overall, 60 to 85% of the applied [15N]TNT was degraded and 52 to 64% was found as nonextractable residues in the soil matrix. Three percent was detected as 2-amino-4,6-dinitrotoluene and 4-amino-2,6-dinitrotoluene.
Passive air sampling of polycyclic aromatic hydrocarbons and polychlorinated naphthalenes across europe
Authors: Jaward Foday M. , Farrar Nick J. , Harner Tom , Sweetman Andrew J. , Jones Kevin C.
Published: November 2004

This study presents concurrently sampled ambient air data for a range of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated naphthalenes (PCNs) at the continental scale. This was achieved with a passive air sampling system, by deploying polyurethane foam disks, which were prepared in one laboratory, sealed to prevent contamination, sent out by courier to volunteers participating in different countries, exposed for six weeks, collected, resealed, and returned to the laboratory for analysis. The study area was Europe, a region with a history of extensive persistent organic pollutants usage and emission, and with marked national differences in population density, the degree of urbanization and industrial and agricultural development. Samplers were deployed at remote, rural, and urban locations in 22 countries. Calculated air concentrations were broadly in line with those obtained by conventional active air sampling techniques, for both compound classes and for compounds existing predominantly in the gas and particle phases. The geographical compound distribution reflected suspected regional emission patterns and highlighted localized source areas. Both PAH and PCN levels varied by more than two orders of magnitude. The implications for sources are discussed.
Aquatic persistence of eight pharmaceuticals in a microcosm study
Authors: Lam Monica W. , Young Cora J. , Brain Richard A. , Johnson David J. , Hanson Mark A. , Wilson Christian J. , Richards Sean M. , Solomon Keith R. , Mabury Scott A.
Published: November 2004

The persistence of eight pharmaceuticals from multiple classes was studied in aquatic outdoor field microcosms. A method was developed for the determination of a mixture of acetaminophen, atorvastatin, caffeine, carbarnazepine, levofloxacin, sertraline, sulfamethoxazole, and trimethoprim at μg/L levels from surface water of the microcosms using solid phase extraction and high-performance liquid chromatography-ultraviolet (HPLC-UV) and liquid chromatography tandem mass spectrometry (LC-MS-MS). Half-lives in the field ranged from 1.5 to 82 d. Laboratory persistence tests were performed to determine the relative importance of possible loss processes in the microcosms over the course of the study. Results from dark control experiments suggest hydrolysis was not important in the loss of the compounds. No significant differences were observed between measured half-lives of the pharmaceuticals in sunlight-exposed pond water and autoclaved pond water, which suggests photodegradation was important in limiting their persistence, and biodegradation was not an important loss process in surface water over the duration of the study. Observed photoproducts of several of the pharmaceuticals remained photoreactive, which led to further degradation in irradiated surface waters.
Interactive effects of p,p′-dichlorodiphenyldichloroethylene and methoxychlor on hormone synthesis in largemouth bass ovarian cultures
Authors: Borgert Christopher J. , Gross Timothy S. , Guiney Patrick D. , Osimitz Tomas G. , Price Bertram , Wells Christopher
Published: November 2004

p,p′-Dichlorodiphenyldichloroethylene (DDE) and methoxychlor were tested alone and in combination to assess the similarity of their actions on hormone synthesis in gonadal tissue from largemouth bass (Micropterus salmoides floridanus), a species whose reproductive fitness has relevance to ecosystem health in Florida (USA). Gonads were harvested from adult female bass (age, two to three years) during the peak reproductive season (January–May), minced, and incubated in culture medium with or without test agents for 48 h. Duplicates of each treatment were performed in each of three experiments using tissue from a different female. Both 17β-estradiol and testosterone were measured in aliquots of culture medium by validated radioimmunoassay procedures. Dose–response relationships of individual agents were characterized over a 6-log concentration range (1 × 10−2 to 1 × 104 ppb). Both DDE and methoxychlor, tested individually, produced a dose-dependent decrease in testosterone levels. 17β-Estradiol levels were unaffected. Mixtures of the agents were tested at all concentration combinations of 0.01, 1, 100, and 10,000 ppb in culture medium. Statistical tests indicated that of 16 dose combinations tested, 15 were antagonistic, and only 1 was additive based on the Loewe additivity model of no interaction. These results imply that methoxychlor and DDE inhibit testosterone production by different mechanisms in bass ovaries.
Quantitative measurement of fathead minnow vitellogenin by liquid chromatography combined with tandem mass spectrometry using a signature peptide of vitellogenin
Authors: Zhang Fagen , Bartels Michael J. , Brodeur Julie C. , Woodburn Kent B.
Published: November 2004

Vitellogenin (VTG) has been proposed as a sensitive biomarker of exposure to environmental estrogenic contaminants that induce VTG production in oviparous species. Enzyme-linked immunosorbent assay (ELISA) methods are currently widely used to measure the VTG levels. In this paper, a new liquid chromatography combined with tandem mass spectrometry (LC/ESI-MS/MS) method for the quantitative analysis of VTG in the plasma of fathead minnows exposed to 17α-ethinylestradiol (EE2) has been developed. This method includes, first, the selection of the signature peptide, which involves sodium dodecyl sulfate-poly-arylamide gel electrophoresis separation, in-gel digestion, LC/ESI-MS/MS analysis with an ion trap mass spectrometer, and sequence determination with the TurboSEQUEST MS/MS database application; second, optimization of the selected signature peptide in multireaction monitor (MRM) mode with a triple quadrupole mass spectrometer; and third, trypsin digestion of plasma and VTG quantitation via MRM-mode LC/ESI-MS/MS. A series of plasma samples from fathead minnows following exposure to EE2 was assayed. A good correlation was found when EE2-induced plasma samples from fathead minnows were analyzed with ELISA and the described new method. Although used here with fathead minnow, the new LC/ESI-MS/MS method could be easily applied to the analysis of VTG expressed in any other fish species. Quantitation of VTG by this method was found to be highly specific and linear. The absence of potential artifactual measurements of VTG at low exposure levels could also be critical in future studies that evaluate weakly estrogenic compounds in aquatic species.
Putting science into persistence, bioaccumulation, and toxicity evaluations
Authors: Webster Eva , Cowan-Ellsberry Christina E. , McCarty Lynn
Published: November 2004

In recent decades, advances have been made in the processes used to identify substances as persistent, bioaccumulative, and toxic (PBT). Key processes have been identified, and scientifically sound assessment methods have been developed. Regulatory agencies around the world have sought practical methods for implementing policies to protect both environment and human health. In the present paper, we review the various contributions that Mackay (in collaboration with his students and colleagues) has made to the development of scientifically sound methods for the identification of PBT substances and persistent organic pollutants. These contributions include efforts to clearly define the terminology and to develop scientifically defensible assessment models and evaluation frameworks.
A food web bioaccumulation model for organic chemicals in aquatic ecosystems
Authors: Arnot Jon A. , Gobas Frank A. P. C.
Published: November 2004

The present study examines a new bioaccumulation model for hydrophobic organic chemicals in aquatic food webs. The purpose of the model is to provide site-specific estimates of chemical concentrations and associated bioconcentration factors, bioaccumulation factors, and biota-sediment accumulation factors in organisms of aquatic food webs using a limited number of chemical, organism, and site-specific data inputs. The model is a modification of a previous model and incorporates new insights regarding the mechanism of bioaccumulation derived from laboratory experiments and field studies as well as improvements in model parameterization. The new elements of the model include: A model for the partitioning of chemicals into organisms; kinetic models for predicting chemical concentrations in algae, phytoplankton, and zooplankton; new allometric relationships for predicting gill ventilation rates in a wide range of aquatic species; and a mechanistic model for predicting gastrointestinal magnification of organic chemicals in a range of species. Model performance is evaluated using empirical data from three different freshwater ecosystems involving 1,019 observations for 35 species and 64 chemicals. The effects of each modification on the model's performance are illustrated. The new model is able to provide better estimates of bioaccumulation factors in comparison to the previous food web bioaccumulation model while the model input requirements remain largely unchanged.
Environmental quality criteria for organic chemicals predicted from internal effect concentrations and a food web model
Authors: Traas Theo P. , van Wezel Annemarie P. , Hermens Joop L. M. , Zorn Mathilde , van Hattum Albertus G. M. , van Leeuwen Cornelis J.
Published: November 2004

Environmental quality criteria (EQC) for hydrophobic organic chemicals were calculated with a model for bioaccumulation in food webs. The model was calibrated and verified using polychlorinated biphenyl concentrations in food webs of shallow lakes. The EQCs in water and sediment were derived based on internal effect concentrations (IECs) for several modes of toxic action. By reverse calculation with the food web model for each organism in the web, a different water or sediment concentration is calculated corresponding to the IEC in each organism. A statistical procedure with an acute-to-chronic value is used to derive chronic EQCs based on bioaccumulation. The model-based chronic EQCs were compared with previously established EQCs. The EQCs calculated with the food web model generally are within an order of magnitude of the previously derived EQCs based on toxicity data on individual chemicals. Some previously derived EQCs are much lower than model predictions and usually based on small samples of toxicity data such as no-observed-effect concentrations (NOECs) with large assessment factors. When faced with data gaps, it is proposed to use model-based chronic EQCs for (polar) narcotic chemicals. Other modes of action require a different model concept to account for receptor-based toxicity.
Association of heavy metals with metallothionein and other proteins in hepatic cytosol of marine mammals and seabirds
Authors: Ikemoto Tokutaka , Kunito Takashi , Anan Yasumi , Tanaka Hiroyuki , Baba Norihisa , Miyazaki Nobuyuki , Tanabe Shinsuke
Published: November 2004

Distribution of Cu, Zn, Cd, Ag, Hg, and Se were determined in hepatocytosol of northern fur seals (Callorhinus ursinus), black-footed albatrosses (Diomedea nigripes), and Dall's porpoises (Phocoenoides dalli). Copper, Zn, and Cd were accumulated preferentially in metallothionein (MT) fraction and their contents in MT fraction increased with the amounts in the hepatocytosol. Silver was bound to both high-molecular-weight substances (HMWS) and MT in the hepatocytosol for all three species, whereas the distribution of Ag in the cytosol was different among the three species. In northern fur seals, Ag mainly was bound to MT, whereas it mainly was associated with HMWS in Dall's porpoises. In contrast, Ag was distributed almost equally in both HMWS and MT for black-footed albatrosses. Mercury content in HMWS and Se content in HMWS and low-molecular-weight substances (LMWS) increased with their contents in hepatocytosol for all the three species. A significant positive correlation was found between Se and Hg contents in high-molecular weight (HMW) fraction in cytosol. The molar ratio of Hg and Se was close to unity in HMW fraction of the specimens with high Hg concentration in cytosol, implying that the Hg–Se complex was bound to the HMWS. Analysis of metals in the hepatocytosol by high-performance liquid chromatography/inductively coupled plasma–mass spectrometry (HPLC/ICP-MS) suggests that multiple isoforms of MT are present in hepatocytosol of the three species and that the metal profiles in hepatocytosols are different among the species. To our knowledge, this is the first report on the association of Ag with HMWS and MT in hepatocytosol of marine mammals and seabirds. Also, distribution and interaction of Hg and Se were investigated for the first time in hepatocytosol of the higher trophic marine animals.
Osmotic distress: A probable cause of fish kills on exposure to a subbloom concentration of the toxic alga Chattonella marina
Authors: Tang Janet Y. M. , Au Doris W. T.
Published: November 2004

Mortality, changes in blood osmolality, and pO2 in the goldlined seabream (Rhabdosargus sarba) on exposure to a subbloom concentration (2,000 cells/ml) of a toxic red tide alga, Chattonella marina, were investigated and related to quantitative ultrastructural alterations of the gill. The median lethal time (LT50) was 6 h. Significant induction of filamental chloride cells (CCs) (increases in CC density, apical opening area, fractional area, volume densities of CCs, and mitochondria within CCs), concomitant with a significant reduction in blood osmolality, was found within 3 h of exposure to C. marina. Further reduction in blood osmolality (67%) and a drastic decline of pO2 (70%) were detected in moribund fish after 6 h. Fish were also subjected to severe salinity stress (abrupt transfer to 0 and 60‰ salinities), and the same parameters were measured. Our quantitative ultrastructural and physiological data suggest that fish exposed for 6 h to C. marina (2,000 cells/ml) suffered similar but more severe osmotic distress as compared to that induced by abrupt transfer to 60‰ persaline water. Results of the salinity stress experiment also showed that suffocation was not a secondary response induced by osmotic impairment in the moribund fish. Osmoregulatory failure in conjunction with suffocation may be the cause of death following exposure to C. marina. The findings of this study provide evidence that C. marina, even in concentrations below visible blooms, can pose a significant threat to marine fish.
Incorporating monte carlo analysis into multimedia environmental fate models
Authors: Citra Mario J.
Published: November 2004

We have incorporated a Monte Carlo module into a steady state nonequilibrium level III fugacity model in order to account for variability in degradation half-lives and observe the effects that this variability has on the model outputs. This method leads to a distribution of important output parameters such as the overall persistence time, which can be used in decision-making processes or risk assessment. For herbicides such as atrazine, where the emission rate primarily is to the soil compartment, it is shown that the main contribution to the variability in overall persistence time is the soil degradation half-life.
Maternal transfer of selenium in Alligator mississippiensis nesting downstream from a coal-burning power plant
Authors: Roe John H. , Hopkins William A. , Baionno Jennifer A. , Staub Brandon P. , Rowe Christopher L. , Jackson Brian P.
Published: November 2004

Selenium (Se) is embryotoxic in many oviparous vertebrates, but little is known about maternal transfer of Se and its impact in reptiles. Over a four-year period, we collected three clutches of eggs of the American alligator (Alligator mississippiensis) from a single nest at a site contaminated with Se and compared egg and hatchling Se concentrations and clutch viability from this nest to nests downstream from the contaminated site (two clutches from two nests) and at a reference site (two clutches from two nests). Eggs and hatchlings from the nest at the Se-contaminated site and downstream nests had elevated Se concentrations (2.1–7.8 ppm) and lower viability (30–54%) compared to reference nests (1.4–2.3 ppm and 67–74% viability), but Se concentrations did not exceed reproductive toxicity thresholds established for other oviparous vertebrates. Selenium concentrations were higher in chorioallantoic membranes of eggs from Se-contaminated sites, suggesting that this tissue may be useful as a nondestructive index of Se exposure for embryos of A. mississippiensis. Examination of these data suggests that further studies on uptake, accumulation, and reproductive success of crocodilian embryos exposed to excessive Se are warranted.
The enhanced biodegradation of fenamiphos in soils from previously treated sites and the effect of soil fumigants
Authors: Karpouzas Dimitrios Georgios , Hatziapostolou Polydoros , Papadopoulou-Mourkidou Euphemia , Giannakou Ioannis O. , Georgiadou Athena
Published: November 2004

The application of fenamiphos either alone or in combination with soil fumigants is a common practice in greenhouses and potato-cultivation areas in Greece. However, repeated applications of fenamiphos in the same field for a number of years can lead to the development of enhanced biodegradation of the nematicide. Studies in previously treated greenhouse sites and potato field sites in Greece were employed in order to investigate the development of enhanced biodegradation of fenamiphos and the respective effect of soil fumigants on the development of the phenomenon. Enhanced biodegradation of fenamiphos in a soil from a previously treated greenhouse site from the area of Aggelohori in Northern Greece was observed using both incubation and bioassay studies with nematodes. Fumigation of the enhanced soil with methyl bromide (MeBr) only temporarily inhibited degradation of fenamiphos unlike metham sodium (MS) whose application significantly reduced microbial degradation of fenamiphos. Similarly, enhanced biodegradation of fenamiphos was evident in soil from potato fields that had a history of previous exposure to fenamiphos. The slow rates of fenamiphos degradation observed in soils from the previously treated sites after sterilization with broad-spectrum antibiotics and also in soils from previously untreated sites suggested that soil microorganisms were responsible for its rapid degradation. The inhibition of enhanced biodegradation of fenamiphos in soil from the previously treated greenhouse site caused by the antibiotic penicillin probably indicates that Gram+ or other bacteria sensitive to penicillin are responsible for the rapid degradation of fenamiphos in this soil. No cross-adaptation was observed between fenamiphos and other nematicides registered in Greece for the control of root-knot and potato cyst nematodes, including cadusafos, ethoprophos, and oxamyl. According to our results, applications of MS followed by fenamiphos or in rotation with other registered nematicides are the most promising means for minimizing the risk of development of enhanced biodegradation of fenamiphos in soils.
Finding and estimating chemical property data for environmental assessment
Authors: Boethling Robert S. , Howard Philip H. , Meylan William M.
Published: November 2004

The ability to predict the behavior of a chemical substance in a biological or environmental system largely depends on knowledge of the physicochemical properties and reactivity of that substance. We focus here on properties, with the objective of providing practical guidance for finding measured values and using estimation methods when necessary. Because currently available computer software often makes it more convenient to estimate than to retrieve measured values, we try to discourage irrational exuberance for these tools by including comprehensive lists of Internet and hard-copy data resources. Guidance for assessors is presented in the form of a process to obtain data that includes establishment of chemical identity, identification of data sources, assessment of accuracy and reliability, substructure searching for analogs when experimental data are unavailable, and estimation from chemical structure. Regarding property estimation, we cover estimation from close structural analogs in addition to broadly applicable methods requiring only the chemical structure. For the latter, we list and briefly discuss the most widely used methods. Concluding thoughts are offered concerning appropriate directions for future work on estimation methods, again with an emphasis on practical applications.
Chemical speciation and cellular deposition of lead in Sesbania drummondii
Authors: Sharma Nilesh C. , Gardea-Torresdey Jorge L. , Parsons Jason , Sahi Shivendra V.
Published: November 2004

The internalized speciation of lead in roots and leaves of Sesbania drummondii, a lead hyperaccumulator, grown in lead nitrate solution was studied using x-ray absorption near-edge structure and extended x-ray absorption fine structure. Lead was predominantly present as lead acetate in both plant tissues. The other dominant forms of accumulation were lead–sulfur compounds. Whereas lead sulfate and sulfide were found in leaves, only lead sulfide was detected in root samples. These observations indicate that S. drummondii is able to biotransform lead nitrate in the nutrient solution to lead acetate and sulfate in its tissues. Complexation with acetate and sulfate may be a lead detoxification strategy in this plant. Transmission-electron microscopy revealed the pattern of lead distribution in and around the cells. Dense distributions of lead grains were detected in root cell walls and plasma membranes, whereas evidence for vacuolar transport of lead was noticed in the stem cells.
Development of toxicity identification evaluation procedures for pyrethroid detection using esterase activity
Authors: Wheelock Craig E. , Miller Jeff L. , Miller Mike J. , Gee Shirley J. , Shan Guomin , Hammock Bruce D.
Published: November 2004

Recent agrochemical usage patterns suggest that the use of organophosphate (OP) pesticides will decrease, resulting in a concomitant increase in pyrethroid usage. Pyrethroids are known for their potential toxicity to aquatic invertebrates and many fish species. Current toxicity identification evaluation (TIE) techniques are able to detect OPs, but have not been optimized for pyrethroids. Organophosphate identification methods depend upon the use of piperonyl butoxide (PBO) to identify OP-induced toxicity. However, the use of PBO in TIE assays will be confounded by the co-occurrence of OPs and pyrethroids in receiving waters. It is necessary, therefore, to develop new TIE procedures for pyrethroids. This study evaluated the use of a pyrethroid-specific antibody, PBO, and carboxylesterase activity to identify pyrethroid toxicity in aquatic toxicity testing with Ceriodaphnia dubia. The antibody caused significant mortality to the C. dubia. Piperonyl butoxide synergized pyrethroid-associated toxicity, but this effect may be difficult to interpret in the presence of OPs and pyrethroids. Carboxylesterase activity removed pyrethroid-associated toxicity in a dose-dependent manner and did not compromise OP toxicity, suggesting that carboxylesterase treatment will not interfere with TIE OP detection methods. These results indicate that the addition of carboxylesterase to TIE procedures can be used to detect pyrethroids in aquatic samples.
Intestinal absorption and biomagnification of organic contaminants in fish, wildlife, and humans
Authors: Kelly Barry C. , Gobas Frank A. P. C. , McLachlan Michael S.
Published: November 2004

Methods for the regulatory assessment of the bioaccumulation potential of organic chemicals are founded on empirical measurements and mechanistic models of dietary absorption and biomagnification. This study includes a review of the current state of knowledge regarding mechanisms and models of intestinal absorption and biomagnification of organic chemicals in organisms of aquatic and terrestrial food chains and also includes a discussion of the implications of these models for assessing the bioaccumulation potential of organic chemicals. Four mechanistic models, including biomass conversion, digestion or gastrointestinal magnification, micelle-mediated diffusion, and fat-flush diffusion, are evaluated. The models contain many similarities and represent an evolution in understanding of chemical bioaccumulation processes. An important difference between the biomagnification models is whether intestinal absorption of an ingested contaminant occurs solely via passive molecular diffusion through serial resistances or via facilitated diffusion that incorporates an additional advective transport mechanism in parallel (i.e., molecular ferrying within gastrointestinal micelles). This difference has an effect on the selection of physicochemical properties that best anticipate the bioaccumulative potential of commercial chemicals in aquatic and terrestrial food chains. Current regulatory initiatives utilizing Kow threshold criteria to assess chemical bioaccumulation potential are shown to be unable to identify certain bioaccumulative substances in air-breathing animals. We urge further research on dietary absorption and biomagnification of organic chemicals to develop better models for assessing the bioaccumulative nature of organic chemicals.
Shortcomings of the laboratory-derived median lethal concentration for predicting mortality in field populations: Exposure duration and latent mortality
Authors: Zhao Yuan , Newman Michael C.
Published: November 2004

Exposure duration and intensity (concentration or dose) determine lethal effects of toxicants. However, environmental regulators have focused on exposure intensity and have considered duration only peripherally. Conventional testing for toxicology tends to fix exposure time and to use the median lethal concentration (LC50) at that time to quantify mortality. Fixing the exposure duration and selecting the 50% mortality level for reasons of statistical and logistical convenience result in the loss of ecologically relevant information generated at all other times and ignore latent mortality that manifests after the exposure ends. In the present study, we used survival analysis, which is widely employed in other fields, to include both time and concentration as covariates and to quantify latent mortality. This was done with two contrasting toxicants, copper sulfate (CuSO4) and sodium pentachlorophenol (NaPCP). Amphipods (Hyalella azteca) were exposed to different toxicant concentrations, and the percentage mortalities were noted both during and after the exposure ended. For CuSO4 at the conventional 48-h LC50 concentrations, the predicted proportions dead after including latent mortality were 65 to 85%, not 50%. In contrast, only 5% or fewer additional animals died if the latent mortality was included for NaPCP. The data (including exposure time, concentration, and proportion dead at each time) for each toxicant were then successfully fit with survival models. The proportion of organisms dying at any combination of exposure concentration and time can be predicted from such models. Survival models including latent mortality produced predictions of lethal effects that were more meaningful in an ecological or field context than those from conventional LC50 methods.
Location-specific ecotoxicological risk assessment of metal-polluted soils
Authors: van Beelen Patrick , Wouterse Marja , Posthuma Leo , Rutgers Michiel
Published: November 2004

When chemical analysis indicates metal pollution, a second-tier method is needed to evaluate whether toxic effects occur at the polluted sites. A method based on pollution-induced community tolerance (PICT) was developed using samples taken from locations polluted with sewage more than 20 years ago. Microorganisms extracted from soil samples were exposed to a concentration range of zinc, nickel, copper, chromium (III), or chromium (VI) salts in a buffer suspension. The remaining activity of the intoxicated microorganisms was determined by color formation with 31 different organic substrates in microtiter plates. Microorganisms from moderately Zn-polluted sites (>45 mg/kg) showed an increased tolerance for zinc. Nickel tolerance was observed at 51 mg Ni/kg soil, chromium (VI) tolerance at 923 mg Cr/kg. In most cases, tolerance also was observed at higher concentrations. High concentrations of 1,494 mg Cu/kg or 3,935 mg Cr/kg did not show PICT, indicating a limited bioavailability of Cu and Cr at these sites. The benefits of our method are its greater sensitivity compared to other tests used at these sites, and its specificity for those metals that exceed allowable levels.
Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments
Authors: Alvarez David A. , Petty Jimmie D. , Huckins James N. , Jones-Lepp Tammy L. , Getting Dominic T. , Goddard Jon P. , Manahan Stanley E.
Published: November 2004

Increasingly it is being realized that a holistic hazard assessment of complex environmental contaminant mixtures requires data on the concentrations of hydrophilic organic contaminants including new generation pesticides, pharmaceuticals, personal care products, and many chemicals associated with household, industrial, and agricultural wastes. To address this issue, we developed a passive in situ sampling device (the polar organic chemical integrative sampler [POCIS]) that integratively concentrates trace levels of complex mixtures of hydrophilic environmental contaminants, enables the determination of their time-weighted average water concentrations, and provides a method of estimating the potential exposure of aquatic organisms to the complex mixture of waterborne contaminants. Using a prototype sampler, linear uptake of selected herbicides and pharmaceuticals with log KowS < 4.0 was observed for up to 56 d. Estimation of the ambient water concentrations of chemicals of interest is achieved by using appropriate uptake models and determination of POCIS sampling rates for appropriate exposure conditions. Use of POCIS in field validation studies targeting the herbicide diuron in the United Kingdom resulted in the detection of the chemical at estimated concentrations of 190 to 600 ng/L. These values are in agreement with reported levels found in traditional grab samples taken concurrently.
Toxicity of wide-range polarity fractions from wood smoke and diesel exhaust particulate obtained using hot pressurized water
Authors: Kubátová Alena , Steckler Tamara S. , Gallagher John R. , Hawthorne Steven B. , Picklo Matthew J.
Published: November 2004

Epidemiological and toxicological studies correlate the adverse health effects of particulate matter (PM) with the available information regarding their chemical characterization, which has focused on nonpolar organics (e.g., polycyclic aromatic hydrocarbons [PAHs]), which are limited to 15 to 50% of total organic carbon. To study both polar and nonpolar species, we have employed hot pressurized (liquid) water for the fractionation of diesel exhaust and wood smoke PM. In agreement with the results of previous studies, nonpolar fractions from both PM samples showed strong cytotoxicity (cell viability decreased to 50–60%) corresponding to the presence of PAHs. Surprisingly, similar decreases in cell viability were also found in polar fractions (50°C) from both diesel exhaust and wood smoke PM. The midpolarity fractions (100−150°C) from wood smoke PM also displayed high cytotoxicity corresponding to methoxyphenols and oxy-PAHs. Although the midpolarity fractions from diesel exhaust PM showed no cytotoxicity, genotoxicity was found in the 150°C fraction, possibly corresponding to nitroaromatics. The present study demonstrates the suitability of hot pressurized water (as a single, nontoxic solvent) for the fractionation and toxicological characterization of wide-range polarity constituents of PM and, possibly, other environmental matrices.
Dynamic coupled metal transport-speciation model: Application to assess a zinc-contaminated lake
Authors: Bhavsar Satyendra P. , Diamond Miriam L. , Gandhi Nilima , Nilsen Joel
Published: November 2004

A coupled metal transport and speciation/complexation model (TRANSPEC) has been developed to estimate the speciation and fate of multiple interconverting species in surface aquatic systems. Dynamic-TRANSPEC loosely, sequentially couples the speciation/complexation and fate modules that, for the unsteady state formulation, run alternatively at every time step. The speciation module first estimates species abundance using, in this version, MINEQL+ considering time-dependent changes in water and pore-water chemistry. The fate module is based on the quantitative water air sediment interaction (QWASI) model and fugacity/aquivalence formulation, with the option of using a pseudo-steady state solution to account for past discharges. Similarly to the QWASI model for organic contaminants, TRANSPEC assumes the instantaneous equilibrium distribution of metal species among dissolved, colloidal, and particulate phases based on ambient chemistry parameters that can be collected through conventional field methods. The model is illustrated with its application to Ross Lake (Manitoba, Canada) that has elevated Zn concentrations due to discharges over 70 years from a mining operation. Using measurements from field studies, the model reproduces year-round variations in Zn water concentrations. A 10-year projection for current conditions suggests decreasing Zn remobilization and export from the lake. Decreasing Zn loadings increases sediment-to-water transport but decreases water concentrations, and vice versa. Species distribution is affected by pH such that a decrease in pH increases metal export from the lake and vice versa.
Induction of aryl hydrocarbon receptor–mediated and estrogen receptor–mediated activities, and modulation of cell proliferation by dinaphthofurans
Authors: Vondráček Jan , Chramostová Kateřina , Plíšková Martina , Bláha Luděk , Brack Werner , Kozubík Alois , Machala Miroslav
Published: November 2004

A group of heterocyclic aromatic compounds, dinaphthofurans (DNFs), recently have been identified as potentially significant contaminants in freshwater sediments. In the present study, a battery of in vitro assays was used for detection of toxic effects of DNFs that are potentially associated with endocrine disruption and tumor promotion. Dinaphthofurans were found to act as relatively potent inducers of aryl hydrocarbon receptor (AhR)–mediated activity in the chemical-activated luciferase reporter gene expression DR-CALUX assay. The relative AhR-inducing potencies of DNFs were similar or even higher than relative potencies of unsubstituted polycyclic aromatic hydrocarbons (PAHs), with dinaphtho[1,2-b;2′3′-d]furan being the most potent AhR agonist. Two compounds, dinaphtho[2,1-b;2′3′-d]furan and dinaphtho[1,2-b;1′2′-d]furan, induced estrogen receptor (ER)–mediated activity in the estrogen receptor–mediated CALUX (the ER-CALUX) assay. Two types of potential tumor-promoting effects of DNFs were investigated, using in vitro bioassays for detection of inhibition of gap-junctional intercellular communication and detection of a release from contact inhibition. Although the acute inhibition of gap-junctional intercellular communication was not observed, all six tested DNFs were able to release rat liver epithelial WB-F344 cells from contact inhibition at concentrations as low as 100 nM. In summary, the present study indicated that DNFs can exert multiple biological effects in vitro, including induction of the AhR-mediated activity, release of cells from contact inhibition, and induction of ER-mediated activity.
Development of a model microbial predator-prey system suitable for studies of the behavior of toxic trace metals
Authors: Patton Leslie E. , Shuler Michael L. , Lion Leonard W
Published: November 2004

Interactions between microbial predators and their prey cans significantly influence the behavior of toxic trace metals. Ingested bacterial prey—bound metals can either accumulate within a predator or be excreted and potentially reintroduced into the dissolved phase. A defined predator—prey system suitable for developing a more fundamental understanding of metal behavior in simple microbial food chains was designed and tested by using lead (Pb) as a representative cationic transition metal. Desired features of this system were the ability to define the chemical speciation of dissolved metals as well as to distinguish between prey- and predator-bound metals. Pseudomonas putida and the ciliate protozoan Tetrahymena thermophila were selected as representative bacterial prey and predator species, respectively. In addition, the use of fluorescent microspheres was evaluated as an experimental surrogate for bacterial prey. Filtration techniques for size-selective separation were developed so that the distribution of Pb between cells of T. thermophila, cells of P. putida or microspheres, and the dissolved phase could be assessed. Filtration units were selected based on their ability to perform separations with minimal metal loss at circumneutral pH. Five-micron polycarbonate filter membranes successfully separated T. thermophila from P. putida with good cell retention and low metal loss. Centrifuge filters successfully separated dissolved and particle-bound metal (<5,000 nominal molecular wt limit). Exemplary experimental results are presented and show that predation on Pb-exposed cells of P. putida or microspheres increases uptake of Pb by T. thermophila.
Tributyltin uptake and depuration in Hyalella azteca: Implications for experimental design
Authors: Bartlett Adrienne J. , Borgmann Uwe , Dixon D. G Eorge , Atchelor Suzanne P. B , Maguire R. James
Published: November 2004

The purpose of this study was to address four aspects of the kinetics of tributyltin (TBT) in the freshwater amphipod Hyalella azteca: time to steady state, route of uptake, depuration rates, and effect of gut clearance. The amphipods accumulated TBT rapidly, reaching steady state within 14 d. Body concentrations were similar between caged and sediment-exposed animals, indicating that the primary route of uptake is via dissolved TBT. However, the rate of uptake was significantly higher in sediment-exposed amphipods. During depuration, body concentrations of TBT exhibited a biphasic decline, with a stronger decrease over the first 24 h that is attributed primarily to gut clearance, followed by a more gradual decrease most likely due to excretion from the body. Gut contents contributed significantly to body concentrations of TBT, accounting for 30% of the initial total body burden in sediment-exposed amphipods. Half-lives of TBT in gut-cleared H. azteca were 8 d and 14 d for amphipods exposed to spiked water and spiked sediment, respectively. The results of this study have significant implications in the experimental design and interpretation of studies involving the effects of TBT in H. azteca.
Metalloporphyrin solubility: A trigger for catalyzing reductive dechlorination of tetrachloroethylene
Authors: Dror Ishai , Schlautman Mark A.
Published: November 2004

Metalloporphyrins are well known for their electron-transfer roles in many natural redox systems. In addition, several metalloporphyrins and related tetrapyrrole macrocycles complexed with various core metals have been shown to catalyze the reductive dechlorination of certain organic compounds, thus demonstrating the potential for using naturally occurring metalloporphyrins to attenuate toxic and persistent chlorinated organic pollutants in the environment. However, despite the great interest in reductive dechlorination reactions and the wide variety of natural and synthetic porphyrins currently available, only soluble porphyrins, which comprise a small fraction of this particular family of organic macrocycles, have been used as electron-transfer shuttles in these reactions. Results from the present study clearly demonstrate that metalloporphyrin solubility is a key factor in their ability to catalyze the reductive dechlorination of tetrachloroethylene and its daughter compounds. Additionally, we show that certain insoluble and nonreactive metalloporphyrins can be activated as catalysts merely by changing solution conditions to bring about their dissolution. Furthermore, once a metalloporphyrin is fully dissolved and activated, tetrachloroethylene transformation proceeds rapidly, giving nonchlorinated and less toxic alkenes as the major reaction products. Results from the present study suggest that if the right environmental conditions exist or can be created, specific metalloporphyrins may provide a solution for cleaning up sites that are contaminated with chlorinated organic pollutants.
Uranium complexation and uptake by a green alga in relation to chemical speciation: The importance of the free uranyl ion
Authors: Fortin Claude , Dutels Laurent , Garnier-Laplace Jacqueline
Published: November 2004

The bioavailability and toxicity of dissolved metals are closely linked to the metals' chemical speciation in solution. Normally the complexation of a metal by a ligand would be expected to decrease its bioavailability. The aqueous speciation of uranium (U) undergoes tremendous changes in the presence of ligands commonly found in natural waters (carbonate, phosphate, hydroxide, and natural organic matter). In the present project, links between speciation, medium composition, and bioavailability of uranium toward Chlamydomonas reinhardtii, a unicellular green alga, were investigated. Short-term metal uptake rates were determined in simple inorganic media at constant low pH (5.0) and hardness with particular emphasis on the differentiation between adsorbed and intracellular metal. While intracellular uptake was fairly linear over 1 h, partly reversible adsorption reached steady-state within minutes. Both adsorption and absorption were saturable processes (with a half-saturation constant Km of 0.51 μM). Addition of phosphate, citrate, or ethylenediaminetetraacetic acid (EDTA) as ligands decreased uranium bioavailability. No evidence indicating the transport of intact uranyl complexes was found (i.e., facilitated diffusion of metal bound to an assimilable ligand such as uranium-phosphate complexes). Within these experimental conditions, uranium uptake was correlated with the free uranyl ion concentration as predicted by the free-ion activity model (FIAM) and biotic ligand model (BLM).
Interaction of tributyltin with hepatic cytochrome P450 and uridine diphosphate-glucuronosyl transferase systems of fish: In vitro studies
Authors: Morcillo Yolanda , Janer Gemma , O'Hara Sean C.M. , Livingstone David R. , Porte Cinta
Published: November 2004

Hepatic microsomes of red mullet (Mullus barbatus) and flounder (Platichthys flesus) were preincubated in the presence of a concentration range of the antifouling agent tributyltin (TBT) chloride, and the interactions of TBT with cytochrome P450 and uridine diphosphate—glucuronyl transferase systems were investigated. The enzyme systems were examined in terms of cytochrome P4501A (CYP1A)-catalyzed 7-ethoxyresorufin O-deethylase (EROD) activity and benzo[a]pyrene (BaP) metabolism and in terms of glucuronidation of testosterone and 17β-estradiol, respectively. Ethoxyresorufin O-deethylase and BaP hydroxylase (BPH) activities of both fish species were progressively inhibited by increasing concentrations of TBT, and the effects were more pronounced for EROD than for BPH (maximal inhibition at 100 μM TBT for EROD and 250–500 μM TBT for BPH). Hydroxylated metabolites of BaP (3-hydroxy-, 7,8-dihydrodiol, and 9,10-dihydrodiol), representing 95% of the total metabolites formed, were reduced up to 75 % in the presence of 100 to 500 μM TBT, whereas the formation of other metabolites was less affected. This may alter BaP toxicity and carcinogenicity. Overall, the results were consistent with a specific inhibitory effect of TBT on CYP1A in the two fish species. Additionally, the conjugation of testosterone was significantly inhibited (20%) at low TBT doses (5 μM), with no effect on the glucuronidation of estradiol.